TWI690634B - Composite nanofiber, its preparation method and application - Google Patents

Composite nanofiber, its preparation method and application Download PDF

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TWI690634B
TWI690634B TW108139351A TW108139351A TWI690634B TW I690634 B TWI690634 B TW I690634B TW 108139351 A TW108139351 A TW 108139351A TW 108139351 A TW108139351 A TW 108139351A TW I690634 B TWI690634 B TW I690634B
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composite
weight percent
sensitized solar
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TW202117111A (en
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粘譽薰
徐慧軒
陳皇華
胡耿銘
周榮泉
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國立雲林科技大學
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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
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    • Y02E10/542—Dye sensitized solar cells

Abstract

本創作提供一種複合奈米纖維、其製法及其應用。該複合奈米纖維包括二氧化鈦奈米纖維及氧化石墨烯；其中該複合奈米纖維的直徑大於或等於180奈米且小於或等於350奈米，複合奈米纖維的比表面積大於或等於70 m 2/g且小於或等於120 m 2/g。藉此令複合奈米纖維應用於染料敏化太陽能電池之光陽極中能減少電子復合的情形，從而提升染料敏化太陽能電池之光伏特性及光電轉換效率。 This creation provides a composite nanofiber, its preparation method and its application. The composite nanofibers include titanium dioxide nanofibers and graphene oxide; wherein the diameter of the composite nanofibers is greater than or equal to 180 nanometers and less than or equal to 350 nanometers, and the specific surface area of the composite nanofibers is greater than or equal to 70 m 2 /g and less than or equal to 120 m 2 /g. This allows composite nanofibers to be used in the photoanode of dye-sensitized solar cells to reduce electron recombination, thereby improving the photovoltaic characteristics and photoelectric conversion efficiency of dye-sensitized solar cells.

Description

複合奈米纖維、其製法及其應用Composite nanofiber, its preparation method and application

本創作關於一種奈米纖維、其製法及其應用材料，尤指一種能適用於染料敏化太陽能電池之複合奈米纖維、其製法以及包含其之光陽極。This work is about a nanofiber, its preparation method and its application materials, especially a composite nanofiber suitable for dye-sensitized solar cells, its preparation method and photoanode containing it.

染料敏化太陽能電池係新一代的太陽能電池，因其具有低製造成本、受日照角度影響小及受高溫環境影響小等有別於傳統太陽能電池的特點，故受到相關領域的關注。Dye-sensitized solar cells are a new generation of solar cells, which are different from traditional solar cells because of their low manufacturing cost, little influence from sunlight angle, and little influence from high temperature environment, so they have received attention from related fields.

染料敏化太陽能電池的主要結構包含光陽極、半導體薄膜層、電解質層、光敏化染料層及對電極等。其中光敏化染料會吸附於光陽極之上，將光能轉換成電能。The main structure of the dye-sensitized solar cell includes a photoanode, a semiconductor thin film layer, an electrolyte layer, a photosensitizing dye layer and a counter electrode. Among them, the photosensitizing dye will be adsorbed on the photoanode to convert light energy into electrical energy.

二氧化鈦為一種具有高光催化性能、高穩定性等特性的材料，故其常作為染料敏化太陽能電池的光陽極所選用的材料。Titanium dioxide is a material with high photocatalytic performance, high stability and other characteristics, so it is often used as the material of choice for the photoanode of dye-sensitized solar cells.

然而，現有技術之光陽極多半採用二氧化鈦奈米顆粒或二氧化鈦奈米纖維為主要成分，因前述二氧化鈦奈米顆粒或及二氧化鈦奈米纖維皆具有較大的直徑、較小的比表面積，故所製得之光陽極具有較弱的染料吸附能力、低電子遷移率等缺點，從而導致所製得之染料敏化太陽能電池普遍存在光伏效率不足的問題，故目前實有必要開發其他改質材料以用於修飾光陽極，進而提升染料敏化太陽能電池的光伏效率。However, most of the prior art photoanodes use titanium dioxide nanoparticles or titanium dioxide nanofibers as the main component. Because the aforementioned titanium dioxide nanoparticles or titanium dioxide nanofibers have larger diameters and smaller specific surface areas, they are manufactured The obtained photoanode has the disadvantages of weak dye adsorption capacity, low electron mobility, etc., which leads to the problem of insufficient photovoltaic efficiency of the dye-sensitized solar cells produced, so it is currently necessary to develop other modified materials for use It is used to modify the photoanode to further improve the photovoltaic efficiency of dye-sensitized solar cells.

