TWI391445B - 電解質組合物 - Google Patents
電解質組合物 Download PDFInfo
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- TWI391445B TWI391445B TW098118445A TW98118445A TWI391445B TW I391445 B TWI391445 B TW I391445B TW 098118445 A TW098118445 A TW 098118445A TW 98118445 A TW98118445 A TW 98118445A TW I391445 B TWI391445 B TW I391445B
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- electrolyte composition
- integer
- oxide
- polyether
- electrolyte
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- 239000000203 mixture Substances 0.000 title claims description 36
- 239000003792 electrolyte Substances 0.000 title claims description 35
- 229920000570 polyether Polymers 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 claims description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 239000007784 solid electrolyte Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- -1 polyoxyethylene Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical compound CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BYMHZVKNCWHDQH-UHFFFAOYSA-N [P].P(=O)(Cl)(Cl)Cl Chemical compound [P].P(=O)(Cl)(Cl)Cl BYMHZVKNCWHDQH-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Description
本發明係關於一種電解質組合物,特別係關於一種用於染料敏化太陽能電池(dye sensitized solar cell,DSSC)中作為固態電解質之電解質組合物。
太陽能是一種永不耗盡且無污染的能源,因此在解決傳統石化能源所面臨的污染與短缺的問題時,一直都是替代能源的考量之一。因此,可將太陽能轉換為電能的太陽能電池便成為目前相當重要的研究及發展課題。
近年,由於染料敏化太陽能電池(DSSC)具有可透光、可撓曲、製程簡單與價格低廉等特性,且具有大的有效受光面積,相較於晶矽太陽能電池,其更能有效利用太陽能源。一般而言,染料敏化太陽能電池的結構包含四部份,分別為提供電流流動通路的陰/陽電極、作為電子傳輸用之半導體材料(如二氧化鈦)、染料層以及傳輸電洞的電解質。上述染敏太陽能電池之各部分的材質以及各部分之間的介面結構皆會對元件效率造成影響。
目前業界常用的電解質為液態,然液態電解質有易揮發及不易封裝等缺點,穩定性較差,因此便有膠態或固態電解質的發展,以改善穩定性不佳的問題。然固態電解質卻又衍生出電解質不易滲入二氧化鈦中及離子擴散率慢所導致之導電度低等缺點因此,技藝中亟欲尋求可改善上述問題之固態電解質。
本發明旨在提供一種電解質組合物,其包含聚氧化乙烯、聚醚型高分子和氧化還原電對。
