CN105591113A - Anode material for solid oxide fuel cell and preparation method of anode material - Google Patents
Anode material for solid oxide fuel cell and preparation method of anode material Download PDFInfo
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- CN105591113A CN105591113A CN201610137793.0A CN201610137793A CN105591113A CN 105591113 A CN105591113 A CN 105591113A CN 201610137793 A CN201610137793 A CN 201610137793A CN 105591113 A CN105591113 A CN 105591113A
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- anode material
- oxide
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- powder
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- 239000010405 anode material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000446 fuel Substances 0.000 title abstract description 12
- 239000007787 solid Substances 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 46
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 5
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 32
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 27
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 26
- 238000001556 precipitation Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000004020 conductor Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 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 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- PNEVPHWGBQXOBP-UHFFFAOYSA-N [Co].[Sr].[Mg] Chemical compound [Co].[Sr].[Mg] PNEVPHWGBQXOBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002927 oxygen compounds Chemical class 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims 1
- 235000004515 gallic acid Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 68
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 47
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 43
- 238000010248 power generation Methods 0.000 description 30
- 238000007639 printing Methods 0.000 description 23
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 20
- 239000006256 anode slurry Substances 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 15
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 13
- 238000000975 co-precipitation Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 238000003801 milling Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000006257 cathode slurry Substances 0.000 description 9
- 229910003101 Y(NO3)3·6H2O Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 3
- -1 oxonium ion Chemical class 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052773 Promethium Inorganic materials 0.000 description 2
- UPEMFLOMQVFMCZ-UHFFFAOYSA-N [O--].[O--].[O--].[Pm+3].[Pm+3] Chemical compound [O--].[O--].[O--].[Pm+3].[Pm+3] UPEMFLOMQVFMCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 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
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016289 MxO2 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- SYJBLFMEUQWNFD-UHFFFAOYSA-N magnesium strontium Chemical compound [Mg].[Sr] SYJBLFMEUQWNFD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(III) nitrate Inorganic materials [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-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
- 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
-
- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- 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
- H01M4/8828—Coating with slurry or ink
- H01M4/8835—Screen printing
-
- 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
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- 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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an anode material for a solid oxide fuel cell and a preparation method of the anode material. The anode material is oxide powder [(LnOalpha)x(CeyZr1-yO2)1-x]1-z[MObeta]z, wherein x is larger than or equal to 0 and smaller than or equal to 0.3, y is larger than or equal to 0.02 and smaller than or equal to 0.95, z is larger than or equal to 0 and smaller than or equal to 0.3, LnOalpha is corresponding oxide of Ca, Mg, Sc, Y, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and MObeta is corresponding oxide of Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt and Au. The method comprises the following steps that 1, nitrate of elements with a corresponding amount is evenly dissolved in distilled water; 2, ammonium hydroxide is slowly and dropwise added into the solution, and sediment is separated out; 3, the sediment is filtered out, and sintering is carried out after drying; 4, the sintered powder is subjected to wet ball milling. Compared with a traditional composite anode material, the anode material has better heat expanding stability and more excellent oxidation resisting durability, and the long-term running cost of the fuel cell can be reduced.
Description
Technical field
The present invention relates to a kind of anode material, be specifically related to a kind of SOFC anode materialMaterial.
Background technology
SOFC be a kind of can be the chemical energy in fuel by electrochemical reactionMode is converted into all solid state energy conversion device of electric energy. It is mainly by anode, negative electrode and electrolyte ingredient.Conventionally, there is oxygen reduction reaction at the three phase boundary place of negative electrode inside in the air (oxygen) passing in negative electrode,Three phase boundary place and hydrogen that the oxonium ion that reaction generates is transmitted to anode interior by solid electrolyte are sent outRaw hydroxide reaction, the electronics that reaction generates flows into negative electrode formation closed circuit by foreign current loop and sends outElectricity acting.
The anode material of SOFC is mainly by electronic conductive material and oxide ion conduction materialMaterial mixes, and the oxygen-ion conductive material in anode is made up of electrolyte conventionally, at present three major typesElectrolyte is stable zirconia (Stabilized-ZrO2Flourite), the cerium oxide of doping(Doped-CeO2And the lanthanum gallate series (Doped-Lanthanum of Ishihara invention Flourite)GallatesPerovskite; US6844098B1). Electronic conductive material in anode is reduced by nickel oxideThe nickel forming forms, and metallic nickel is the good catalyst of anode of solid oxide fuel cell reaction simultaneously.So the anode material of SOFC can be expressed as NiO-Zirconia, NiO-Ceria,NiO-DopedLanthanumGallates (nickel oxide is reduced to metallic nickel after anode passes into fuel).
Because the anode of SOFC is nickel and oxide ion conduction oxide mixture, anodeHydroxide reaction just occur on the contact-making surface of metallic nickel and oxide ion conduction oxide, this interface is calledThe three phase boundary of anode. Under extreme conditions, when leaking-in air in anode makes reducing atmosphere quilt in anodeDestroy, metallic nickel is oxidized to nickel oxide and makes anode three phase boundary destroyed, causes battery performance decayReduce battery.
