TWI462369B - Dye-sensitized solar cell and method for preparing the same - Google Patents
Dye-sensitized solar cell and method for preparing the same Download PDFInfo
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- TWI462369B TWI462369B TW098108210A TW98108210A TWI462369B TW I462369 B TWI462369 B TW I462369B TW 098108210 A TW098108210 A TW 098108210A TW 98108210 A TW98108210 A TW 98108210A TW I462369 B TWI462369 B TW I462369B
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- 238000000034 method Methods 0.000 title claims description 24
- 239000011521 glass Substances 0.000 claims description 120
- 239000000758 substrate Substances 0.000 claims description 101
- 239000003792 electrolyte Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000012780 transparent material Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 29
- 239000000975 dye Substances 0.000 description 19
- 238000007789 sealing Methods 0.000 description 17
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- 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
-
- 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
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Filling, Topping-Up Batteries (AREA)
- Glass Compositions (AREA)
Description
本發明係有關於一種染料敏化的太陽能電池及其製備方法，特別係有關於一種可以防止一暴露在嚴苛外在環境下且於其中操作之太陽能電池之電解質由一密封部揮發，藉此延長耐用壽命，且提供一具有對濕氣與氣體極佳密封效果，可在低溫輕易地加工，並且具有抵抗外來衝擊或破壞性質及極佳強度之密封，藉此延長一太陽能電池之壽命並增加其耐用性的染料敏化的太陽能電池及其製備方法。The present invention relates to a dye-sensitized solar cell and a method of fabricating the same, and more particularly to an electrolyte capable of preventing a solar cell operating in and operating in a severe external environment from being volatilized by a sealing portion, thereby Extends durability and provides a seal that has excellent sealing against moisture and gas, can be easily processed at low temperatures, and is resistant to external impact or damage properties and excellent strength, thereby extending the life of a solar cell and increasing it. A durable dye-sensitized solar cell and a method of preparing the same.
由於在1991年已由瑞士聯邦技術學院洛桑分校之Michael Gratzel等人發展出一染料敏化奈米粒子氧化鈦太陽能電池，故有關這方面之許多研究正在進行。因為該染料敏化的太陽能電池相較於現有太陽能電池具有相低之製造成本，所以它可取代現有非晶質矽太陽能電池。又，該染料敏化的太陽能電池是一主要由可以吸收可見光以產生電子-電洞對之染料分子、及用以傳送所產生電子之過渡金屬氧化物構成的光電化學太陽能電池。Since a dye-sensitized nanoparticle titanium oxide solar cell has been developed by Michael Gratzel et al. of the Swiss Federal Institute of Technology in Lausanne in 1991, much research is being carried out in this regard. Since the dye-sensitized solar cell has a relatively low manufacturing cost compared to the existing solar cell, it can replace the existing amorphous germanium solar cell. Further, the dye-sensitized solar cell is a photoelectrochemical solar cell mainly composed of a dye molecule capable of absorbing visible light to generate an electron-hole pair and a transition metal oxide for transporting the generated electron.
通常，一染料敏化的太陽能電池之單元電池包含上與下透明基材、分別形成在該等透明基材上之導電透明電極、一形成在該導電透明電極上且對應於一第一電極之吸附染料過渡金屬氧化物多孔層、一形成在該導電透明電極上且對應於一第二電極之觸媒薄膜電極、及一填充在如TiO2 之過渡金屬氧化物多孔電極與該觸媒薄膜電極之間的電解質。Generally, a unit cell of a dye-sensitized solar cell comprises upper and lower transparent substrates, conductive transparent electrodes respectively formed on the transparent substrates, and a conductive transparent electrode formed on the conductive transparent electrodes and corresponding to a first electrode. a porous layer of adsorbed dye transition metal oxide, a catalyst film electrode formed on the conductive transparent electrode and corresponding to a second electrode, and a transition metal oxide porous electrode such as TiO 2 and the catalyst film electrode Between the electrolytes.
因此，為了穩定地維持填充在該等第一與第二電極間之電解質，一熱塑性聚合物膜放置在該等第一與第二電極之間且被熱壓以將它們結合在一起，藉此形成一可將一電解質注入且儲存在該等第一與第二電極之間的空間。Therefore, in order to stably maintain the electrolyte filled between the first and second electrodes, a thermoplastic polymer film is placed between the first and second electrodes and is hot pressed to bond them together, whereby A space is formed in which an electrolyte can be injected and stored between the first and second electrodes.
但是，因為該熱塑性聚合物膜沒有一緊緻結構，所以它會被高溫、強烈之陽光、熱循環等輕易地破壞，且該電解質會因夜/日或冬/夏之熱循環而揮發，使一太陽能電池之效率降低，最後終結其壽命。又，由於其有限之機械強度，該熱塑性聚合物膜會因外來衝擊而輕易地受損，使一太陽能電池之壽命，並因此造成耐用性之問題。However, since the thermoplastic polymer film does not have a compact structure, it is easily destroyed by high temperature, strong sunlight, thermal cycling, etc., and the electrolyte is volatilized by the thermal cycle of night/day or winter/summer, so that The efficiency of a solar cell is reduced, and finally its life is terminated. Moreover, due to its limited mechanical strength, the thermoplastic polymer film is easily damaged by external impact, causing the life of a solar cell and thus causing durability problems.
為了解決先前技術之前述問題，本發明之一目的係提供一種染料敏化的太陽能電池，其可以防止一暴露在嚴苛外在環境下且於其中操作之太陽能電池之電解質由一密封部揮發，藉此延長耐用壽命，且提供一具有對濕氣與氣體極佳密封效果之密封，可在低溫輕易地加工，並且具有抵抗外來衝擊或破壞性質及極佳強度之密封，藉此延長一太陽能電池之壽命並增加其耐用性。In order to solve the aforementioned problems of the prior art, it is an object of the present invention to provide a dye-sensitized solar cell capable of preventing an electrolyte exposed to a severe external environment and operating in a solar cell from being volatilized by a sealing portion. This extends the durability and provides a seal with excellent sealing effect on moisture and gas, can be easily processed at low temperatures, and has a seal against external impact or damage properties and excellent strength, thereby extending a solar cell. Life and increase its durability.
為了達成本發明之目的，本發明提供一種染料敏化的太陽能電池，其包含：一第一電極，係由一在其表面上具有一包含染料之多孔膜之透明基材構成；一第二電極，係相對該第一電極配置；及一電解質，係在該等第一與第二電極之間，其中該電解質被填充在一由燒結玻料形成之空間中，且該燒結玻料密封該等第一與第二電極並使它們以一定之間距分開，又，該燒結玻料係藉塗布玻料並將之燒結而形成，而該玻料包含P2 O5 0~30mol%；V2 O5 0~50mol%；ZnO 0~20mol%；BaO 0~15mol%；As2 O3 0~20mol%；Sb2 O3 0~20mol%；In2 O3 0~5mol%；Fe2 O3 0~10mol%；Al2 O3 0~5mol%；B2 O3 0~20mol%；Bi2 O3 0~10mol%；及TiO2 0~10mol%。In order to achieve the object of the present invention, the present invention provides a dye-sensitized solar cell comprising: a first electrode composed of a transparent substrate having a porous film containing a dye on its surface; a second electrode Relative to the first electrode arrangement; and an electrolyte between the first and second electrodes, wherein the electrolyte is filled in a space formed by the sintered glass, and the sintered glass seals the same The first and second electrodes are separated by a certain distance. Further, the sintered glass is formed by coating and sintering the glass, and the glass comprises P 2 O 5 0 30 mol%; V 2 O 5 0 ~ 50mol%; ZnO 0 ~ 20mol%; BaO 0 ~ 15mol%; As 2 O 3 0 ~ 20mol%; Sb 2 O 3 0 ~ 20mol%; In 2 O 3 0 ~ 5mol%; Fe 2 O 3 0 ~10 mol%; Al 2 O 3 0-5 mol%; B 2 O 3 0-20 mol%; Bi 2 O 3 0-10 mol%; and TiO 2 0-10 mol%.
