CN102354605B - Method for preparing doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of microwave auxiliary reaction supercharge method - Google Patents
Method for preparing doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of microwave auxiliary reaction supercharge method Download PDFInfo
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- CN102354605B CN102354605B CN2011102827778A CN201110282777A CN102354605B CN 102354605 B CN102354605 B CN 102354605B CN 2011102827778 A CN2011102827778 A CN 2011102827778A CN 201110282777 A CN201110282777 A CN 201110282777A CN 102354605 B CN102354605 B CN 102354605B
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- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000084 colloidal system Substances 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000010992 reflux Methods 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000008236 heating water Substances 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 16
- 238000007789 sealing Methods 0.000 abstract description 13
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000011056 performance test Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 235000014121 butter Nutrition 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
- 238000000151 deposition Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical group CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PNCDAXYMWHXGON-UHFFFAOYSA-N ethanol;niobium Chemical compound [Nb].CCO.CCO.CCO.CCO.CCO PNCDAXYMWHXGON-UHFFFAOYSA-N 0.000 description 1
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for preparing a doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of a microwave auxiliary reaction supercharge method and belongs to a low-temperature synthesis method of a solar battery photoelectrode. The preparation method comprises the following steps: 1, adding a titaniferous precursor into alcohol, uniformly mixing, then adding an adulterant, stirring, then adding a hydrolysis inhibitor, and slowly dropwise adding deionized water, thus obtaining a mixed solution; 2, heating the mixed solution in a water bath, stirring, refluxing and reacting until the reaction is over, thus obtaining a titaniferous and element-doped colloid; 3, cooling the colloid to room temperature, then transferring the cooled colloid into a high-pressure vessel, adding a decomposition agent and then rapidly sealing the vessel; 4, placing the vessel into a microwave reaction device, rapidly heating, keeping stirring, filtering reaction products, washing with deionized water, and drying, thus obtaining doping-type crystalline titanium dioxide. The method provided by the invention has the advantages that the doping-type crystalline titanium dioxide with grains of about 120nm can be prepared at low temperature; the dispersibility is better; the preparation process time is shorter; and long-term follow-up high-temperature crystallization treatment is not required.
Description
Technical field
The present invention relates to a kind of low-temperature synthetic method of solar cell photoelectric pole, particularly a kind of microwave assisted reaction supercharge method low temperature prepares doping type crystalline state titanium dioxide photoelectrode.
Background technology
Doping type titanium dioxide is the main material of solar cell photoelectric pole, and the preparation method can be divided into physical deposition method and chemical preparation method.The common depositing temperature of physical deposition method is higher, and the depositing device complex and expensive.The chemical method preparation method mainly contains liquid-phase precipitation method, sol-gal process and hydro thermal method.What liquid-phase precipitation method and sol-gal process were prepared is unbodied titanium dioxide, is transformed into the titanium dioxide of crystalline state such as need, also will carry out follow-up high-temperature process; Although hydro thermal method can be prepared crystalline state titanium dioxide, reaction temperature is usually more than 150 ℃.If can prepare crystalline state titanium dioxide being no more than under 100 ℃ the cryogenic conditions, be conducive to reduce energy consumption on the one hand, can expand its range of application on the other hand, as can on the plastic-substrates of some non-refractories, directly preparing the crystalline state optoelectronic pole.In addition, because the doping type titanium dioxide of low temperature preparation is amorphous state under the normal condition, in order to improve electricity conversion, need to be transformed into crystalline state by follow-up high-temperature process, this high-temperature process tends to cause the loss of doped chemical, has reduced the doping effect.
Summary of the invention
The objective of the invention is to provide a kind of microwave assisted reaction supercharge method low temperature to prepare doping type crystalline state titanium dioxide photoelectrode, solve the problem that under 85～100 ℃ low temperature, is difficult to prepare doping type crystalline state titanium dioxide.