Summary of the invention
The problem of not growing service life in order to solve conventional composite anode cell, the invention provides oneThe SOFC anode material of excellent in durability.
The invention provides a kind of SOFC anode material, described anode material is oxygenCompound powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein, 0≤x≤0.3,0.02≤y≤0.95,0≤z≤0.3，LnOαFor Ca, Mg, Sc, Y, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb,The corresponding oxide of Dy, Ho, Er, Tm, Yb, Lu, MOβFor Mn, Fe, Co, Ni, Ru,The corresponding oxide of Rh, Pd, Os, Ir, Pt, Au. [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zWithTime there is electron conduction, oxygen conduction and anodic oxidation catalytic effect, can be directly as solid oxygenCompound anode of fuel cell materials'use.
Preferably, oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zParticle diameter be 0-2 μ m.
Preferably, described anode material also comprises the nickel oxide that quality is 0-90%.[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zAlso can be mixed into composite anode materials with nickel oxide.
Preferably, described anode material also comprises oxygen-ion conductive material, and the quality of nickel oxide is nickel oxide30-80% with oxygen-ion conductive material quality sum.
Preferably, oxygen-ion conductive material is that stable zirconia, the cerium oxide of doping, strontium magnesium cobalt mixed altogetherAt least one in assorted lanthanum gallate.
[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zCan be added into NiO-Zirconia, NiO-Ceria,In the two system combination electrodes such as NiO-DopedLanthanumGallates as Section 3 additive. Wherein[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zQuality account for nickel oxide, oxygen-ion conductive material,[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zThe 0-wt100% of quality sum.
The present invention also provides a kind of method of preparing SOFC anode material, the partyMethod comprises the following steps:
(1) according to [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zStoichiometric ratio, by respective amountZrCl2O·8H2O、Ce(NO3)3·6H2O and treat that the nitrate of doped chemical is evenly dissolved in distilled water;
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir;
(3) filter out precipitation, dry after at 800-1400 DEG C sintering 2-20h;
(4) powder after sintering is carried out to wet ball grinding, obtain described oxide powder[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z。
Preferably, in step (4), the medium of wet ball grinding is ethanol, and ball material mass ratio is 30/1-50/1,Rotating speed is 200-800rpm, and Ball-milling Time is 5-30h.
Preferably, in the time that described anode material comprises nickel oxide, the method is further comprising the steps of: by oxygenCompound powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zAfter mixing with nickel oxide powder, carry out wet method ballMill.
Preferably, in the time that described anode material comprises nickel oxide and oxygen-ion conductive material, the method is also wrappedDraw together following steps: by oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, nickel oxide powder,Oxygen-ion conductive material powder carries out wet ball grinding after mixing.
Preferably, the condition of wet ball grinding is: ball material mass ratio is 30/1-50/1, and rotating speed is 200-800Rpm, Ball-milling Time is 5-30h.
Anode material of the present invention, than conventional composite anode material, has better thermal expansion stability,More outstanding anti-oxidant durability. High-durability means that can reduce the long-term of fuel cell moves intoThis, popularize to the commercialization of SOFC the vital effect of playing.
Brief description of the drawings
Fig. 1 is anode material Ce of the present inventionyZr1-yO2Soild oxide prepared by (y=0.5,0.9,0.1)Electric current～the voltage curve of fuel cell;
Fig. 2 is anode material (Y of the present invention2O3)x(Ce0.5Zr0.5O2)1-x(x=0.01,0.05,0.2) preparationThe electric current～voltage curve of SOFC;
Fig. 3 is anode material [(Y of the present invention2O3)0.05(Ce0.5Zr0.5O2)0.95]1-z[NiO]z(z＝0.05，0.1,0.2) electric current～voltage curve of the SOFC of preparing;
Fig. 4 is anode material Ce of the present invention0.5Zr0.5O2The solid oxygen of preparing with standard composite anode materialsElectric current～the voltage curve of compound fuel cell after 50 redox cycle;
Fig. 5 is anode material (Y of the present invention2O3)0.05(Ce0.5Zr0.5O2)0.95With standard composite anode materialsElectric current～the voltage curve of the SOFC of preparation after 50 redox cycle;
Fig. 6 is anode material (Y of the present invention2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1Compound with standardSOFC prepared by the anode material electric current～voltage song after 50 redox cycleLine chart;
Fig. 7 is anode material (Y of the present invention2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-NiO and standardElectric current～the voltage curve of SOFC prepared by composite anode materials;
Fig. 8 is anode material (Y of the present invention2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-NiO and standardSOFC prepared by the composite anode materials electric current～electricity after 50 redox cycleThe line chart of buckling;
Fig. 9 is anode material (Y of the present invention2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89SOFC prepared by-NiO and standard composite anode materialsElectric current～voltage curve;
Figure 10 is anode material (Y of the present invention2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89SOFC prepared by-NiO and standard composite anode materials existsElectric current～voltage curve after 50 redox cycle;
Figure 11 is anode material (Y of the present invention2O3)0.05(Ce0.5Zr0.5O2)0.95And anode material(Sc2O3)0.05(Ce0.5Zr0.5O2)0.95Electric current～the voltage curve of the SOFC of preparation.