有鑑於上述技術缺陷，本創作一目的在於開發一種複合奈米纖維，使該複合奈米纖維具有較大的比表面積、直徑較小等特點。In view of the above technical shortcomings, one purpose of this work is to develop a composite nanofiber, so that the composite nanofiber has the characteristics of large specific surface area and small diameter.

本創作另一目的在於開發一種複合奈米纖維，其能適用於修飾染料敏化太陽能電池的光陽極。Another purpose of this creation is to develop a composite nanofiber, which can be used to modify the photoanode of dye-sensitized solar cells.

為達成前述目的，本創作提供一種複合奈米纖維，其包括一二氧化鈦奈米纖維及一氧化石墨烯(graphene oxide，GO)；以該複合奈米纖維之總重為基準，該氧化石墨烯之含量大於0重量百分比且小於或等於0.016重量百分比；其中該複合奈米纖維的直徑大於或等於180奈米且小於或等於350奈米，複合奈米纖維的比表面積大於或等於70平方公尺/克(square meter/gram，m 2/g)且小於或等於120 m 2/g。 To achieve the foregoing purpose, the present invention provides a composite nanofiber, which includes a titanium dioxide nanofiber and graphene oxide (GO); based on the total weight of the composite nanofiber, the graphene oxide The content is greater than 0 weight percent and less than or equal to 0.016 weight percent; wherein the diameter of the composite nanofiber is greater than or equal to 180 nanometers and less than or equal to 350 nanometers, and the specific surface area of the composite nanofiber is greater than or equal to 70 square meters/ Gram (square meter/gram, m 2 /g) and less than or equal to 120 m 2 /g.

據此，藉由在複合奈米纖維中添加適量的氧化石墨烯，本創作之複合奈米纖維能兼具較大的比表面積、較小的直徑，故本創作之複合奈米纖維應用於染料敏化太陽能電池之光陽極中能減少電子復合的情形，從而提升染料敏化太陽能電池之光伏特性及光電轉換效率。According to this, by adding an appropriate amount of graphene oxide to the composite nanofibers, the composite nanofibers of this creation can have both a large specific surface area and a small diameter, so the composite nanofibers of this creation are used in dyes The photo-anode of the sensitized solar cell can reduce electron recombination, thereby improving the photovoltaic characteristics and photoelectric conversion efficiency of the dye-sensitized solar cell.

較佳的，所述複合奈米纖維的直徑大於或等於190奈米且小於或等於340奈米；更佳的，所述複合奈米纖維的直徑大於或等於195奈米且小於或等於330奈米；再更佳的，所述複合奈米纖維的直徑大於或等於200奈米且小於或等於325奈米。Preferably, the diameter of the composite nanofiber is greater than or equal to 190 nanometers and less than or equal to 340 nanometers; more preferably, the diameter of the composite nanofiber is greater than or equal to 195 nanometers and less than or equal to 330 nanometers Even better, the diameter of the composite nanofiber is greater than or equal to 200 nanometers and less than or equal to 325 nanometers.

較佳的，所述複合奈米纖維的比表面積大於或等於72 m 2/g且小於或等於115 m 2/g；更佳的，所述複合奈米纖維的比表面積大於或等於75 m 2/g且小於或等於105 m 2/g。 Preferably, the specific surface area of the composite nanofiber is greater than or equal to 72 m 2 /g and less than or equal to 115 m 2 /g; more preferably, the specific surface area of the composite nanofiber is greater than or equal to 75 m 2 /g and less than or equal to 105 m 2 /g.