本發明亦提供一種用以製備一染料敏化的太陽能電池之方法，該染料敏化的太陽能電池包含：一第一電極，係由一在其表面上具有一包含染料之多孔膜之透明基材構成；一第二電極，係相對該第一電極配置；及一電解質，係在該等第一與第二電極之間，且該方法包含以下步驟：將一玻料塗布在該等第一與第二電極間之結合表面上，且該玻料包含：P2 O5 0~30mol%；V2 O5 0~50mol%；ZnO 0~20mol%；BaO 0~15mol%；As2 O3 0~20mol%；Sb2 O3 0~20mol%；In2 O3 0~5mol%；Fe2 O3 0~10mol%；Al2 O3 0~5mol%；B2 O3 0~20mol%；Bi2 O3 0~10mol%；及TiO2 0~10mol%；及燒結該玻料以密封該等第一與第二電極，且使它們以一定間距分開。The invention also provides a method for preparing a dye-sensitized solar cell, the dye-sensitized solar cell comprising: a first electrode comprising a transparent substrate having a porous film containing a dye on a surface thereof Constructing; a second electrode disposed relative to the first electrode; and an electrolyte between the first and second electrodes, and the method comprising the steps of: coating a glass frit in the first The bonding surface between the second electrodes, and the glass material comprises: P 2 O 5 0-30 mol%; V 2 O 5 0-50 mol%; ZnO 0-20 mol%; BaO 0-15 mol%; As 2 O 3 0 ~20mol%; Sb 2 O 3 0~20mol%; In 2 O 3 0~5mol%; Fe 2 O 3 0~10mol%; Al 2 O 3 0~5mol%; B 2 O 3 0~20mol%; Bi 2 O 3 0 to 10 mol%; and TiO 2 0 to 10 mol%; and sintering the glass to seal the first and second electrodes and separating them at a certain interval.
依據本發明，由於可防止一電解質之損失且可以藉由以燒結玻料密封而確保機械強度，故可防止一暴露於嚴苛外部環境且在其中操作之太陽能電池之電解質的揮發，藉此延長耐用壽命。又，提供一具有對濕氣與氣體極佳密封效果，可在低溫輕易地加工，並且具有抵抗外來衝擊或破壞性質及極佳強度之密封，藉此延長一太陽能電池之壽命並增加其耐用性。According to the present invention, since the loss of an electrolyte can be prevented and the mechanical strength can be ensured by sealing with a sintered glass material, the evaporation of the electrolyte of the solar cell exposed to the severe external environment and operated therein can be prevented, thereby prolonging Durable life. Moreover, it provides a seal which has an excellent sealing effect on moisture and gas, can be easily processed at a low temperature, and has resistance against external impact or damage and excellent strength, thereby prolonging the life of a solar cell and increasing its durability. .
第1圖是本發明第一實施例之一染料敏化的太陽能電池的橫截面圖，第2圖是本發明第二實施例之一染料敏化的太陽能電池的橫截面圖，第3圖是本發明第三實施例之一染料敏化的太陽能電池的橫截面圖，第4圖是本發明第四實施例之一染料敏化的太陽能電池的橫截面圖，第5圖是本發明第五實施例之一染料敏化的太陽能電池的橫截面圖，第6圖是本發明第六實施例之一染料敏化的太陽能電池的橫截面圖，第7圖是本發明第七實施例之一染料敏化的太陽能電池的橫截面圖，第8圖是本發明之一染料敏化的太陽能電池的橫截面圖，顯示一電解質入口之密封，且第9圖是本發明之一染料敏化的太陽能電池的橫截面圖，顯示一連接線。1 is a cross-sectional view of a dye-sensitized solar cell according to a first embodiment of the present invention, and FIG. 2 is a cross-sectional view of a dye-sensitized solar cell according to a second embodiment of the present invention, and FIG. 3 is a cross-sectional view A cross-sectional view of a dye-sensitized solar cell according to a third embodiment of the present invention, and FIG. 4 is a cross-sectional view of a dye-sensitized solar cell according to a fourth embodiment of the present invention, and FIG. 5 is a fifth aspect of the present invention. 1 is a cross-sectional view of a dye-sensitized solar cell, and FIG. 6 is a cross-sectional view of a dye-sensitized solar cell according to a sixth embodiment of the present invention, and FIG. 7 is a seventh embodiment of the present invention A cross-sectional view of a dye-sensitized solar cell, FIG. 8 is a cross-sectional view of a dye-sensitized solar cell of the present invention, showing a seal of an electrolyte inlet, and FIG. 9 is a dye-sensitized one of the present invention. A cross-sectional view of a solar cell showing a connecting line.
以下將參照附圖詳細說明本發明。本發明係有關於一染料敏化的太陽能電池，其包含：一第一電極(10)，係由一在其表面上具有一包含染料之多孔膜(13)之透明基材(11)構成；一第二電極(20)，係相對該第一電極(10)配置；及一電解質(30)，係在該等第一與第二電極之間，其中該電解質(30)被填充在一由燒結玻料(40)形成之空間中，且該燒結玻料密封該第一電極(10)與該第二電極(20)並使它們以一定之間距分開，又，該燒結玻料係藉塗布玻料並將之燒結而形成，而該玻料包含P2 O5 0~30mol%；V2 O5 0~50mol%；ZnO 0~20mol%；BaO 0~15mol%；As2 O3 0~20mol%；Sb2 O3 0~20mol%；In2 O3 0~5mol%；Fe2 O3 0~10mol%；Al2 O3 0~5mol%；B2 O3 0~20mol%；Bi2 O3 0~10mol%；及TiO2 0~10mol%。The invention will be described in detail below with reference to the accompanying drawings. The present invention relates to a dye-sensitized solar cell comprising: a first electrode (10) consisting of a transparent substrate (11) having a porous film (13) containing a dye on its surface; a second electrode (20) disposed relative to the first electrode (10); and an electrolyte (30) between the first and second electrodes, wherein the electrolyte (30) is filled in a a space in which the sintered glass (40) is formed, and the sintered glass seals the first electrode (10) and the second electrode (20) and separates them at a certain distance. Further, the sintered glass is coated The glass material is formed by sintering, and the glass material comprises P 2 O 5 0-30 mol%; V 2 O 5 0-50 mol%; ZnO 0-20 mol%; BaO 0-15 mol%; As 2 O 3 0~ 20 mol%; Sb 2 O 3 0 to 20 mol%; In 2 O 3 0 to 5 mol%; Fe 2 O 3 0 to 10 mol%; Al 2 O 3 0 to 5 mol%; B 2 O 3 0 to 20 mol%; Bi 2 O 3 0~10 mol%; and TiO 2 0-10 mol%.