The object of the present invention is achieved like this: the concrete preparation method of doping type crystalline state titanium dioxide photoelectrode is:
One, the presoma that in alcohol, adds titaniferous, mix rear adding alloy, add hydrolysis inhibitor after fully stirring, then slowly drip deionized water, make mixed liquor, wherein the mol ratio of the presoma of titaniferous, alcohol, alloy, hydrolysis inhibitor and deionized water is 1:5～100:0.05～5:0.01 ~ 50:0.5 ~ 50;
Two, with the mixed liquor heating water bath of step 1 preparation, 40～100 ℃ of bath temperatures keep in the heating process stirring, and reflux, and 0.5～2h afterreaction is finished, and makes the colloid of titaniferous and doped chemical;
Three, after the colloid of preparation is cooled to room temperature in step 2, it is moved in the high-pressure-resistant vessel, and add distintegrant, then rapidly with seal of vessel, the mol ratio of the presoma of the titaniferous that wherein adds in distintegrant and the step 1 is 50～1000:1;
Four, the container with good seal in the step 3 is put in the microwave reaction device, microwave power is 100～800W, quickly heat up to 85～100 ℃, insulation 1～4h finishes to reacting, keep in the whole process stirring, product is filtered and wash with deionized water, obtain doping type crystalline state titanium dioxide after the drying.
The presoma of described titaniferous is any in butyl titanate, titanium tetrachloride, the isopropyl titanate.
Described alloy is the water soluble compound that contains in Ag, Zn, Cu, Fe, Al, Co, Sn, Pt, Ru, V, Ta, Nb, Mo, Mn, F, Cl, Br, I, S, B, C, Si, N, the P element any; Or above-mentioned any two combinations; Or the mixture of wantonly three kinds of combinations.
Described hydrolysis inhibitor is divided into acidity, alkalescence or neutral three kinds, wherein acid inhibitor is any in nitric acid, hydrochloric acid, sulfuric acid, lactic acid, the citric acid, the alkalescence inhibitor is monoethanolamine, in diethanol amine, triethanolamine, ammoniacal liquor, NaOH, the potassium hydroxide any, neutral inhibitor are any in polyethylene glycol, the PVP.
Described distintegrant is any in hydrogen peroxide, ammonium carbonate, carbonic hydroammonium, sodium acid carbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, zinc carbonate, ammonium nitrate, ammonium nilrite, the azodiisobutyronitrile.
Beneficial effect owing to having adopted such scheme, in the colloid of the titaniferous for preparing and doped chemical, adds distintegrant, utilizes the principle induced crystallization of chemical reaction supercharging; Then, utilize the method for Microwave-assisted firing, product degree of crystallinity is improved and minimizing reaction required time, under 85～100 ℃ cryogenic conditions, just can prepare fast doping type crystalline state titanium dioxide.By in colloid, adding distintegrant, utilize the principle induced crystallization of chemical reaction supercharging, and utilize the method for Microwave-assisted firing, and product degree of crystallinity is improved and reduce the reaction required time, solved the problem that under 85～100 ℃ low temperature, is difficult to prepare doping type crystalline state titanium dioxide.Reached purpose of the present invention.
Have advantages of following:
1, under 85～100 ℃ cryogenic conditions, can prepare doping type crystalline state titanium dioxide, overcome the shortcoming that follow-up high-temperature process causes doped chemical easily to run off, realize the preparation of the solar cell photoelectric pole of high conversion efficiency.
2, the distintegrant that adds in this invention can be prepared the approximately doping type crystalline state titanium dioxide about 12nm of crystal grain effectively, and better dispersed.
3, the preparation process time of the method is short, need not long follow-up high temperature crystallization and processes.The colloid preparatory phase takes 1～2.5h among the present invention, and the microwave associated phase takes 1～4h, and whole process only needs 2～6.5h.
Description of drawings
Fig. 1 is the X-ray diffraction of mixing tantalum crystalline state titanium dioxide (XRD) collection of illustrative plates of preparation in the embodiment of the invention 1.
Fig. 2 is x-ray photoelectron power spectrum (XPS) figure that mixes Ta 4f in the tantalum crystalline state titanium dioxide of preparation in the embodiment of the invention 1.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1: add the 0.07mol butyl titanate in 2.30mol ethanol, after mixing, add the 0.013mol ethanol tantalum, drip the 0.08mol red fuming nitric acid (RFNA) after fully stirring, slowly drip the 0.20mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 65 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous and tantalum behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 2.90mol hydrogen peroxide, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 200W, quickly heats up to 95 ℃, and insulation 2.5h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make after 60 ℃ of dryings and mix tantalum crystalline state titanium dioxide granule, dispersed better.