Detailed description of the invention
Anode of solid oxide fuel cell material [(LnO of the present inventionα)x(CeyZr1-yO2)1-x]1-z[MOβ]z(0≤x≤0.3，0.02≤y≤0.95，0≤z≤0.3；LnOαFor calcium (Ca), magnesium (Mg), scandium (Sc),Yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd),The correspondence of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu)Oxide; MOβFor manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru),The corresponding oxygen of rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) or gold (Au)Compound. Described anode material powder adopts coprecipitation to be prepared. Described anode material powderConcrete preparation method is as follows:
(1) according to [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zStoichiometric ratio, by respective amountRaw material ZrCl2O·8H2O、Ce(NO3)3·6H2O and treat that the nitrate of doped chemical is evenly dissolved in distilled waterIn;
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir;
(3) filter out precipitation, dry after at 800-1400 DEG C sintering 2-20h;
(4) powder after sintering is carried out to wet ball grinding until particle diameter meets the requirements. As onePreferred embodiment, is ethanol at the medium of wet ball grinding described in described ball milling blend step, ball material qualityThan being 30/1-50/1, rotating speed is 200-800rpm, and Ball-milling Time is 5-30h.
In order to realize good effect, oxide powder [(LnO of the present inventionα)x(CeyZr1-yO2)1-x]1-z[MOβ]zParticle diameter be preferably 0-2 μ m.
The oxide powder being obtained by the method can directly apply to anode of solid oxide fuel cell.
[(LnO of the present inventionα)x(CeyZr1-yO2)1-x]1-z[MOβ]zAfter powder also can mix with nickel oxideAs composite anode materials. Wherein the quality of nickel oxide be nickel oxide and[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zThe 0-90% of powder quality sum. Described composite anode materialThe concrete preparation method of material powder is as follows:
A) by oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zAfter mixing with nickel oxide powderCarry out wet ball grinding mixing. As a kind of preferred embodiment, wet described in described ball milling blend stepThe medium of method ball milling is ethanol, and ball material mass ratio is 30/1-50/1, and rotating speed is 200-800rpm, ball millingTime is 5-30h.
B) in order to realize good effect, [(LnO of the present inventionα)x(CeyZr1-yO2)1-x]1-z[MOβ]zBe preferably and be not more than 5 μ m with the particle diameter of nickel oxide.
[(LnO of the present inventionα)x(CeyZr1-yO2)1-x]1-z[MOβ]zPowder also can add traditional answeringIn composite electrode material as catalytic additive. Wherein [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zPowderQuality is nickel oxide, oxygen-ion conductive material and [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zPowder matterThe 0-100% of amount sum. The concrete preparation method of described three-system composite anode materials powder is as follows:
A) by [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zPowder and nickel oxide powder and oxonium ion are ledElectric material powder carries out wet ball grinding mixing after mixing. As a kind of preferred embodiment, at described ball millingDescribed in blend step, the medium of wet ball grinding is ethanol, and ball material mass ratio is 30/1-50/1, and rotating speed is200-800rpm, Ball-milling Time is 5-30h.
B) in order to realize good effect, [(LnO of the present inventionα)x(CeyZr1-yO2)1-x]1-z[MOβ]z，The particle diameter of nickel oxide and oxygen-ion conductive material is preferably and is not more than 5 μ m.
In above-mentioned composite anode materials, described oxygen-ion conductive material is preferably the oxygen of metal oxide stabilityChange at least one in zirconium, the cerium oxide of doped metallic oxide and the lanthanum gallate of strontium magnesium cobalt codope. UnderIn the face of these three kinds of oxygen-ion conductive materials are discussed in detail.
Zirconia (the StabilizedZrO of metal oxide stability2) in, conventional metal oxide is oxidationCalcium (CaO), magnesia (MgO), yittrium oxide (Y2O3), scandium oxide (Sc2O3), lanthana (La2O3)、Praseodymium oxide (Pr2O3), neodymia (Nd2O3), promethium oxide (Pm2O3), samarium oxide (Sm2O3), oxygenChange europium (Eu2O3), gadolinium oxide (Gd2O3), terbium oxide (Tb2O3), dysprosia (Dy2O3), oxidationHolmium (Ho2O3), erbium oxide (Er2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3)。Preferably, in the zirconia of described metal oxide stability, the content of described metal oxide is1-20mol%. 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％Sc2O3With1mol％CeO2The ZrO of doping2[(Sc2O3)0.1(CeO2)0.01(ZrO2)0.89]，10mol％Sc2O3With1mol％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 DopedCeO of doped metallic oxide2) in, conventional metal oxide is calcium oxide(CaO), magnesia (MgO), and one or more in some rare earth oxides. Described rare earth unitElement oxide can be yittrium oxide (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), oxygenChange erbium (Er2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3). These goldBelong to oxide M O or M2O3CeO after doping2For: Ce1-xMxO2(0.05≤x≤0.3), M isAbove-mentioned metallic element be calcium, magnesium, yttrium, scandium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium,One or more in holmium, erbium, thulium, ytterbium and lutetium. General material has (Ce0.90Gd0.10)O1.95、(Ce0.80Gd0.20)O1.9、(Ce0.85Sm0.15)O1.925、(Ce0.80Sm0.20)O1.9。
Lanthanum gallate (Sr, Mg, the andCoco-dopedLaGaO of strontium magnesium cobalt codope3) in, described strontium magnesium cobaltThe lanthanum gallate of codope meets following chemical general formula: La0.8Sr0.2Ga0.8Mg0.2-xCoxO3(0≤x≤0.15)。
Above-mentioned oxygen-ion conductive material powder can by solid reaction process, solution combustion synthetic method, coprecipitation,Traditional inorganic material synthetic method preparation such as hydrothermal synthesis method, collosol and gel synthetic method, polymer precursor method.Also can directly buy from companies such as FuelCellMaterials.