大體上，一染料敏化的太陽能電池包含一由一在其表面上具有一包含染料之多孔膜(13)之透明基材(11)構成的第一電極(10)；一相對該第一電極(10)配置之第二電極(20)；及一在該等第一與第二電極之間的電解質(30)。在本發明中，為了穩定地維持在該等第一與第二電極間之電解質一段長時間，該等第一與第二電極係配置成互相分開，且在其間之空間係被可以在低溫燒結並形成一氣密密封之燒結玻料，並且該密封空間填充有一電解質。實例係如第1至9圖所示者，且其解釋將在以下說明。In general, a dye-sensitized solar cell comprises a first electrode (10) consisting of a transparent substrate (11) having a porous film (13) containing a dye on its surface; a first electrode opposite to the first electrode (10) a second electrode (20) configured; and an electrolyte (30) between the first and second electrodes. In the present invention, in order to stably maintain the electrolyte between the first and second electrodes for a long period of time, the first and second electrode systems are disposed to be separated from each other, and the space therebetween is sintered at a low temperature. And forming a hermetically sealed sintered glass, and the sealed space is filled with an electrolyte. Examples are as shown in Figures 1 to 9, and the explanation thereof will be explained below.
在此可使用染料被吸附於其上之各種習知多孔膜作為該多孔膜，且塗布且燒結例如，具有10至15nm尺寸之TiO2 等過渡金屬氧化物以獲得一多孔膜。該多孔膜形成於其上之透明基材不必限制於一平坦基材且它可包含一彎曲基材，並且可使用包括一由可見光或特定波長之波可穿過之材料製成之基材(例如，玻璃)之供一太陽能電池共用的各種透明基材。最好使用一導電基材作為一電極，且透明基材之實例包括習知透明玻璃、透明樹脂、PET、ITO或FTO等。又，為了賦予導電性，除了前述材料以外，一導電膜或塗層(ITO、FTO或導電聚合物)可進一步包含在該多孔膜與該基材之間。由於該第二電極相對該第一電極配置，所以可使用供一太陽能電池之一第二電極共用之任一種基材，且不必受限於一平坦基材並且可包含一彎曲基材。較佳地，它是由可見光或特定波長之波可穿過之材料製成，且就此而言，它可由習知透明玻璃、透明樹脂、PET、ITO或FTO等製成。較佳地，為了賦予導電性，可以更包含一導電膜或塗層(ITO、FTO或導電聚合物)。又，為了增加太陽光吸收效率並啟動反應，可在該第一電極之最外側更包含一如Pt等觸媒金屬層。Here, various conventional porous films to which the dye is adsorbed may be used as the porous film, and a transition metal oxide such as TiO 2 having a size of 10 to 15 nm may be coated and sintered to obtain a porous film. The transparent substrate on which the porous film is formed is not necessarily limited to a flat substrate and it may comprise a curved substrate, and a substrate comprising a material which is permeable to visible light or a wave of a specific wavelength may be used ( For example, glass) is a variety of transparent substrates that are shared by a solar cell. It is preferable to use a conductive substrate as an electrode, and examples of the transparent substrate include conventional transparent glass, transparent resin, PET, ITO or FTO, and the like. Further, in order to impart conductivity, in addition to the foregoing materials, a conductive film or coating layer (ITO, FTO or conductive polymer) may be further included between the porous film and the substrate. Since the second electrode is disposed relative to the first electrode, any one of the substrates common to the second electrode of a solar cell can be used, and is not necessarily limited to a flat substrate and can include a curved substrate. Preferably, it is made of a material through which visible light or a wave of a specific wavelength can pass, and in this regard, it can be made of a conventional transparent glass, a transparent resin, PET, ITO or FTO or the like. Preferably, in order to impart conductivity, a conductive film or coating (ITO, FTO or conductive polymer) may be further included. Further, in order to increase the solar light absorbing efficiency and initiate the reaction, a catalytic metal layer such as Pt may be further included on the outermost side of the first electrode.
該燒結玻料係藉將一包含玻料之玻料糊沿該等基材邊緣塗布在該等基材間且將之燒結以形成一密封形成固體而獲得，且該玻料包含P2 O5 0~30mol%；V2 O5 0~50mol%；ZnO 0~20mol%；BaO 0~15mol%；As2 O3 0~20mol%；Sb2 O3 0~20mol%；In2 O3 0~5mol%；Fe2 O3 0~10mol%；Al2 O3 0~5mol%；B2 O3 0~20mol%；Bi2 O3 0~10mol%；及TiO2 0~10mol%。The sintered glass material is obtained by coating a glass frit containing glass material between the substrates along the edge of the substrate and sintering it to form a seal to form a solid, and the glass material comprises P 2 O 5 . 0~30mol%; V 2 O 5 0~50mol%; ZnO 0~20mol%; BaO 0~15mol%; As 2 O 3 0~20mol%; Sb 2 O 3 0~20mol%; In 2 O 3 0~ 5 mol%; Fe 2 O 3 0-10 mol%; Al 2 O 3 0-5 mol%; B 2 O 3 0-20 mol%; Bi 2 O 3 0-10 mol%; and TiO 2 0-10 mol%.
較佳地，該玻料糊組成物包含a)該玻料；b)一有機黏合劑；及一有機溶劑，且最好是a)60至90重量份之玻料；b)0.1至5重量份之有機黏合劑；及c)5至35重量份之有機溶劑。Preferably, the glass paste composition comprises a) the glass material; b) an organic binder; and an organic solvent, and preferably a) 60 to 90 parts by weight of glass; b) 0.1 to 5 weight An organic binder; and c) 5 to 35 parts by weight of an organic solvent.
較佳地，該玻料包含P2 O5 10~25mol%；V2 O5 40~50mol%；ZnO 10~20mol%；BaO 1~15mol%；Sb2 O3 1~10mol%；Fe2 O3 1~10mol%；Al2 O3 0.1~5mol%；B2 O3 0.1~5mol%；Bi2 O3 1~10mol%；及TiO2 0.1~5mol%，且更佳地，包含P2 O5 15~20mol%；V2 O5 40~50mol%；ZnO 10~20mol%；BaO 5~10mol%；Sb2 O3 3~7mol%；Fe2 O3 5~10mol%；Al2 O3 0.1~5mol%；B2 O3 0.1~5mol%；Bi2 O3 1~5mol%；及TiO2 0.1~5mol%。Preferably, the glass material comprises P 2 O 5 10-25 mol%; V 2 O 5 40-50 mol%; ZnO 10-20 mol%; BaO 1-15 mol%; Sb 2 O 3 1-10 mol%; Fe 2 O 3 1 to 10 mol%; Al 2 O 3 0.1 to 5 mol%; B 2 O 3 0.1 to 5 mol%; Bi 2 O 3 1 to 10 mol%; and TiO 2 0.1 to 5 mol%, and more preferably, P 2 O 5 15~20mol%; V 2 O 5 40~50mol%; ZnO 10~20mol%; BaO 5~10mol%; Sb 2 O 3 3~7mol%; Fe 2 O 3 5~10mol%; Al 2 O 3 0.1 ~5 mol%; B 2 O 3 0.1 to 5 mol%; Bi 2 O 3 1 to 5 mol%; and TiO 2 0.1 to 5 mol%.
如果該玻料組分之含量超出前述範圍，則可能無法達成透明化，且會明顯破壞防水性，或無法進行雷射燒結。If the content of the glass component exceeds the above range, transparency may not be achieved, and water repellency may be significantly impaired, or laser sintering may not be performed.
特別地，如果ZnO之含量超過20mol%，則會析出晶相，因此使密封困難，且如果BaO之含量超過15mol%，則玻璃會不穩定，因此產生失透明作用。In particular, if the content of ZnO exceeds 20 mol%, the crystal phase is precipitated, so that sealing is difficult, and if the content of BaO exceeds 15 mol%, the glass is unstable, and thus a devitrification effect occurs.