本發明之電解質組合物包含a)聚氧化乙烯(polyethylene oxide;PEO)、b)聚醚型高分子(polyether polymer)以及c)氧化還原電對(redox pair)。
聚氧化乙烯是一種線性結晶性高分子,主鏈上有氧等陰電性大的元素可表現出極性鍵(polar bonding),可幫助鹽類解離。離子藉由與高分子間產生離子鍵(ionic bonding)來形成鍵結,這種鍵結力屬於一級共價鍵力(primary valance forces),此鍵結能力是可逆的,因此離子可藉由高分子鏈段的運動而產生移動,但因離子只會在高柔軟性的醚基(-O-)鏈段上移動且限於高分子非結晶區中,因此單純使用聚氧化乙烯作為電解質之基材,離子擴散率太低(造成導電度低),無法符合業界需求,故本發明以聚醚型高分子混合聚氧化乙烯作為基材,利用聚醚型高分子提供更多醚基鏈段並破壞聚氧化乙烯規則的排列,以降低聚氧化乙烯結晶的形成,達到提高離子擴散率(提高導電度)的目的。本發明電解質組合物所含a)聚氧化乙烯與b)聚醚型高分子之重量比為0.2:1至3:1,較佳為0.5:1至2:1,尤佳為0.7:1至1.5:1。當聚氧化乙烯與聚醚型高分子之重量比低於0.2,陰電性大元素含量低,鹽類解離能力下降,導電度因此變低;當聚氧化乙烯與聚醚型高分子之重量比高於3,易形成聚氧化乙烯結晶,而離子無法在高分子結晶區中移動,導電度也會因此變低。
可用於本發明中之聚氧化乙烯,純度需達90%以上,平均分子量範圍為500,000至8,000,000,較佳之平均分子量在4,000,000至5,000,000範圍內者。
在一具體實施例中,本發明所使用之聚醚型高分子為具式(I)之聚醚型聚氨酯(polyether urethane),
其中R為芳基或C3-6
環烷基;n為2至4之整數;m為6至100之整數,較佳者為6至50之整數,尤佳者為6至15之整數;以及k為2至4之整數。
根據一較佳實施態樣,式(I)中之R為甲苯基,k為2,即,聚醚型高分子具下式(I1
)之結構,
其中,n、m係如先前所述。
根據一最佳實施態樣,式(I)中之R為甲苯基,n為2,m為6至50之整數,k為2。
本發明所使用之聚醚型聚氨酯,可藉本發明所屬技術領域具有通常知識者所習知的方法獲得,例如可由經含羥基化合物與含異氰酸酯基化合物聚合,形成一聚醚型聚氨酯,所使用之含羥基化合物對含異氰酸酯基化合物之莫耳數比介於0.8至4.0間,較佳介於0.8至2.0間,尤佳介於0.8至1.5間。
根據本發明,含異氰酸酯基化合物為包括一個或多個異氰酸酯基之化合物,或包括含有不同異氰酸酯基數之化合物的混合物。該含異氰酸酯基化合物係選自以下所組成之群:甲苯二異氰酸酯(toluene diisocyanate;TDI)、二苯甲烷二異氰酸酯(methylenediphenylene diisocyanate;MDI)、異佛爾酮二異氰酸酯(isophoronediisocyanate;IPDI)、二環己烷亞甲基二異氰酸酯(dicyclohexanemethylene diisocyanate)、二甲苯二異氰酸酯(xylene diisocyanate)及氫化二甲苯二異氰酸酯(hydrogenated xylene diisocyanate)。較佳者為甲苯二異氰酸酯。
前述之含羥基化合物為包括一個或多個羥基之化合物,或包括具有不同數目羥基化合物之混合物,例如選自由以下所組成之群:聚乙二醇(polyethylene glycol;PEG)、聚丙二醇(polypropyleneglycol;PPG)及聚丁二醇(polytetramethylene glycol;PTMG)。較佳者係聚乙二醇。
在另一具體實施例中,可用於本發明中之聚醚型高分子為如式(II)所示之含磷聚醚:
其中i為2至4之整數;j為6至100之整數,較佳為6至50之整數,尤佳為6至15之整數。根據一較佳實施態樣,式(II)中之i為2,j為6至50之整數。
根據本發明,上述含磷聚醚可藉由一含羥基化合物與三氯氧磷聚合,形成一含磷聚醚,其中所使用之含羥基化合物對三氯氧磷之莫耳數比係介於0.8至3間,較佳介於0.9至1.9間,其中含羥基化合物如前所述。