較佳的，所述氧化石墨烯的含量大於或等於0.010重量百分比且小於或等於0.016重量百分比。Preferably, the content of the graphene oxide is greater than or equal to 0.010 weight percent and less than or equal to 0.016 weight percent.

除了前述氧化石墨烯之外，於其中一實施態樣中，該複合奈米纖維可進一步包含一銀(silver，Ag)，但並非僅限於此。In addition to the aforementioned graphene oxide, in one embodiment, the composite nanofiber may further include a silver (Ag), but it is not limited to this.

於其中一實施態樣中，以該複合奈米纖維之總重為基準，該銀之含量大於0重量百分比且小於或等於1.9重量百分比，該氧化石墨烯及該銀之總含量大於或等於0.2重量百分比且小於或等於1.91重量百分比。In one embodiment, based on the total weight of the composite nanofibers, the silver content is greater than 0 weight percent and less than or equal to 1.9 weight percent, and the total content of the graphene oxide and silver is greater than or equal to 0.2 Weight percent and less than or equal to 1.91 weight percent.

較佳的，以該複合奈米纖維之總重為基準，該銀之含量大於或等於0.2重量百分比且小於或等於1.9重量百分比，該氧化石墨烯及該銀之總含量大於或等於0.5重量百分比且小於或等於1.91重量百分比。更佳的，以該複合奈米纖維之總重為基準，該銀之含量大於或等於0.5重量百分比且小於或等於1.9重量百分比，該氧化石墨烯及該銀之總含量大於或等於1重量百分比且小於或等於1.91重量百分比。Preferably, based on the total weight of the composite nanofibers, the silver content is greater than or equal to 0.2 weight percent and less than or equal to 1.9 weight percent, and the total content of the graphene oxide and the silver is greater than or equal to 0.5 weight percent And less than or equal to 1.91 weight percent. More preferably, based on the total weight of the composite nanofibers, the silver content is greater than or equal to 0.5 weight percent and less than or equal to 1.9 weight percent, and the total content of the graphene oxide and the silver is greater than or equal to 1 weight percent And less than or equal to 1.91 weight percent.

較佳的，所述複合奈米纖維的直徑大於或等於190奈米且小於或等於310奈米；更佳的，所述複合奈米纖維的直徑大於或等於200奈米且小於或等於305奈米。Preferably, the diameter of the composite nanofiber is greater than or equal to 190 nanometers and less than or equal to 310 nanometers; more preferably, the diameter of the composite nanofiber is greater than or equal to 200 nanometers and less than or equal to 305 nanometers Meter.

較佳的，所述複合奈米纖維的比表面積大於或等於90 m 2/g且小於或等於110 m 2/g；更佳的，所述複合奈米纖維的比表面積大於或等於95 m 2/g且小於或等於105 m 2/g。 Preferably, the specific surface area of the composite nanofiber is greater than or equal to 90 m 2 /g and less than or equal to 110 m 2 /g; more preferably, the specific surface area of the composite nanofiber is greater than or equal to 95 m 2 /g and less than or equal to 105 m 2 /g.

較佳的，所述二氧化鈦奈米纖維的晶相含有鋭鈦礦、金紅石或其組合，但並非僅限於此。Preferably, the crystalline phase of the titanium dioxide nanofiber contains brookite, rutile, or a combination thereof, but it is not limited to this.

為達成前述目的，本創作另提供一種複合奈米纖維之製法，其包括以下步驟： 步驟(a)：於一極性有機溶劑之存在下，令異丙醇鈦混合氧化石墨烯，以獲得一膠體溶液；以該膠體溶液之總重為基準，該氧化石墨烯之含量大於0重量百分比且小於或等於0.016重量百分比； 步驟(b)：令該膠體溶液進行靜電紡絲法，得到一靜電紡絲產物；以及 步驟(c)：令該靜電紡絲產物於大於或等於450°C且小於或等於600°C之溫度下，持續鍛燒1小時以上，以製得一複合奈米纖維。 In order to achieve the aforementioned purpose, this work also provides a method for preparing composite nanofibers, which includes the following steps: Step (a): mixing titanium isopropoxide with graphene oxide in the presence of a polar organic solvent to obtain a colloidal solution; based on the total weight of the colloidal solution, the content of the graphene oxide is greater than 0 weight percent And less than or equal to 0.016 weight percent; Step (b): subject the colloidal solution to electrospinning to obtain an electrospinning product; and Step (c): The electrospinning product is continuously calcined at a temperature greater than or equal to 450°C and less than or equal to 600°C for more than 1 hour to obtain a composite nanofiber.