又，如果Al2 O3 之含量超過5mol%，則玻璃會不穩定，且如果B2 O3 之含量超過20mol%，則軟化溫度超過500℃，因此使低溫密封困難。Further, when the content of Al 2 O 3 exceeds 5 mol%, the glass is unstable, and if the content of B 2 O 3 exceeds 20 mol%, the softening temperature exceeds 500 ° C, so that low-temperature sealing is difficult.
如果Bi2 O3 之含量超過10mol%，則熱膨脹係數增加，因此使密封困難，且如果TiO2 之含量超過10mol%，則熱膨脹係數增加，因此使低溫密封困難。When the content of Bi 2 O 3 exceeds 10 mol%, the coefficient of thermal expansion increases, so that sealing is difficult, and if the content of TiO 2 exceeds 10 mol%, the coefficient of thermal expansion increases, so that low-temperature sealing is difficult.
較佳地，該玻料具有由300至400℃之玻璃轉化溫度(Tg )及由300至400℃之軟化溫度(Tdsp )。在這些範圍內，低溫下之燒結穩定性極佳。Preferably, the glass has a glass transition temperature (T g ) of from 300 to 400 ° C and a softening temperature (T dsp ) of from 300 to 400 °C. Within these ranges, the sintering stability at low temperatures is excellent.
又，該玻料較佳地具有0.1至20μm之粒子尺寸。在這範圍內，可進行一低溫加工，因此適用於一對熱不穩定之裝置的氣密密封，且可進行一雷射加工，因此增加電氣裝置之密封效率。Further, the glass frit preferably has a particle size of 0.1 to 20 μm. Within this range, a low temperature process can be performed, so that it is suitable for hermetic sealing of a pair of thermally unstable devices, and a laser process can be performed, thereby increasing the sealing efficiency of the electrical device.
在該玻料糊組成物中，該a)玻料係如前所述，且可使用市售有機黏合劑作為該b)有機黏合劑，而該有機黏合劑之實例包括乙基纖維素型或丙烯酸型共聚物。又，可使用與本發明之玻料糊組成物所使用相容之任何有機溶劑作為該c)有機溶劑，且實例包括乙基纖維素型有機黏合劑、丁卡必醇醋酸酯(BCA)、松脂醇(TPN)、鄰苯二甲酸二丁酯(DBP)或其混合物。較佳地，100重量份欲使用有機溶劑中之30至70重量份有機溶劑與一有機黏合劑混合以製備一載體，且接著將剩餘有機溶劑及玻料與所製備之載體混合以製備一玻料糊組成物，這可進一步改良該玻料糊組成物之分散性。更佳地，在製備該載體時，該30至70重量份有機溶劑係由55重量份BCA、3至10重量份TPN、及1至5重量份DBP組成，且與該玻料混合時，使用BCA作為該溶劑。In the glass paste composition, the a) glass material is as described above, and a commercially available organic binder may be used as the b) organic binder, and examples of the organic binder include an ethyl cellulose type or Acrylic copolymer. Further, any organic solvent compatible with the glass paste composition of the present invention may be used as the organic solvent of the c), and examples include an ethyl cellulose type organic binder, butyl carbitol acetate (BCA), Resin (TPN), dibutyl phthalate (DBP) or a mixture thereof. Preferably, 100 parts by weight of an organic solvent to be used in an organic solvent is mixed with an organic binder to prepare a carrier, and then the remaining organic solvent and glass are mixed with the prepared carrier to prepare a glass. The paste composition, which further improves the dispersibility of the glass frit composition. More preferably, in the preparation of the carrier, the 30 to 70 parts by weight of the organic solvent is composed of 55 parts by weight of BCA, 3 to 10 parts by weight of TPN, and 1 to 5 parts by weight of DBP, and is used when mixed with the glass material. BCA is used as the solvent.
為了控制熱膨脹係數，該玻料糊組成物可更包含一填充劑。該填充劑之實例包括0.1至20μm之堇青石，且其量最好是0.1至30重量份。In order to control the coefficient of thermal expansion, the glass frit composition may further comprise a filler. Examples of the filler include cordierite of 0.1 to 20 μm, and the amount thereof is preferably 0.1 to 30 parts by weight.
又，該玻料糊組成物最好具有500至50000cp之黏度，且以2000至35000cp更佳。在這範圍內，可藉網印法塗布，因此進一步改善可加工性。Further, the glass frit composition preferably has a viscosity of from 500 to 50,000 cp, more preferably from 2,000 to 35,000 cp. Within this range, it can be applied by screen printing, thereby further improving the workability.
依據本發明之染料敏化的太陽能電池之一較佳實施例，該第一電極(10)包含一由透明材料製成之透明基材(11)；一形成在該透明基材(11)上，且以一定間距與該透明基材之邊緣(12)分開至內側之多孔膜(13)；及被吸附至該多孔膜(13)之染料。該第二電極(20)包含一支持基材(21)及一觸媒金屬層(23)，且該觸媒金屬層(23)形成在整個支持基材(21)上或在該支持基材上且以一定間距與該支持基材之邊緣(22)分開至內側。該第一電極(10)與該第二電極(20)係配置成使得該多孔膜(13)與該觸媒金屬層(23)互相相向，且該燒結玻料(40)形成在未形成該多孔膜之該透明基材邊緣(12)與該支持基材(21)之觸媒金屬層(23)或未形成該觸媒金屬層之該支持基材邊緣(22)之間，以密封在該第一電極(10)與該第二電極(20)之間的空間。According to a preferred embodiment of the dye-sensitized solar cell of the present invention, the first electrode (10) comprises a transparent substrate (11) made of a transparent material; and a transparent substrate (11) is formed on the first substrate (10). And a porous film (13) separated from the edge (12) of the transparent substrate to the inner side at a certain interval; and a dye adsorbed to the porous film (13). The second electrode (20) comprises a support substrate (21) and a catalyst metal layer (23), and the catalyst metal layer (23) is formed on the support substrate (21) or on the support substrate. It is separated from the edge (22) of the support substrate to the inner side at a certain interval. The first electrode (10) and the second electrode (20) are configured such that the porous film (13) and the catalytic metal layer (23) face each other, and the sintered glass (40) is formed without forming the The transparent substrate edge (12) of the porous film is sealed between the catalyst metal layer (23) of the support substrate (21) or the support substrate edge (22) where the catalyst metal layer is not formed. a space between the first electrode (10) and the second electrode (20).
又，可使用各種習知透明基材作為該透明基材(11)，且例如，它可由如ITO或FTO等導電透明材料製成，如第1、2或7圖所示，或者一ITO或FTO塗層或一透明導電聚合物塗層等可設置在該玻璃基材(或如PET等透明聚合物基材)上。該導電膜可利用結合於其上之燒結玻料密封，如第3、4與6圖所示，或者該導電膜可與該多孔膜同樣地與該玻璃基材之邊緣以一定間距分開，且該燒結玻料可直接結合至該玻璃基材，如第5圖所示。在後者之情形中，應將一用以電性連接之連接線拉出至該導電膜外。Also, various conventional transparent substrates can be used as the transparent substrate (11), and for example, it can be made of a conductive transparent material such as ITO or FTO, as shown in Figures 1, 2 or 7, or an ITO or An FTO coating or a transparent conductive polymer coating or the like may be disposed on the glass substrate (or a transparent polymer substrate such as PET). The conductive film may be sealed with a sintered glass material bonded thereto, as shown in Figures 3, 4 and 6, or the conductive film may be spaced apart from the edge of the glass substrate by a distance from the porous film, and The sintered glass can be bonded directly to the glass substrate as shown in Figure 5. In the latter case, a connecting wire for electrical connection should be pulled out of the conductive film.