適用於染料敏化太陽能電池的氧化還原電對並無一定限制,只要氧化還原電對所產生的氧化還原能階可與染料的最高填電子能階(Highest Occupied Molecular Orbital,HOMO)相匹配即可。例如但不限於、Br -
/Br 2
、SCN -
/(SCN
)2
或SeCN -
/(SeCN
)2
。其中,由於碘離子的擴散速率較快,所以為較佳之氧化還原電對選擇。
為增加導電度與強度,本發明之電解質組合物可進一步添加奈米粒子。藉由添加奈米粒子,可破壞聚氧化乙烯的結晶性,並增加非結晶的區域,形成離子通道,使得獲得之固態電解質的導電度因此提高。另一方面,亦利用奈米粒子的硬度來增加所得之固態電解質的機械強度。本發明所使用之奈米粒子的種類並無特殊限制,例如可選自於由以下組成之群:二氧化矽、氧化鋁、硫化鎘、氧化鋯、磷酸鈣、氧化鈣、二氧化鈦及氧化鋅。較佳者可選用二氧化矽、二氧化鈦或其混合物;最佳者為二氧化矽。該奈米粒子之含量,以電解質組合物之(a)聚氧化乙烯和(b)聚醚型高分子合計100重量份計,為0.5重量份至5重量份,較佳為0.5重量份至3重量份。一般而言,奈米粒子之粒徑約為1至50奈米。
此外,本發明電解質組合物亦可視需要添加任何習知之添加劑,一般而言,係添加用以修飾奈米粒子相關性質以改善電池效率之添加劑。常用添加劑可選自由以下組成之群:第三丁基吡啶(4-tert-butylpyridine;TBP)、N-甲基苯并咪唑(N-methyl-benzimidazole;MBI)、1,2-二甲基-3-丙基咪唑碘鹽(1,2-Dimethyl-3-Propylimidazolium Iodide;DMP II)、碘化鋰(LiI)及碘化鈉(NaI)。當在電解質中加入小體積的碘化鋰或碘化鈉時,鋰離子(Li+
)或鈉離子(Na+
)會吸附半導體材料(如二氧化鈦)的表面。此時吸附在表面的Li+
可與傳導帶電子形成Li+
-e-
。由於表面的Li+
-e-
既可在二氧化鈦表面遷移,也有可能脫離二氧化鈦表面遷移,因此可縮短傳導帶電子在相鄰或不相鄰的二氧化鈦之間傳輸的阻力和距離,改善電子在二氧化鈦表面的傳輸,提高太陽能電池的短路電流密度(JSC
),但在此同時,Li+
-e-
與電解質中I3 -
再結合的速率也快,使電壓(VOC
)減小。另外,藉由加入第三丁基吡啶、1,2-二甲基-3-丙基咪唑碘鹽或N-甲基苯并咪唑可提高染料的最低未填電子能階(Lowest Unoccupied Molecular Orbital,LUMO)與二氧化鈦之傳導帶間的費米能階,增加電池的電壓。所以為考量電池各性質的表現,可視需要添加一種、二種或二種以上的添加劑。
本發明之電解質組合物之製造方法,例如利用如先前所定義之聚氧化乙烯混合如上所定義之聚醚型高分子作為電解質組合物之基材,之後再添加可產生氧化還原電對之氧化還原系統,並選擇性加入奈米粒子和添加劑,混合均勻,即可得到能提供較佳的導電度及/或機械強度之用於染料敏化太陽能電池中作為固態電解質之電解質組合物。
根據本發明之較佳具體實施例,利用本發明電解質組合物製造太陽能電池中固態電解質之方法包括以下步驟:
(a)將聚醚型高分子分散於第一溶劑中,形成第一溶液;
(b)取聚氧化乙烯溶解於第二溶劑中,形成第二溶液;
(c)使該第一溶液與第二溶液混合,形成第三溶液;
(d)於所得第三溶液中加入可產生氧化還原電對的氧化還原系統(如LiI/I2
),並選擇性加入奈米粒子及/或添加劑,攪拌均勻,形成第四溶液;及
(e)將第四溶液慢慢滴至工作電極表面,並放置一段時間,使溶液慢慢滲透至半導體材料孔洞,以提高電子電洞的傳遞效率,待滲透完全後,再進行低溫乾燥,去除殘留溶劑。
可用於上述製程中步驟(a)之第一溶劑並無特殊限制,其可選自由以下組成之群:四氫呋喃(tetrahydrafuran;THF)、乙醇(ethanol)、丙酮(acetone)、二***(diethyl ether)、乙腈(acetonitrile)、二氯甲烷(dichloromethane)、己烷(hexane)及乙酸乙酯(ethyl acetate)。較佳為四氫呋喃。