Among Fig. 1, the X-ray diffraction of mixing tantalum crystalline state titanium dioxide (XRD) figure of preparation, its diffraction maximum shows that products therefrom is the mixed crystal attitude titanium dioxide of Anatase and Rutile Type, calculates by Scherrer formula (Scherrer equation), and its crystal average diameter is 12.9nm.Among Fig. 2, x-ray photoelectron power spectrum (XPS) collection of illustrative plates of mixing Ta 4f in the tantalum crystalline state titanium dioxide of preparation shows that tantalum is doped in the titanium dioxide.The assembling of solar cell and test as follows:
(1) assembling of solar cell: the doping type crystalline state titanium dioxide for preparing with after a certain amount of absolute ethyl alcohol mixes, is fully ground 30min in agate mortar, obtain doping type crystalline state titania slurry.The employing silk screen printing is filmed, and with the dry 10min in 60 ℃ of drying boxes of film elder generation for preparing, then at 100 ℃ Muffle furnace low temperature sintering 10min, is incubated 10min.Then this nano-crystal film is immersed in the acetonitrile that contains the N719 dyestuff and the butanol solution and steep 8h, with the ethanol washing, 80 ℃ of dryings can make the doping type crystalline state titanium dioxide photoelectrode of dye sensitization after taking out.As work electrode, the electrically-conductive backing plate of platinum plating is as to electrode, with containing 0.5M LiI, 0.05M I with the optoelectronic pole for preparing
2With the acetonitrile solution of 0.5M four tertiary butyl pyridines as liquid electrolyte, be assembled into the DSSC of " sandwich " structure.
(2) performance test methods of solar cell: the photoelectric properties of battery use computer-controlled Oriel sunlight analogue system at room temperature to test, and incident intensity is 100mW/cm
2, illuminating area is 0.25cm
2
Test result shows, open circuit voltage is 0.78V, and short circuit current is 12.74mA/cm
2, fill factor, curve factor is 0.650, photoelectric conversion efficiency is 6.46%.
Embodiment 2: add the 0.05mol butyl titanate in 1.60mol ethanol, after mixing, add the 0.03mol zinc acetate, drip the 0.04mol red fuming nitric acid (RFNA) after fully stirring, slowly drip the 0.10mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 60 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous and zinc behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.05mol zinc carbonate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 300W, quickly heats up to 90 ℃, and insulation 2h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make after 60 ℃ of dryings and mix zinc crystalline state titanium dioxide, average grain diameter is 12.0nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.77V, and short circuit current is 11.76mA/cm
2, fill factor, curve factor is 0.647, photoelectric conversion efficiency is 5.86%.
Embodiment 3: add the 0.20mol butyl titanate in the 3.05mol isopropyl alcohol, after mixing, add the 0.20mol butter of tin, drip the 0.15mol red fuming nitric acid (RFNA) after fully stirring, slowly drip the 0.40mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 70 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous and tin behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.04mol ammonium carbonate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 500W, quickly heats up to 98 ℃, and insulation 2.5h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make after 60 ℃ of dryings and mix tin crystalline state titanium dioxide, average grain diameter is 13.5nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.76V, and short circuit current is 12.71mA/cm
2, fill factor, curve factor is 0.631, photoelectric conversion efficiency is 6.10%.
Embodiment 4: add the 0.15mol titanium tetrachloride in 1.50mol ethanol, after mixing, add 0.05mol butter of tin and 0.05mol zinc acetate, drip the 0.015mol polyethylene glycol after fully stirring, slowly drip the 0.20mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 50 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, tin and zinc behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.15mol sodium acid carbonate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 180W, quickly heats up to 85 ℃, and insulation 3.5h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make tin, zinc co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 11.1nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.72V, and short circuit current is 11.79mA/cm
2, fill factor, curve factor is 0.620, photoelectric conversion efficiency is 5.26%.
Embodiment 5: add the 0.15mol butyl titanate in 4.50mol ethanol, after mixing, add 0.010mol Boratex and 0.018mol tetraethoxysilane, drip 0.16mol ammoniacal liquor after fully stirring, slowly drip the 0.21mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 75 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, boron and silicon behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add 0.12mol carbonic hydroammonium, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 500W, quickly heats up to 97 ℃, and insulation 2h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make boron, silicon coblended crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 12.7nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.71V, and short circuit current is 11.36mA/cm
2, fill factor, curve factor is 0.637, photoelectric conversion efficiency is 5.14%.