Above-mentioned [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zAnode material, by nickel oxide and[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zMix two system composite anode materials and by nickel oxide,Oxygen-ion conductive material and [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zThe three-system composite anode material mixingThe using method of material, comprising: first, above-mentioned three kinds of anode materials and organic bond are mixed and made into electricityUtmost point slurry; Then, utilize the method for serigraphy described electrode slurry to be printed in to bath surface, electricityUtmost point THICKNESS CONTROL is at 10-100 μ m; By described electrode sintering 1-10h in 1000-1400 DEG C.
Adopt full battery testing method test to adopt the SOFC of different anode materials belowMonocell power generation performance curve. In each embodiment, be also provided with the normal cell of contrast, this contrast standardIt is (the Sc of 200 μ m that the electrolyte of battery adopts thickness2O3)0.10(CeO2)0.01(ZrO2)0.89Electrolyte, sunUtmost point material is the NiO-(Sc of mass ratio 56:442O3)0.10(CeO2)0.01(ZrO2)0.89Composite, negative electrodeMaterial is the (La of mass ratio 50:500.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89CompoundMaterial. Battery material powder all obtains from FuelCellMaterials company. Adopt method for printing screen to existElectrolyte sheet one side printing top surface area 0.64cm2NiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89AnodeSlurry, after being dried, at 1100-1400 DEG C, (the contrast standard battery using in following examples is all 1300At DEG C, carry out) in sintering 1-5h (the equal sintering of contrast standard battery using in following examples 4h).Adopt the method printing top surface area 0.64cm of serigraphy at the opposite side of electrolyte sheet2's(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry, dry after1100-1300 DEG C (the contrast standard battery using in following examples all carries out at 1200 DEG C)Middle sintering 1-5h (the equal sintering of contrast standard battery using in following examples 4h).
The monocell performance test methods of following examples and normal cell is as follows: under 800 DEG C of furnace temperature, enterThe performance test of row monocell, anode passes into the hydrogen that is mixed with 3vol% steam, and negative electrode passes into air.
Embodiment 1
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein, whenX=0, y=0.5, when z=0, oxide powder is Ce0.5Zr0.5O2; Work as x=0, y=0.9, when z=0,Oxide powder is Ce0.9Zr0.1O2; Work as x=0, y=0.1, when z=0, oxide powder is Ce0.1Zr0.9O2。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O is according to the molar percentage of Zr and Ce elementBe dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2h.
(3) filter out precipitation, at 120 DEG C, be dried after 24h sintering 10h at 1300 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 600rpm, under the condition of ball material mass ratio 35/1Ball milling 5h to particle average grain diameter be 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2CeyZr1-yO2(y=0.5,0.9,0.1) anode slurry is doneFor anode, dry after in 1300 DEG C sintering 4h. Adopt serigraphy at the opposite side of electrolyte sheetMethod printing top surface area 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as negative electrode, dry after in 1200 DEG C sintering 4h.
Fig. 1 has shown employing CeyZr1-yO2The monocell power generation performance of (y=0.5,0.9,0.1) anode, asScheme known, in the time of y=0.5, CeyZr1-yO2Anode has optimum power generation performance. At 400mAcm-2'sUnder discharging condition, cell voltage is 0.41V, and power output is 163.6mWcm-2。
Embodiment 2
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein, whenX=0.05, y=0.5, z=0, when Ln=Y (yttrium), oxide powder is (Y2O3)0.05(Ce0.5Zr0.5O2)0.95；Work as x=0.01, y=0.5, z=0, when Ln=Y (yttrium), oxide powder is (Y2O3)0.01(Ce0.5Zr0.5O2)0.99；Work as x=0.2, y=0.5, z=0, when Ln=Y (yttrium), oxide powder is (Y2O3)0.2(Ce0.5Zr0.5O2)0.8。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O according to Zr, Ce andThe molar percentage of Y element is dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2h.