此外，多數染料被吸附至形成在該透明基材上之多孔膜，因此構成該透明基材之一側。該多孔膜(13)最好形成在該透明基材(11)上，且與該透明基材之邊緣(12)以一定間距分開至內側，藉此防止一電解質通過該多孔膜漏出。Further, most of the dye is adsorbed to the porous film formed on the transparent substrate, thus constituting one side of the transparent substrate. The porous film (13) is preferably formed on the transparent substrate (11) and is spaced apart from the edge (12) of the transparent substrate to the inner side at a certain interval, thereby preventing an electrolyte from leaking through the porous film.
又，可使用一染料敏化的太陽能電池所通用之各種染料作為該染料，且它可以藉各種在先前技術中習知之方法被吸附至該多孔膜。Further, various dyes common to a dye-sensitized solar cell can be used as the dye, and it can be adsorbed to the porous film by various methods known in the prior art.
另外，該第一電極可更包含在該多孔膜上之過渡金屬氧化物的塊狀層，如第7圖所示。詳而言之，可藉塗布400至500nmTiO2 並將之燒結而獲得一塊狀層，這可增加太陽光吸收效率。In addition, the first electrode may further comprise a bulk layer of a transition metal oxide on the porous film, as shown in FIG. In detail, it is possible to obtain a layer of a layer by coating 400 to 500 nm of TiO 2 and sintering it, which increases solar light absorption efficiency.
又，可使用各種習知支持基材作為該第二電極之支持基材(21)，且最好使用一透明基材。例如，它可由如ITO或FTO等導電透明材料製成，如第1、2或7圖所示，或者一ITO或FTO塗層或一透明導電聚合物塗層等可設置在該玻璃基材(或如PET等透明聚合物基材)上。該導電膜可利用結合於其上之燒結玻料密封，如第4圖所示，或者該導電膜可與該第一電極之多孔膜同樣地與該玻璃基材之邊緣以一定間距分開，且該燒結玻料可直接結合至該玻璃基材或ITO/FTO基材，如第5圖所示。在後者之情形中，應將一用以電性連接之連接線拉出至該導電膜外。Further, various conventional support substrates can be used as the support substrate (21) of the second electrode, and a transparent substrate is preferably used. For example, it may be made of a conductive transparent material such as ITO or FTO, as shown in Figures 1, 2 or 7, or an ITO or FTO coating or a transparent conductive polymer coating or the like may be disposed on the glass substrate ( Or on a transparent polymer substrate such as PET). The conductive film may be sealed with a sintered glass material bonded thereto, as shown in FIG. 4, or the conductive film may be spaced apart from the edge of the glass substrate by a distance from the porous film of the first electrode, and The sintered glass can be bonded directly to the glass substrate or ITO/FTO substrate as shown in FIG. In the latter case, a connecting wire for electrical connection should be pulled out of the conductive film.
除了該支持基材(21)以外，該第二電極更包含一觸媒金屬層(23)。該觸媒金屬層可以i)形成在該支持基材之整個表面上，如第1與3圖所示，或ii)形成在該支持基材上，且與該支持基材以一定間距分開至內側，如第2與4-7圖所示。In addition to the support substrate (21), the second electrode further comprises a catalyst metal layer (23). The catalyst metal layer may be formed i) on the entire surface of the support substrate, as shown in Figures 1 and 3, or ii) formed on the support substrate and separated from the support substrate by a certain distance to Inside, as shown in Figures 2 and 4-7.
藉此，該燒結玻料可以結合至該第二電極之觸媒金屬層(第1與3圖)，或它可以選擇性地結合至該玻璃基材(第5圖)、ITO/FTO基材(第2、6與7圖)或導電膜層(第4圖)。Thereby, the sintered glass frit can be bonded to the catalytic metal layer of the second electrode (Figs. 1 and 3), or it can be selectively bonded to the glass substrate (Fig. 5), the ITO/FTO substrate. (Figures 2, 6, and 7) or conductive film layers (Fig. 4).
該等第一與第二電極係配置成使得該多孔膜與該觸媒金屬層互相相向，且該燒結玻料(40)形成在未形成該多孔膜之該透明基材邊緣及i)該支持基材之觸媒金屬層或ii)未形成該觸媒金屬層之該支持基材邊緣之間，以密封在該等第一與第二電極之間的空間。The first and second electrode systems are configured such that the porous film and the catalytic metal layer face each other, and the sintered glass (40) is formed on the edge of the transparent substrate on which the porous film is not formed and i) the support The catalyst metal layer of the substrate or ii) the edge of the support substrate where the catalyst metal layer is not formed to seal the space between the first and second electrodes.
此外，本發明之染料敏化的太陽能電池可包含一用以將一電解質(30)注入之入口。較佳地，該第二電極(20)包含一用以注入一電解質之入口(25)，且該電解質入口(25)被燒結玻料(50)密封，其較佳實施例係如第8圖所示，藉此防止該電解質通過該入口漏出，以確保一太陽能電池之耐用性。Further, the dye-sensitized solar cell of the present invention may comprise an inlet for injecting an electrolyte (30). Preferably, the second electrode (20) comprises an inlet (25) for injecting an electrolyte, and the electrolyte inlet (25) is sealed by a sintered glass (50). The preferred embodiment is as shown in FIG. This is shown to prevent the electrolyte from leaking through the inlet to ensure the durability of a solar cell.
此外，本發明之染料敏化的太陽能電池可更包含一由該第一電極(10)或第二電極(20)拉出至一單元電池外側之連接線(60)，且較佳地，該連接線(60)被選擇性地埋置於該燒結玻料(70)中且連接至該太陽能電池之側邊。詳而言之，一單元電池係指一如第1至9圖所示之單元，且各單元電池具有一用以連接它們或將由其獲得之電力傳送至該外部裝置的連接線。如果該連接線暴露於外側，則可能會發生短路或放電。如此，為了防止短路或放電，該連接線之外側塗覆有一絕緣玻料，且為了防止因外來衝擊對該連接線產生破壞，它最好結合於一太陽能電池之側邊。如此，若該連接線(60)被拉出至一太陽能電池之側邊，則塗布且燒結玻料，使得該連接線被埋置於該燒結玻料(70)中且連接於一太陽能電池之側邊。Furthermore, the dye-sensitized solar cell of the present invention may further comprise a connecting line (60) pulled out from the first electrode (10) or the second electrode (20) to the outside of a unit cell, and preferably, A connecting wire (60) is selectively embedded in the sintered glass (70) and attached to the side of the solar cell. In detail, a unit cell refers to a unit as shown in FIGS. 1 to 9, and each unit cell has a connection line for connecting them or transmitting power obtained therefrom to the external device. If the cable is exposed to the outside, a short circuit or discharge may occur. Thus, in order to prevent short circuit or discharge, the outer side of the connecting wire is coated with an insulating glass, and in order to prevent damage to the connecting wire due to external impact, it is preferably bonded to the side of a solar cell. Thus, if the connecting wire (60) is pulled out to the side of a solar cell, the glass frit is coated and sintered so that the connecting wire is buried in the sintered glass (70) and connected to a solar cell. Side.