Embodiment 6: add the 0.22mol butyl titanate in the 4.15mol propylene glycol, after mixing, add 0.016mol zirconium oxychloride and 0.010mol copper nitrate, drip 0.13mol lactic acid after fully stirring, slowly drip the 0.18mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 80 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, zirconium and copper behind the reaction 1h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.15mol diammonium hydrogen phosphate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 500W, quickly heats up to 93 ℃, and insulation 3h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make the crystalline state titanium dioxide of zirconium, copper codope after 60 ℃ of dryings, average grain diameter is 12.09nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.75V, and short circuit current is 11.09mA/cm
2, fill factor, curve factor is 0.628, photoelectric conversion efficiency is 5.22%.
Embodiment 7: add the 0.16mol butyl titanate in 5.10mol ethanol, after mixing, add 0.04mol zinc acetate and 0.15mol ammonium fluoride, add the 0.006mol PVP after fully stirring, slowly drip the 0.17mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 85 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, zinc and fluorine behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.26mol ammonium nilrite, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 700W, quickly heats up to 98 ℃, and insulation 2.5h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make zinc, fluorin-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 13.6nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.75V, and short circuit current is 12.24mA/cm
2, fill factor, curve factor is 0.648, photoelectric conversion efficiency is 5.95%.
Embodiment 8: add the 0.01mol butyl titanate in 0.04mol ethanol, after mixing, add 0.005mol manganese sulfate, 0.002mol cobalt nitrate and 0.015mol glucose, drip the 0.01mol monoethanolamine after fully stirring, slowly drip the 0.02mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 65 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, manganese, cobalt and chlorine behind the reaction 2h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.05mol hydrogen peroxide, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 450W, quickly heats up to 81 ℃, and insulation 3h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make manganese, cobalt, chlorine co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 11.3nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.74V, and short circuit current is 12.18mA/cm2, and fill factor, curve factor is 0.638, and photoelectric conversion efficiency is 5.75%.
Embodiment 9: add the 0.40mol isopropyl titanate in 4.80mol ethanol, after mixing, add 0.02mol chloroplatinic acid, 0.02mol ruthenium trichloride, 0.30mol ammonium bromide, drip the 0.13mol red fuming nitric acid (RFNA) after fully stirring, slowly drip the 0.30mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 90 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, platinum, ruthenium, sulphur behind the reaction 0.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add 0.08mol ammonium nitrate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 650W, quickly heats up to 99 ℃, and insulation 3h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make the crystalline state titanium dioxide of platinum, ruthenium and sulphur codope after 60 ℃ of dryings, average grain diameter is 13.9nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.78V, and short circuit current is 12.63mA/cm
2, fill factor, curve factor is 0.662, photoelectric conversion efficiency is 6.52%.
Embodiment 10: add the 0.025mol butyl titanate in 0.90mol ethanol, after mixing, add 0.002mol vanadium trichloride, 0.002mol molybdenum pentachloride and 0.028mol ammonium iodide, drip the 0.03mol concentrated sulfuric acid after fully stirring, slowly drip the 0.05mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 80 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, vanadium, molybdenum and iodine behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.055mol diammonium hydrogen phosphate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 380W, quickly heats up to 92 ℃, and insulation 3.5h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make the crystalline state titanium dioxide of vanadium, molybdenum and iodine codope after 60 ℃ of dryings, average grain diameter is 12.5nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.69V, and short circuit current is 12.03mA/cm
2, fill factor, curve factor is 0.621, photoelectric conversion efficiency is 5.15%.
Embodiment 11: add the 0.19mol isopropyl titanate in 2.30mol ethanol, after mixing, add 0.005mol silver nitrate, 0.002mol ferric nitrate and 0.055mol urea, drip the 0.08mol diethanol amine after fully stirring, slowly drip the 0.16mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 75 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, silver, iron and nitrogen behind the reaction 1.5h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.041mol ammonium dihydrogen phosphate, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 550W, quickly heats up to 91 ℃, and insulation 2h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make silver, iron, nitrogen co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 11.6nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.72V, and short circuit current is 11.21mA/cm
2, fill factor, curve factor is 0.610, photoelectric conversion efficiency is 4.92%.