據此，藉由在複合奈米纖維中添加適量的氧化石墨烯與控制靜電紡絲法條件及鍛燒條件，本創作之複合奈米纖維能兼具較大的比表面積、較小的直徑，故本創作之複合奈米纖維應用於染料敏化太陽能電池之光陽極中能減少電子復合的情形，從而提升染料敏化太陽能電池之光伏特性及光電轉換效率。Accordingly, by adding an appropriate amount of graphene oxide to the composite nanofibers and controlling the conditions of the electrospinning method and the calcination conditions, the composite nanofibers of this creation can have both a large specific surface area and a small diameter. Therefore, the composite nanofibers of this creation can be used in the photoanode of dye-sensitized solar cells to reduce the electron recombination, thereby improving the photovoltaic characteristics and photoelectric conversion efficiency of dye-sensitized solar cells.

於本說明書中，所述靜電紡絲法係採用靜電紡絲設備製作靜電紡絲；較佳的，所述靜電紡絲設備所設定的電壓為15千伏特(kilovoltage，kV)至20 kV；所述靜電紡絲設備的不銹鋼針的針尖及滾筒收集器之間的距離為11至15公分；所述靜電紡絲設備所設定的流量為0.035毫升/分鐘(milliliter/minute，mL/min)至0.045 mL/min。In this specification, the electrospinning method uses electrospinning equipment to produce electrospinning; preferably, the voltage set by the electrospinning equipment is 15 kilovolts (kV) to 20 kV; The distance between the tip of the stainless steel needle of the electrospinning device and the drum collector is 11 to 15 cm; the flow rate set by the electrospinning device is 0.035 milliliters/minute (mL/min) to 0.045 mL/min.

較佳的，所述鍛燒溫度大於或等於450°C且小於或等於550°C；所述鍛燒時間大於或等於1小時且小於或等於3小時。Preferably, the calcination temperature is greater than or equal to 450°C and less than or equal to 550°C; the calcination time is greater than or equal to 1 hour and less than or equal to 3 hours.

於其中一實施態樣中，所述膠體溶液可進一步包含銀，但並非僅限於此。In one embodiment, the colloidal solution may further include silver, but it is not limited to this.

較佳的，以該膠體溶液之總重為基準，該銀之含量大於0重量百分比且小於或等於1.9重量百分比，該氧化石墨烯及該銀之總含量大於或等於0.2重量百分比且小於或等於1.91重量百分比。Preferably, based on the total weight of the colloidal solution, the silver content is greater than 0 weight percent and less than or equal to 1.9 weight percent, and the total content of the graphene oxide and silver is greater than or equal to 0.2 weight percent and less than or equal to 1.91 weight percent.

為達成前述目的，本創作另提供一種光陽極，其係包括如所述複合奈米纖維以及一導電基板，該複合奈米纖維形成於該導電基板上。To achieve the foregoing objective, the present invention further provides a photoanode, which includes the composite nanofiber as described above and a conductive substrate, the composite nanofiber is formed on the conductive substrate.

據此，藉由使用本創作之複合奈米纖維所修飾之光陽極，亦能具有類似複合奈米纖維之組成及特性，故本創作之複合奈米纖維應用於染料敏化太陽能電池之光陽極中能減少電子復合的情形，從而提升染料敏化太陽能電池之光伏特性及光電轉換效率。According to this, the photoanode modified by using the composite nanofibers created in this invention can also have the composition and characteristics similar to the composite nanofibers, so the composite nanofibers created in this application are applied to the photoanode of dye-sensitized solar cells Zhongneng can reduce the recombination of electrons, thereby improving the photovoltaic characteristics and photoelectric conversion efficiency of dye-sensitized solar cells.