本發明亦提供一種用以製備一染料敏化的太陽能電池之方法，該染料敏化的太陽能電池包含：一第一電極(10)，係由一在其表面上具有一包含染料之多孔膜(13)之透明基材(11)構成；一第二電極(20)，係相對該第一電極(10)配置；及一電解質(30)，係在該等第一與第二電極之間，且該方法包含以下步驟：將一玻料塗布在該等第一與第二電極間之結合表面上，且該玻料包含：P2 O5 0~30mol%；V2 O5 0~50mol%；ZnO 0~20mol%；BaO 0~15mol%；As2 O3 0~20mol%；Sb2 O3 0~20mol%；In2 O3 0~5mol%；Fe2 O3 0~10mol%；Al2 O3 0~5mol%；B2 O3 0~20mol%；Bi2 O3 0~10mol%；及TiO2 0~10mol%；及燒結該玻料以密封該等第一與第二電極，且使它們以一定間距分開。The present invention also provides a method for preparing a dye-sensitized solar cell comprising: a first electrode (10) having a porous film containing a dye on its surface ( 13) a transparent substrate (11); a second electrode (20) disposed relative to the first electrode (10); and an electrolyte (30) between the first and second electrodes, And the method comprises the steps of: coating a glass frit on the bonding surface between the first and second electrodes, and the glass material comprises: P 2 O 5 0-30 mol%; V 2 O 5 0-50 mol% ZnO 0~20mol%; BaO 0~15mol%; As 2 O 3 0~20mol%; Sb 2 O 3 0~20mol%; In 2 O 3 0~5mol%; Fe 2 O 3 0~10mol%; Al 2 O 3 0~5 mol%; B 2 O 3 0-20 mol%; Bi 2 O 3 0-10 mol%; and TiO 2 0-10 mol%; and sintering the glass to seal the first and second electrodes, And separate them at a certain distance.
如此，在本發明中，特定玻料被塗布在該第一電極與該第二電極之間，且被燒結使得在該等第一與第二電極之間的密封係藉特定燒結玻料形成。Thus, in the present invention, a specific glass frit is coated between the first electrode and the second electrode, and is sintered such that a seal between the first and second electrodes is formed by a specific sintered glass.
該玻料可藉在先前技術中習知之各種方法塗布，較佳地，沿著該等第一與第二電極之邊緣塗布一包含該玻料之糊。該燒結可藉在先前技術中習知之任何方法進行，或以雷射僅加熱該塗布有玻料之部份並將之燒結，這可將剩餘部份之熱衝擊減至最小。The glass material can be coated by various methods known in the prior art. Preferably, a paste comprising the glass material is applied along the edges of the first and second electrodes. The sintering can be carried out by any method known in the prior art, or by laser only heating the portion coated with the glass and sintering it, which minimizes the thermal shock of the remaining portion.
較佳地，本發明之用以製備一染料敏化的太陽能電池的方法包含以下步驟：提供一由透明材料製成之透明基材作為一第一電極；在該透明基材上形成一以一定間距與該玻璃基材之邊緣分開至內側之多孔膜；將染料吸附至該多孔膜；提供一支持基材作為一第二電極；在該支持基材之整個表面上或以一定間距與該支持基材之邊緣分開至內側之方式在該支持基材上形成一觸媒金屬層；將該玻料塗布在未形成該多孔膜之該透明基材邊緣與該支持基材之觸媒金屬層或未形成該觸媒金屬層之該支持基材邊緣之間；及結合該第一電極與該第二電極，使得該多孔膜與該觸媒金屬層互相相向，且燒結所塗布之玻料以密封該等第一與第二電極。Preferably, the method for preparing a dye-sensitized solar cell of the present invention comprises the steps of: providing a transparent substrate made of a transparent material as a first electrode; forming a certain a porous film spaced apart from the edge of the glass substrate to the inner side; adsorbing the dye to the porous film; providing a support substrate as a second electrode; supporting the support on the entire surface of the support substrate or at a certain pitch Forming a catalyst metal layer on the support substrate by separating the edges of the substrate to the inner side; coating the glass material on the edge of the transparent substrate on which the porous film is not formed and the catalytic metal layer of the support substrate or Between the edges of the support substrate where the catalyst metal layer is not formed; and bonding the first electrode and the second electrode such that the porous film and the catalytic metal layer face each other, and the coated glass is sintered to seal The first and second electrodes.
該透明基材可以是在先前技術中習知之任何透明基材，例如，它可由一具有一導電膜之如ITO、FTO、玻璃或PET等絕緣材組成。該多孔膜可以是在先前技術中習知之任何多孔膜，且較佳地，它可藉塗布具有10至15nm之尺寸之TiO2 且將之燒結來獲得。又，染料可藉在先前技術中習知之任何方法吸附至該多孔膜，且較佳地，以一其中溶解有染料之混合溶液浸漬具有形成於其上之多孔膜的基材，以吸附該染料。該染料吸附步驟不一定在這階段進行，且可以在形成第7圖所示之一塊狀層後進行，或在結合該等第一與第二電極之後與在填充一電解質(藉通過一電解質入口注入一混合溶液)之前進行。不論其順序為何，均可進行該染料吸附步驟，只要它可將染料吸附至該多孔膜即可。又，在該多孔膜上可更包含一塊狀層。The transparent substrate may be any transparent substrate known in the prior art, for example, it may be composed of an insulating material such as ITO, FTO, glass or PET having a conductive film. The porous film may be any porous film known in the prior art, and preferably, it can be obtained by coating and sintering TiO 2 having a size of 10 to 15 nm. Further, the dye may be adsorbed to the porous film by any method known in the prior art, and preferably, the substrate having the porous film formed thereon is impregnated with a mixed solution in which the dye is dissolved to adsorb the dye. . The dye adsorption step is not necessarily performed at this stage, and may be performed after forming one of the bulk layers shown in FIG. 7, or after combining the first and second electrodes and after filling an electrolyte (by an electrolyte) The inlet is injected before a mixed solution). Regardless of the order, the dye adsorption step can be carried out as long as it can adsorb the dye to the porous film. Further, a bulk layer may be further included on the porous film.
接著，該第二電極係藉提供前述支持基材且藉電鍍、濺鍍等將一觸媒金屬層塗覆於其上而形成。Next, the second electrode is formed by applying the support substrate and applying a catalyst metal layer thereon by electroplating, sputtering, or the like.
該多孔膜最好形成在該透明基材上，且以一定間距與該邊緣分開至內側。該觸媒金屬層可形成在該支持基材上，且以一定間距與該邊緣分開至內側，但它可以形成在整個支持基材上。The porous film is preferably formed on the transparent substrate and separated from the edge to the inner side at a certain interval. The catalyst metal layer may be formed on the support substrate and separated from the edge to the inner side at a certain interval, but it may be formed on the entire support substrate.
如此製備之第一與第二電極係藉將玻料糊並將之燒結(包括雷射加熱燒結)來密封，如第1至9圖所示。The first and second electrodes thus prepared are sealed by sintering the glass frit paste (including laser heat sintering) as shown in Figures 1 to 9.
此外，本發明之用以製備一染料敏化的太陽能電池之方法可更包含以下步驟：在該第二電極中形成一用以注入一電解質之入口；將一電解質注入該入口；及將該玻料塗布在該入口上且將之燒結以密封該入口。形成該電解質入口之步驟可以在注入該電解質之前的任何階段進行，如此，這步驟可以在提供該支持基材之前或之後進行，或在形成該觸媒金屬層之後進行，或者在結合該等第一與第二電極之後進行。In addition, the method for preparing a dye-sensitized solar cell of the present invention may further comprise the steps of: forming an inlet for injecting an electrolyte into the second electrode; injecting an electrolyte into the inlet; The material is coated on the inlet and sintered to seal the inlet. The step of forming the electrolyte inlet may be performed at any stage prior to the injection of the electrolyte, such that the step may be performed before or after the support substrate is provided, or after the formation of the catalyst metal layer, or in combination with the The first and second electrodes are performed afterwards.