可用於上述製程中步驟(b)之第二溶劑,可選自由以下組成之群:四氫呋喃、乙醇、丙酮、二***、乙腈、二氯甲烷、己烷及乙酸乙酯。較佳者為乙腈。
上述步驟(e)之工作電極的製造方法,例如包括將半導體材料(如二氧化鈦)塗料均勻塗佈於導電基材表面,形成一薄膜,在高溫(400℃~600℃)下進行燒結,之後浸入染料中,以形成工作電極(electrode)。
以下實施例係用於對本發明作進一步說明,唯非用以限制本發明之範圍。任何熟悉此項技藝之人士可輕易達成之修飾及改變均包括於本案說明書揭示內容及所附申請專利範圍之範圍內。
聚醚型高分子的製備
1. 聚醚型聚氨酯:將聚乙二醇(Mw:400)加熱烘烤,去除聚乙二醇中的水分後,在氮氣的環境中,逐漸加入1莫耳聚乙二醇及1莫耳的甲苯二異氰酸酯,反應兩小時,使兩成分聚合,即可獲得一聚醚型聚氨酯。
2. 含磷聚醚:將聚乙二醇加熱烘烤,去除聚乙二醇中的水分後,加入三氯氧磷(Phosphoryl chloride;POCl3
)(POCl3
:PEG的莫耳比為1:2),於60℃攪拌1小時,使兩成分聚合,即可獲得一含磷聚醚。
根據以下描述之步驟製造用於染料敏化太陽能電池中作為固態電解質之電解質組合物,各實施例之組成係如表1所列。
電解質組合物的配製:
1. 製作第一溶液:取聚醚型聚氨酯或含磷聚醚置於樣品瓶中,加入四氫呋喃攪拌混合均勻。
2. 製作第二溶液:取聚氧化乙烯(Mw:4,000,000)置於樣品瓶中,加入乙腈,攪拌至完全溶解。
3. 將第一溶液與第二溶液混合均勻後形成第三溶液。
4. 將碘化鋰/碘(LiI/I2
)加入於第三溶液中,於室溫攪拌至溶解,並視需要加入二氧化矽奈米粒子(7nm)及/或添加劑,攪拌均勻,形成第四溶液。
太陽能電池的製備:將二氧化鈦漿料塗敷在處理好的導電玻璃上,高溫處理後浸入染料(N719)中(N-719為Solaronix公司生產之染料商品),吸附14-24小時形成電池的工作電極,將配置完成的電解質組合物慢慢滴至工作電極表面,並放置一段時間,使溶液慢慢滲透後低溫乾燥,蓋上鍍鉑的相對電極(counter electrode),以固定器具或密封膠固定工作電極與相對電極。置入40℃烘箱,並抽至真空,乾燥24小時後,即可製備成染料敏化太陽能電池。
電池性能測試:從電池的工作電極和相對電極分別引出導線,接到電池性能測試裝置上,用太陽光模擬器模擬太陽光,將光強度調整至100mW/cm2
,測其電池性能,測試結果如表2所示。
Claims (13)
- 一種電解質組合物,其包含:(a)聚氧化乙烯;(b)聚醚型高分子,其係選自由聚醚型聚氨酯及含磷聚醚所組成之群,其中該聚醚型聚氨酯具式(I1 )之結構,
- 如請求項1所述之電解質組合物,其中m為6至50之整數。
- 如請求項1所述之電解質組合物,其中n為2。
- 如請求項1所述之電解質組合物,其中j為6至50之整數。
- 如請求項1所述之電解質組合物,進一步包含奈米粒子。
- 如請求項5所述之電解質組合物,其中該奈米粒子係選 自由二氧化矽、氧化鋁、硫化鎘、氧化鋯、磷酸鈣、氧化鈣、二氧化鈦及氧化鋅所組成之群。
- 如請求項6所述之電解質組合物,其中該奈米粒子係為二氧化矽、二氧化鈦或其混合物。
- 如請求項6所述之電解質組合物,其中該奈米粒子係為二氧化矽。
- 如請求項5所述之電解質組合物,其中該奈米粒子之粒徑為約1至50奈米。
- 如請求項1所述之電解質組合物,其中聚氧化乙烯與聚醚型高分子之重量比為約0.2:1至3:1。
- 如請求項1所述之電解質組合物,其中聚氧化乙烯與聚醚型高分子之重量比為約0.5:1至2:1。
- 如請求項1所述之電解質組合物,其中該氧化還原電對為/I - 、Br - /Br 2 、SCN - /(SCN )2 或SeCN - /(SeCN )2 。
- 如請求項12所述之電解質組合物,其中該氧化還原電對為/I - 。
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