(3) filter out precipitation, at 120 DEG C, be dried after 24h sintering 10h at 1300 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 600rpm, under the condition of ball material mass ratio 35/1Ball milling 5h to particle average grain diameter be 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2(Y2O3)x(Ce0.5Zr0.5O2)1-x(x＝0.01，0.05，0.2)Anode slurry is as anode, dry after in 1300 DEG C sintering 4h. Opposite side at electrolyte sheet adoptsThe method printing top surface area 0.64cm of serigraphy2's(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as negative electrode, dry afterSintering 4h in 1200 DEG C.
Fig. 2 has shown employing (Y2O3)x(Ce0.5Zr0.5O2)1-xThe monocell of (x=0.01,0.05,0.2) anodePower generation performance. As figure shows in the time of x=0.05, (Y2O3)x(Ce0.5Zr0.5O2)1-xAnode has optimum generatingPerformance, at 400mAcm-2Discharging condition under, cell voltage is 0.54V, power output is214.7mWcm-2。
Embodiment 3
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein, whenX=0.05, y=0.5, z=0.05, Ln=Y (yttrium), when M=Ni (nickel), oxide powder is(Y2O3)0.0475(Ce0.5Zr0.5O2)0.9025(NiO)0.05; Work as x=0.05, y=0.5, z=0.1, Ln=Y (yttrium),When M=Ni (nickel), oxide powder is (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1; Work as x=0.05,Y=0.5, z=0.2, Ln=Y (yttrium), when M=Ni (nickel), oxide powder is(Y2O3)0.04(Ce0.5Zr0.5O2)0.76(NiO)0.2。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Ni(NO3)2·6H2OAccording to being dissolved in distilled water according to the molar percentage of Zr, Ce, Y and Ni element.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2h.
(3) filter out precipitation, at 120 DEG C, be dried after 24h sintering 10h at 1300 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 400rpm, under the condition of ball material mass ratio 35/1Ball milling 10h to particle average grain diameter be 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2's [(Y2O3)0.05(Ce0.5Zr0.5O2)0.95]1-z(NiO)z(z=0.05,0.1,0.2) anode slurry is as anode, dryAfter dry in 1300 DEG C sintering 4h. Adopt the method for serigraphy to print table at electrolyte sheet opposite sideArea 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry conductNegative electrode, dry after in 1200 DEG C sintering 4h.
Fig. 3 has shown employing [(Y2O3)0.05(Ce0.5Zr0.5O2)0.95]1-z(NiO)z(z=0.05,0.1,0.2) sunThe monocell power generation performance of the utmost point. As figure shows, in the time of z=0.1,[(Y2O3)0.05(Ce0.5Zr0.5O2)0.95]1-z(NiO)zAnode has optimum power generation performance. At 400mAcm-2'sUnder discharging condition, cell voltage is 0.69V, and power output is 277.7mWcm-2。
Embodiment 4
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein, x=0,Y=0.5, z=0, oxide powder is Ce0.5Zr0.5O2。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O is dissolved in distillation according to molar percentage 1:1In water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2h.
(3) filter out precipitation, at 120 DEG C, be dried after 24h sintering 20h at 800 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 600rpm, under the condition of ball material mass ratio 30/1Ball milling 5h to particle average grain diameter be 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2Ce0.5Zr0.5O2Anode slurry is as anode, after being driedSintering 4h in 1300 DEG C. Adopt the method printing upper surface of serigraphy at the opposite side of electrolyte sheetLong-pending 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as the moonThe utmost point, dry after in 1200 DEG C sintering 4h.
Fig. 4 has shown monocell power generation performance after anode-side is carried out 50 redox cycle. AdoptNiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell of composite anode carries out 50 oxidations in anode-sideAfter reduction circulation, power generation performance decay obviously. At 200mAcm-2Place's cell voltage decays to from 0.89V0.61V, at 400mAcm-2Place's cell voltage decays to 0.41V from 0.8V. Adopt Ce0.5Zr0.5O2OxygenThe monocell of compound anode carries out after 50 redox cycle in anode-side, and power generation performance is microwave attenuation slightly.At 200mAcm-2Place's cell voltage decays to 0.67V from 0.68V, at 400mAcm-2Place's cell voltageDecay to 0.39V from 0.41V. Visible, Ce0.5Zr0.5O2Oxide anode has good redox resistance toProperty for a long time, and after decay, still keep higher power generation performance.
Embodiment 5
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein,X=0.05, y=0.5, z=0, Ln=Y (yttrium), oxide powder is (Y2O3)0.05(Ce0.5Zr0.5O2)0.95。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O is according to molar percentage47.5:47.5:10 is dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2h.
(3) filter out precipitation, at 150 DEG C, be dried after 20h sintering 10h at 1400 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 600rpm, under the condition of ball material mass ratio 40/1Ball milling 5h to particle average grain diameter be 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2(Y2O3)0.05(Ce0.5Zr0.5O2)0.95Anode slurry conductAnode, dry after in 1300 DEG C sintering 4h. Adopt the side of serigraphy at the opposite side of electrolyte sheetMethod printing top surface area 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89CloudyUtmost point slurry is as negative electrode, dry after in 1200 DEG C sintering 4h.