Embodiment 12: add the 0.03mol butyl titanate in 0.80mol ethanol, after mixing, add 0.016mol ethanol niobium, 0.007mol thiocarbamide and 0.005mol ammonium chloride, drip the 0.001mol polyethylene glycol after fully stirring, slowly drip the 0.04mol deionized water after stirring 5min, keep high-speed stirred in the dropping process, make mixed liquor.With the above-mentioned mixed liquor heating water bath that makes, 90 ℃ of bath temperatures keep not stopping to stir, and reflux, and make the colloid of titaniferous, niobium, sulphur and chlorine behind the reaction 2h.After colloid to be prepared is cooled to room temperature, move in the high-pressure-resistant vessel, then add the 0.02mol azodiisobutyronitrile, and rapidly that container is airtight.The container of sealing is put in the microwave reaction device, and microwave power is 600W, quickly heats up to 92 ℃, and insulation 3h finishes to reaction, keeps in the whole process stirring.Product is filtered and use deionized water rinsing, make niobium, sulphur, chlorine co-doped crystalline state titanium dioxide after 60 ℃ of dryings, average grain diameter is 12.8nm, and dispersed better.The assembling of solar cell and performance test are identical with embodiment 1.Test result shows, open circuit voltage is 0.75V, and short circuit current is 11.27mA/cm
2, fill factor, curve factor is 0.667, photoelectric conversion efficiency is 5.64%.
Claims (5)
1. a microwave assisted reaction supercharge method low temperature prepares doping type crystalline state titanium dioxide photoelectrode, and it is characterized in that: the concrete preparation method of doping type crystalline state titanium dioxide photoelectrode is:
One, the presoma that in alcohol, adds titaniferous, mix rear adding alloy, add hydrolysis inhibitor after fully stirring, then slowly drip deionized water, make mixed liquor, wherein the mol ratio of the presoma of titaniferous, alcohol, alloy, hydrolysis inhibitor and deionized water is 1:5～100:0.05～5:0.01 ~ 50:0.5 ~ 50;
Two, with the mixed liquor heating water bath of step 1 preparation, 40～100 ℃ of bath temperatures keep in the heating process stirring, and reflux, and 0.5～2h afterreaction is finished, and makes the colloid of titaniferous and doped chemical;
Three, after the colloid of preparation is cooled to room temperature in step 2, it is moved in the high-pressure-resistant vessel, and add distintegrant, then rapidly with seal of vessel, the mol ratio of the presoma of the titaniferous that wherein adds in distintegrant and the step 1 is 50～1000:1;
Four, the container with good seal in the step 3 is put in the microwave reaction device, microwave power is 100～800W, quickly heat up to 85～100 ℃, insulation 1～4h finishes to reacting, keep in the whole process stirring, product is filtered and wash with deionized water, obtain doping type crystalline state titanium dioxide after the drying.
2. microwave assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode, and it is characterized in that: the presoma of described titaniferous is any in butyl titanate, titanium tetrachloride, the isopropyl titanate.
3. microwave assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode, it is characterized in that: described alloy is the water soluble compound that contains in Ag, Zn, Cu, Fe, Al, Co, Sn, Pt, Ru, V, Ta, Nb, Mo, Mn, F, Cl, Br, I, S, B, C, Si, N, the P element any; Or above-mentioned any two combinations; Or the mixture of wantonly three kinds of combinations.
4. microwave assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode, it is characterized in that: described hydrolysis inhibitor is divided into acidity, alkalescence or neutral three kinds, wherein acid inhibitor is any in nitric acid, hydrochloric acid, sulfuric acid, lactic acid, the citric acid, the alkalescence inhibitor is monoethanolamine, in diethanol amine, triethanolamine, ammoniacal liquor, NaOH, the potassium hydroxide any, neutral inhibitor are any in polyethylene glycol, the PVP.
5. microwave assisted reaction supercharge method low temperature according to claim 1 prepares doping type crystalline state titanium dioxide photoelectrode, and it is characterized in that: described distintegrant is any in hydrogen peroxide, ammonium carbonate, carbonic hydroammonium, sodium acid carbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, zinc carbonate, ammonium nitrate, ammonium nilrite, the azodiisobutyronitrile.
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