接著，通過所形成之電解質入口注入一製備一染料敏化的太陽能電池所需之電解質，且將一玻料糊塗布在該入口上並將之燒結以密封該入口，如第8圖所示。Next, an electrolyte required for preparing a dye-sensitized solar cell is injected through the formed electrolyte inlet, and a glass paste is coated on the inlet and sintered to seal the inlet, as shown in Fig. 8.
此外，對第9圖所示之構造而言，本發明之用以製備一染料敏化的太陽能電池的方法可更包含以下步驟：結合一由該第一或第二電極拉出之至一單元電池之外側之連接線；及選擇性地將該連接線拉至該太陽能電池之側邊，將該玻料塗布在該連接線四週與該太陽能電池之側邊且將它燒結，使得該連接線連接至該太陽能電池之側邊。結合該連接線之步驟可以在一適當階段進行，使得該連接線可以由該等第一與第二電極拉出，使電子可移動，或者它可以透過進一步加工來進行。又，由於一般太陽能電池需要一連接線，該連接線可以藉習知技術來拉出。In addition, for the configuration shown in FIG. 9, the method for preparing a dye-sensitized solar cell of the present invention may further comprise the steps of: combining a unit pulled by the first or second electrode to a unit; a connecting line on the outer side of the battery; and selectively pulling the connecting line to the side of the solar cell, coating the glass material around the connecting line and the side of the solar cell and sintering it so that the connecting line Connect to the side of the solar cell. The step of joining the connecting wires can be performed at an appropriate stage such that the connecting wires can be pulled out by the first and second electrodes to make the electrons moveable, or it can be carried out by further processing. Moreover, since a general solar cell requires a connection line, the connection line can be pulled out by conventional techniques.
接著，該拉出連接線之絕緣及與一太陽能電池側邊之連接不一定在完成一太陽能電池之製備後進行，且這些步驟可以在任何階段進行，只要該等第一與第二電極結合且該太陽能電池之側邊形狀不再改變即可。該玻料之燒結可以藉一般燒結方法進行，或者它可藉以雷射僅加熱塗布有該玻料之部份來燒結。Then, the insulation of the pull-out cable and the connection to the side of a solar cell are not necessarily performed after the preparation of a solar cell is completed, and the steps may be performed at any stage as long as the first and second electrodes are combined The shape of the side of the solar cell is no longer changed. The sintering of the glass material can be carried out by a general sintering method, or it can be sintered by laser only heating a portion coated with the glass material.
本發明將參照以下例子來說明，但是，這些例子僅用以說明本發明且本發明之範圍不受限於此。The invention will be described with reference to the following examples, but these examples are only intended to illustrate the invention and the scope of the invention is not limited thereto.
[例1]玻料之製備[Example 1] Preparation of glass material
例1至7之玻料係以在以下表1中所述之組成物來製備。在表1中，各值係以mol%為基準。The glass materials of Examples 1 to 7 were prepared as the compositions described in Table 1 below. In Table 1, each value is based on mol%.
[例8]一玻料糊組成物之製備及密封測試[Example 8] Preparation and sealing test of a glass paste composition
利用例1至7之各前述所製備玻料來製備一玻料糊組成物。藉由將5重量份之乙基纖維素型有機黏合劑溶解於BCA：TPN：DBP=75：15：5重量比之一混合溶劑中，以製備一載體，且均勻地混合17重量份之所製備載體、12重量份之作為一有機溶劑之BCA及71重量份之例1至7之各所製備玻料，製備該玻料糊組成物。A glass frit composition was prepared using each of the foregoing prepared glass materials of Examples 1 to 7. 5 parts by weight of the ethyl cellulose type organic binder is dissolved in a mixed solvent of BCA:TPN:DBP=75:15:5 by weight to prepare a carrier, and uniformly mixed 17 parts by weight The glass frit composition was prepared by preparing a carrier, 12 parts by weight of BCA as an organic solvent, and 71 parts by weight of each of the prepared glass materials of Examples 1 to 7.
一太陽能電池之密封測試係利用所製備之玻料糊組成物進行。將例1至7之各玻料糊組成物網印、乾燥、預燒結及照射雷射，以形成一密封。該雷射係使用Ti：藍寶石(810nm)雷射，且該基材係使用透明玻璃基材(Samsung Corning Company，商品名：Eagle 2000)。在密封時，在該玻璃板上無法觀察到可辨別之溫度增加或裂縫。A solar cell sealing test was carried out using the prepared glass paste composition. Each of the glass frit compositions of Examples 1 to 7 was screen printed, dried, pre-sintered, and irradiated with a laser to form a seal. The laser system used a Ti: sapphire (810 nm) laser, and the substrate was a transparent glass substrate (Samsung Corning Company, trade name: Eagle 2000). At the time of sealing, no discernible temperature increase or crack was observed on the glass plate.
例1-7之玻料糊組成物係如下地進行評價，且結果係節錄在以下表2中。The glass paste compositions of Examples 1-7 were evaluated as follows, and the results are summarized in Table 2 below.
1.玻璃轉移溫度(Tg )1. Glass transition temperature (T g )
以DTA裝置(DTG-60H Shimatz)測量一玻璃轉移溫度。A glass transition temperature was measured with a DTA apparatus (DTG-60H Shimatz).
2.軟化溫度(Tdsp )2. Softening temperature (T dsp )
以DTA裝置(DTG-60H Shimatz)且以10℃/分升高之溫度測量一軟化溫度。A softening temperature was measured with a DTA apparatus (DTG-60H Shimatz) and at a temperature of 10 ° C/min.
3.熱膨脹係數(CTE(×10-7 /℃))3. Thermal expansion coefficient (CTE (×10 -7 / ° C))
以TMA裝置(TMA-Q400 TA設備)且以5℃/分升高之溫度測量一熱膨脹係數。A coefficient of thermal expansion was measured with a TMA device (TMA-Q400 TA device) and at a temperature of 5 ° C / min.
4.防水4. Waterproof
將該密封之OLED樣本浸在80℃純水中且測量重量，以顯示增加速度小於0.5%者為O，且增加速度小於0.5%者為X。The sealed OLED sample was immersed in pure water at 80 ° C and the weight was measured to show that the increase rate was less than 0.5% for O, and the increase rate was less than 0.5% for X.
5.雷射密封測試5. Laser seal test
將該玻料糊組成物網印、乾燥與燒結以形成一密封圖案，且接著以雷射進行密封測試。使用Spectra-physics' integra-MP在13mm/秒之條件下進行密封測試，且決定是否已密封。The glass frit composition was screen printed, dried and sintered to form a seal pattern, and then subjected to a sealing test with a laser. The seal test was performed using a Spectra-physics' integra-MP at 13 mm/sec and it was decided whether it was sealed.
○：密封良好 ×：密封不佳○: Sealed well ×: Poor seal
如上表2中所示，本發明之玻料糊組成物提供良好低溫加工性及極佳防水與雷射密封。As shown in Table 2 above, the glass paste composition of the present invention provides good low temperature processability and excellent water and laser sealing.
本發明不限於前述例子與其附圖，並且在不偏離以下申請專利範圍所述之本發明特性與範疇之情形下，發明所屬技術領域中具有通常知識者可進行各種修改與變化。The present invention is not limited to the foregoing examples and the accompanying drawings, and various modifications and changes can be made by those skilled in the art without departing from the scope of the invention.