Fig. 5 has shown monocell power generation performance after anode-side is carried out 50 redox cycle. AdoptNiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell of composite anode carries out 50 oxidations in anode-sideAfter reduction circulation, power generation performance decay obviously. At 200mAcm-2Place's cell voltage decays to from 0.89V0.61V, at 400mAcm-2Place's cell voltage decays to 0.41V from 0.8V. Adopt (Y2O3)0.05(Ce0.5Zr0.5O2)0.95The monocell of oxide anode carries out 50 redox in anode-side and followsAfter ring, power generation performance is microwave attenuation slightly. At 200mAcm-2Place's cell voltage decays to 0.74V from 0.75V,At 400mAcm-2Place's cell voltage decays to 0.52V from 0.54V. It is visible,(Y2O3)0.05(Ce0.5Zr0.5O2)0.95Oxide anode has good redox durability, and decay after stillSo keep higher power generation performance.
Embodiment 6
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein,X=0.05, y=0.5, z=0.1, Ln=Y (yttrium), M=Ni (nickel), oxide powder is(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Ni(NO3)2·6H2OAccording to molar percentage, 42.75:42.75:9:10 is dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2 hours.
(3) filter out precipitation, dry after 24 hours at 120 DEG C, sintering 2 hours at 1400 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 400rpm, under the condition of ball material mass ratio 50/1Ball milling 10 hours to particle average grain diameter is 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1AnodeSlurry is as anode, dry after in 1300 DEG C sintering 4 hours. Opposite side at electrolyte sheet adoptsThe method printing top surface area 0.64cm of serigraphy2's(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as negative electrode, dry afterSintering 4 hours in 1200 DEG C.
Fig. 6 has shown monocell power generation performance after anode-side is carried out 50 redox cycle. AdoptNiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell of composite anode carries out 50 oxidations in anode-sideAfter reduction circulation, power generation performance decay obviously. At 200mAcm-2Place's cell voltage decays to from 0.89V0.61V, at 400mAcm-2Place's cell voltage decays to 0.41V from 0.8V. Adopt(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1The monocell of oxide anode carries out oxygen 50 times in anode-sideChange after reduction circulation, generating property is microwave attenuation slightly. At 200mAcm-2Place's cell voltage decays to from 0.85V0.84V, at 400mAcm-2Place's cell voltage decays to 0.66V from 0.69V. It is visible,(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1Oxide anode has good redox durability, andAfter decay, still keep higher power generation performance.
Embodiment 7
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein,X=0.05, y=0.5, z=0.1, Ln=Y (yttrium), M=Ni (nickel), oxide powder is(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Ni(NO3)2·6H2OAccording to molar percentage, 42.75:42.75:9:10 is dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2 hours.
(3) filter out precipitation, dry after 24 hours at 120 DEG C, at 1300 DEG C, sintering 10 is littleTime.
(4), after sintering, at ethanol medium, rotating speed is 400rpm, under the condition of ball material mass ratio 35/1Ball milling 10 hours to particle average grain diameter is 1.2 μ m.
At above-mentioned (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1In powder, add nickel oxide powder, mixAnd grind, grinding condition is as follows: ball milling 10 hours in ethanol medium, rotating speed 200rpm, ball material qualityThan 35/1, finally obtain the composite anode materials powder of two systems. Wherein,(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1Account for the quality percentage of the composite anode materials powder of two systems44% (than being(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1/(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-NiO＝44/100)。
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-NiOAnode slurry is as anode, dry after in 1300 DEG C sintering 4 hours. At the opposite side of electrolyte sheetAdopt the method printing top surface area 0.64cm of serigraphy2's(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as negative electrode, dry afterSintering 4 hours in 1200 DEG C.
Fig. 7 has shown employing (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1The monocell of-NiO anode is sent outElectrical property, at 400mAcm-2Discharging condition under, cell voltage is 0.88V, power output is354.7mWcm-2. In figure, also show that to adopt mass ratio be 56:44NiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell power generation performance of standard composite anode,400mAcm-2Discharging condition under, cell voltage is 0.79V, power output is 315.8mWcm-2. AsScheme known (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1It is compound that the power generation performance of-NiO anode is better than standardAnode material.
Fig. 8 has shown monocell power generation performance after anode-side is carried out 50 redox cycle. AdoptNiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell of composite anode carries out 50 oxidations in anode-sideAfter reduction circulation, power generation performance decay obviously. At 200mAcm-2Place's cell voltage decays to from 0.89V0.61V, at 400mAcm-2Place's cell voltage decays to 0.41V from 0.8V. Adopt(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1The monocell of-NiO composite anode carries out 50 times in anode-sideAfter redox cycle, generating property is microwave attenuation slightly. At 200mAcm-2Place's cell voltage is decayed from 0.98VTo 0.92V, at 400mAcm-2Place's cell voltage decays to 0.76V from 0.89V. It is visible,(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-NiO composite anode has good redox durability,And after decay, still keep higher power generation performance.
Embodiment 8
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein,X=0.05, y=0.5, z=0.1, Ln=Y (yttrium), M=Ni (nickel), oxide powder is(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Ni(NO3)2·6H2OAccording to molar percentage, 42.75:42.75:9:10 is dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2 hours.
(3) filter out precipitation, dry after 24 hours at 120 DEG C, at 1300 DEG C, sintering 10 is littleTime.
(4), after sintering, at ethanol medium, rotating speed is 800rpm, under the condition of ball material mass ratio 35/1Ball milling 5 hours to particle average grain diameter is 0.05 μ m.
At standard two system composite anode materials NiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89(wherein(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Quality account for whole standard composite anode materials quality 44%, averageGranularity is that 1.2 μ add above-mentioned (Y in m)2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1Powder, mixes and grindsMill, grinding condition is as follows: ball milling 10 hours in ethanol medium, rotating speed 200rpm, ball material mass ratio 35/1,Finally obtain the composite anode materials powder of three-system. Wherein, above-mentioned(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1Powder accounts for the quality of the composite anode materials powder of three-systemPercentage is 30% (i.e. (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1/(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89-NiO＝3/7)。
[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zPowder joins two system composite anodes as additiveIn material, [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zThe particle diameter of powder is 0.02-1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2's(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89-NiO anode slurryAs anode, dry after in 1300 DEG C sintering 4 hours. Opposite side at electrolyte sheet adopts silk screenThe method printing top surface area 0.64cm of printing2's(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as negative electrode, dry afterSintering 4 hours in 1200 DEG C.
Fig. 9 has shown employing(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The list of-NiO anodeCell power generation performance, at 400mAcm-2Discharging condition under, cell voltage is 0.83V, power outputFor 325.6mWcm-2. In figure, also show that to adopt mass ratio be 56:44NiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell power generation performance of standard composite anode,400mAcm-2Discharging condition under, cell voltage is 0.79V, power output is 315.8mWcm-2. AsScheme known (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89-NiO sunThe power generation performance of the utmost point is better than standard composite anode materials.
Figure 10 has shown monocell power generation performance after anode-side is carried out 50 redox cycle. AdoptNiO-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell of composite anode carries out 50 oxidations in anode-sideAfter reduction circulation, power generation performance decay obviously. At 200mAcm-2Place's cell voltage decays to from 0.89V0.61V, at 400mAcm-2Place's cell voltage decays to 0.41V from 0.8V. Adopt(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89-NiO composite anodeMonocell carry out after 50 redox cycle in anode-side, generating property is microwave attenuation slightly. ?200mAcm-2Place's cell voltage decays to 0.89V from 0.94V, at 400mAcm-2Place cell voltage from0.83V decays to 0.74V. It is visible,(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(NiO)0.1-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89-NiO composite anodeThere is good redox durability, and still keep higher power generation performance after decay.
Embodiment 9
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein,X=0.05, y=0.5, z=0, Ln=Sc (scandium), oxide powder is (Sc2O3)0.05(Ce0.5Zr0.5O2)0.95。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Sc(NO3)3·6H2O is according to a mole percentageBe dissolved in distilled water than 47.5:47.5:10.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2h.
(3) filter out precipitation, at 120 DEG C, be dried after 24h sintering 10h at 1300 DEG C.
(4), after sintering, at ethanol medium, rotating speed is 600rpm, under the condition of ball material mass ratio 35/1Ball milling 5h to particle average grain diameter be 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2(Sc2O3)0.05(Ce0.5Zr0.5O2)0.95Anode slurry conductAnode, dry after in 1300 DEG C sintering 4h. Adopt the side of serigraphy at the opposite side of electrolyte sheetMethod printing top surface area 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89CloudyUtmost point slurry is as negative electrode, dry after in 1200 DEG C sintering 4h.
Figure 11 has shown employing (Sc2O3)0.05(Zr0.5Ce0.5O2)0.95(Y2O3)0.05(Zr0.5Ce0.5O2)0.95SunThe monocell power generation performance of utmost point material. Adopt (Sc2O3)0.05(Zr0.5Ce0.5O2)0.95Anode material exists400mAcm-2Discharging condition under, cell voltage is 0.58V, power output is 229mWcm-2. AdoptWith (Y2O3)0.05(Zr0.5Ce0.5O2)0.95Anode material is at 400mAcm-2Discharging condition under, cell voltageFor 0.54V, power output is 214.7mWcm-2. Adopt as figure shows (Sc2O3)0.05(Zr0.5Ce0.5O2)0.95Anode material be slightly better than employing (Y2O3)0.05(Zr0.5Ce0.5O2)0.95The power generation performance of anode material. ButSc is more expensive than Y element, considers composite factor, can choice for use.
Embodiment 10
With coprecipitation synthesis oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein,X=0.05, y=0.5, z=0.1, Ln=Y (yttrium), M=Co (cobalt), oxide powder is(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(CoOβ)0.1。
(1) by ZrCl2O·8H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Co(NO3)2·6H2OAccording to molar percentage, 42.75:42.75:9:10 is dissolved in distilled water.
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir 2 hours.