10．．．第一電極10. . . First electrode
11．．．透明基材11. . . Transparent substrate
12．．．邊緣12. . . edge
13．．．多孔膜13. . . Porous membrane
15．．．導電膜15. . . Conductive film
16．．．塊狀層16. . . Block layer
20．．．第二電極20. . . Second electrode
21．．．支持基材twenty one. . . Support substrate
22．．．邊緣twenty two. . . edge
23．．．觸媒金屬層twenty three. . . Catalytic metal layer
25．．．入口25. . . Entrance
26．．．導電膜26. . . Conductive film
30．．．電解質30. . . Electrolyte
40．．．燒結玻料40. . . Sintered glass
50．．．燒結玻料50. . . Sintered glass
60．．．連接線60. . . Cable
70．．．燒結玻料70. . . Sintered glass
第1圖是本發明第一實施例之一染料敏化的太陽能電池的橫截面圖，Figure 1 is a cross-sectional view showing a dye-sensitized solar cell according to a first embodiment of the present invention,
第2圖是本發明第二實施例之一染料敏化的太陽能電池的橫截面圖，Figure 2 is a cross-sectional view showing a dye-sensitized solar cell according to a second embodiment of the present invention,
第3圖是本發明第三實施例之一染料敏化的太陽能電池的橫截面圖，Figure 3 is a cross-sectional view showing a dye-sensitized solar cell according to a third embodiment of the present invention,
第4圖是本發明第四實施例之一染料敏化的太陽能電池的橫截面圖，Figure 4 is a cross-sectional view showing a dye-sensitized solar cell according to a fourth embodiment of the present invention,
第5圖是本發明第五實施例之一染料敏化的太陽能電池的橫截面圖，Figure 5 is a cross-sectional view showing a dye-sensitized solar cell according to a fifth embodiment of the present invention,
第6圖是本發明第六實施例之一染料敏化的太陽能電池的橫截面圖，Figure 6 is a cross-sectional view showing a dye-sensitized solar cell of a sixth embodiment of the present invention,
第7圖是本發明第七實施例之一染料敏化的太陽能電池的橫截面圖，Figure 7 is a cross-sectional view showing a dye-sensitized solar cell according to a seventh embodiment of the present invention,
第8圖是本發明之一染料敏化的太陽能電池的橫截面圖，顯示一電解質入口之密封，且Figure 8 is a cross-sectional view of a dye-sensitized solar cell of the present invention showing a seal of an electrolyte inlet, and
第9圖是本發明之一染料敏化的太陽能電池的橫截面圖，顯示一連接線。Figure 9 is a cross-sectional view of a dye-sensitized solar cell of the present invention showing a connecting line.
10．．．第一電極10. . . First electrode
11．．．透明基材11. . . Transparent substrate
13．．．多孔膜13. . . Porous membrane
20．．．第二電極20. . . Second electrode
21．．．支持基材twenty one. . . Support substrate
23．．．觸媒金屬層twenty three. . . Catalytic metal layer
30．．．電解質30. . . Electrolyte
40．．．燒結玻料40. . . Sintered glass
Claims (12)
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| KR1020080025960A KR101510658B1 (en) | 2008-03-20 | 2008-03-20 | Dye-sensitized solar cell and method for manufacturing the same |
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| JP5713422B2 (en) * | 2009-10-16 | 2015-05-07 | 日本電気硝子株式会社 | Dye-sensitized solar cell glass composition and dye-sensitized solar cell material |
| JP5507954B2 (en) * | 2009-10-19 | 2014-05-28 | 三星エスディアイ株式会社 | Glass paste composition, electrode substrate, production method thereof, and dye-sensitized solar cell |
| KR101130614B1 (en) * | 2010-03-24 | 2012-04-02 | 주식회사 앰브로 | Dye sensitized solar cells |
| KR20120028494A (en) * | 2010-09-15 | 2012-03-23 | 주식회사 동진쎄미켐 | Dye sensitized solar cell with advanced power efficiency |
| KR20120040322A (en) * | 2010-10-19 | 2012-04-27 | 주식회사 동진쎄미켐 | Dye-sensitized solar cell with light scattering layer, and manufacturing method thereof |
| KR101982852B1 (en) * | 2011-03-21 | 2019-05-29 | 서울시립대학교 산학협력단 | Solar cell with separator and method of the manufacturing of the same |
| KR101976377B1 (en) * | 2011-03-23 | 2019-05-10 | 서울시립대학교 산학협력단 | Hybrid dye sensitized solar cell and method of the manufacturing of the same |
| JP5118233B2 (en) * | 2011-06-08 | 2013-01-16 | シャープ株式会社 | Photoelectric conversion element and photoelectric conversion element module |
| US10916382B2 (en) | 2011-06-08 | 2021-02-09 | Sharp Kabushiki Kaisha | Photoelectric conversion element and photoelectric conversion element module |
| KR101255779B1 (en) * | 2011-11-03 | 2013-04-22 | 주식회사 다이온 | Dye sensitized solar cell with excellent sealability and durability |
| KR101301482B1 (en) * | 2011-11-03 | 2013-08-29 | 주식회사 아이엠티에스 | Composition for protecting electrode with excellent anti-corrosion and dye sensitized solar cell using the composition |
| CN102385992A (en) * | 2011-11-18 | 2012-03-21 | 中国科学院等离子体物理研究所 | Method and device for sealing dye sensitization solar cell electrolyte filling hole |
| CN102709062B (en) * | 2012-06-05 | 2016-07-13 | 南昌航空大学 | A kind of encapsulating method of dye-sensitized solar cells |
| EP2913883A4 (en) * | 2012-10-23 | 2015-10-14 | Univ Tokyo Sci Educ Found | Photoelectrode for dye-sensitized solar cells, and dye-sensitized solar cell |
| KR101445773B1 (en) * | 2013-04-10 | 2014-10-07 | 재단법인대구경북과학기술원 | Dye sensitized solar cell and the fbricationg method thereof |
| KR101570740B1 (en) | 2014-05-21 | 2015-11-23 | 주식회사 오리온 | Glass materials for large scale dye-sensitized solar cell sealing |
| KR101581798B1 (en) | 2014-05-27 | 2015-12-31 | 공주대학교 산학협력단 | Sealing frit composition for oled display with enhanced adhesion and paste composition containing the same |
| KR101755550B1 (en) | 2015-07-24 | 2017-07-07 | (주)세라 | Sealant composition for tempered glass panel |
| KR101957743B1 (en) * | 2016-07-29 | 2019-03-14 | 공주대학교 산학협력단 | Glass materials possible to co-fired TiO2 for large scale dye-sensitized solar cell sealing application |
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| US3885975A (en) * | 1972-04-24 | 1975-05-27 | Corning Glass Works | Low melting vanadate glasses |
| US5346863A (en) * | 1992-12-11 | 1994-09-13 | Nippon Electric Glass Co., Ltd. | Low temperature sealing composition |
| JP2004319197A (en) * | 2003-04-15 | 2004-11-11 | Fujikura Ltd | Photoelectric conversion element and its manufacturing method |
| KR100685845B1 (en) * | 2005-10-21 | 2007-02-22 | 삼성에스디아이 주식회사 | Organic eletroluminescence display device and method for fabricating of the same |
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| JP5481081B2 (en) | 2014-04-23 |
| TW200947791A (en) | 2009-11-16 |
| KR20090100649A (en) | 2009-09-24 |
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| KR101510658B1 (en) | 2015-05-06 |
| DE102009012544A1 (en) | 2009-10-22 |
| JP2009231284A (en) | 2009-10-08 |
| CN101540233B (en) | 2013-01-09 |
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