(3) filter out precipitation, dry after 24 hours at 120 DEG C, at 1300 DEG C, sintering 10 is littleTime.
(4), after sintering, at ethanol medium, rotating speed is 400rpm, under the condition of ball material mass ratio 35/1Ball milling 10 hours to particle average grain diameter is 1.2 μ m.
Adopt following methods to test the performance of this anode material powder:
First, in above-mentioned composite anode powder, add organic bond to make composite anode slurry, whereinThe mass ratio of above-mentioned composite anode powder and organic binder bond is 5:5.
Then, adopt the method for serigraphy at the (Sc of 200 μ m2O3)0.10(CeO2)0.01(ZrO2)0.89ElectricitySeparate matter sheet one side printing top surface area 0.64cm2(Y2O3)0.045(Ce0.5Zr0.5O2)0.855(CoOβ)0.1AnodeSlurry is as anode, dry after in 1300 DEG C sintering 4 hours. Opposite side at electrolyte sheet adoptsThe method printing top surface area 0.64cm of serigraphy2's(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is as negative electrode, dry afterSintering 4 hours in 1200 DEG C.
Adopt (Y2O3)0.045(Ce0.5Zr0.5O2)0.855(CoOβ)0.1Anode material and employing(Y2O3)0.045(Zr0.5Ce0.5O2)0.855(NiO)0.1The monocell power generation performance of anode material, at 400mAcm-2Under discharging condition, the cell voltage drawing and the result of power output are roughly the same. But Co compares NiWant expensive a lot, consider, preferentially select Ni element.
Preferred embodiment of the present invention, not in order to limit the present invention, all in essence of the present inventionAny amendment of doing in content, be equal to and replace and simple modifications etc., all should be included in of the present inventionWithin protection domain.
Claims (10)
1. a SOFC anode material, is characterized in that, described anode materialFor oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, wherein, 0≤x≤0.3,0.02≤y≤0.95，0≤z≤0.3，LnOαFor Ca, Mg, Sc, Y, La, Pr, Nd, Pm, Sm, Eu,The corresponding oxide of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, MOβFor Mn, Fe, Co,The corresponding oxide of Ni, Ru, Rh, Pd, Os, Ir, Pt, Au.
2. SOFC anode material according to claim 1, its feature existsIn, oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zParticle diameter be 0-2 μ m.
3. SOFC anode material according to claim 1, its feature existsIn, described anode material also comprises the nickel oxide that quality is 0-90%.
4. SOFC anode material according to claim 3, its feature existsIn, described anode material also comprises oxygen-ion conductive material, and the quality of nickel oxide is nickel oxide and oxonium ionThe 30-80% of conductive material quality sum.
5. SOFC anode material according to claim 3, its feature existsIn, oxygen-ion conductive material is stable zirconia, the cerium oxide of doping, the gallic acid of strontium magnesium cobalt codopeAt least one in lanthanum.
6. prepare a method for SOFC claimed in claim 1 anode material,It is characterized in that, the method comprises the following steps:
(1) according to [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zStoichiometric ratio, by respective amountZrCl2O·8H2O、Ce(NO3)3·6H2O and treat that the nitrate of doped chemical is evenly dissolved in distilled water;
(2) stir to slowly splashing into ammoniacal liquor in solution and continuing, until after all precipitations all separate outContinue again to stir;
(3) filter out precipitation, dry after at 800-1400 DEG C sintering 2-20h;
(4) powder after sintering is carried out to wet ball grinding, obtain described oxide powder[(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z。
7. the preparation method of anode material for SOFC according to claim 6,It is characterized in that, in step (4), the medium of wet ball grinding is ethanol, and ball material mass ratio is 30/1-50/1,Rotating speed is 200-800rpm, and Ball-milling Time is 5-30h.
8. the preparation method of anode material for SOFC according to claim 6,It is characterized in that, in the time that described anode material comprises nickel oxide, the method is further comprising the steps of: by oxygenCompound powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]zAfter mixing with nickel oxide powder, carry out wet method ballMill.
9. the preparation method of anode material for SOFC according to claim 6,It is characterized in that, in the time that described anode material comprises nickel oxide and oxygen-ion conductive material, the method is also wrappedDraw together following steps: by oxide powder [(LnOα)x(CeyZr1-yO2)1-x]1-z[MOβ]z, nickel oxide powder,Oxygen-ion conductive material powder carries out wet ball grinding after mixing.
10. the preparation of anode material for SOFC according to claim 8 or claim 9Method, is characterized in that, the condition of wet ball grinding is: ball material mass ratio is 30/1-50/1, and rotating speed is200-800rpm, Ball-milling Time is 5-30h.
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| 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 |
| CN110676472A (en) * | 2019-09-30 | 2020-01-10 | 潍柴动力股份有限公司 | A kind of fuel pretreatment catalyst for solid oxide fuel cell system and preparation method thereof |
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| 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 |
| CN110676472A (en) * | 2019-09-30 | 2020-01-10 | 潍柴动力股份有限公司 | A kind of fuel pretreatment catalyst for solid oxide fuel cell system and preparation method thereof |
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