較佳的，所述導電基板包含氟摻雜氧化錫(fluorine-doped tin oxide，FTO)玻璃，但並非僅限於此。Preferably, the conductive substrate includes fluorine-doped tin oxide (FTO) glass, but it is not limited to this.

為達成前述目的，本創作另提供一種染料敏化太陽能電池，其係由前述光陽極所製得。In order to achieve the foregoing purpose, the present invention also provides a dye-sensitized solar cell, which is manufactured by the foregoing photoanode.

據此，藉由使用本創作之複合奈米纖維所修飾之光陽極應用於染料敏化太陽能電池，亦能具有類似複合奈米纖維之組成及特性，故能兼具良好的光伏特性及光電轉換效率。According to this, by using the photoanode modified by the composite nanofibers of this creation to be applied to dye-sensitized solar cells, it can also have the composition and characteristics similar to composite nanofibers, so it can have both good photovoltaic characteristics and photoelectric conversion effectiveness.

於本說明書中，所述染料敏化太陽能電池包含一光陽極、一對電極、一半導體薄膜層、一光敏化染料層及一電解質層；較佳的，所述光陽極與該光敏化染料層及該電解質層相連接，該電解質層之相對一側與該半導體薄膜層相連接，該半導體薄膜層之相對一側與該對電極相連接。In this specification, the dye-sensitized solar cell includes a photoanode, a pair of electrodes, a semiconductor thin film layer, a photosensitizing dye layer and an electrolyte layer; preferably, the photoanode and the photosensitizing dye layer It is connected to the electrolyte layer, the opposite side of the electrolyte layer is connected to the semiconductor thin film layer, and the opposite side of the semiconductor thin film layer is connected to the pair of electrodes.

較佳的，所述光敏化染料層中的染料含有釕金屬錯合物，但並非僅限於此。更佳的，所述光敏化染料層中的染料含有釕-N719(N719，C 58H 86N 8O 8RuS 2)，但並非僅限於此。 Preferably, the dye in the photosensitizing dye layer contains a ruthenium metal complex, but it is not limited to this. More preferably, the dye in the photosensitizing dye layer contains ruthenium-N719 (N719, C 58 H 86 N 8 O 8 RuS 2 ), but it is not limited to this.

較佳的，所述電解質層中的電解質含有碘化物，但並非僅限於此。更佳的，所述電解質層中的電解質含有碘化鋰，但並非僅限於此。Preferably, the electrolyte in the electrolyte layer contains iodide, but it is not limited to this. More preferably, the electrolyte in the electrolyte layer contains lithium iodide, but it is not limited to this.

在下文中，本領域技術人員可經由本說明書之內容很輕易地了解本創作所能達成之優點及功效。因此，應當理解本文提出的敘述僅用於說明優選的實施方式而不是用於侷限本創作的範圍，並且於不悖離本創作之精神和範圍下，可以進行各種修飾及變更，以便實施或應用本創作之內容。In the following, those skilled in the art can easily understand the advantages and effects achieved by this creation through the content of this specification. Therefore, it should be understood that the descriptions presented herein are only for describing preferred embodiments and not for limiting the scope of the creation, and various modifications and changes can be made for implementation or application without departing from the spirit and scope of the creation The content of this creation.

以下實施例所用儀器型號： 1.    超音波震盪器：DC600H，購自DELTA； 2.    pH計：Sension3，購自HACH； 3.    冷凍乾燥機：FD-series，購自PAMCHUM； 4.    高壓電源耗材：MATSUSADA，購自Precision Inc.； 5.    注射幫浦：Fusion 200，購自Chemyx Inc.； 6.    台式工業爐：FD1545M，購自Clarkson Laboratory & Supply Inc.； 7.    多功能測試儀：HP 34401A，購自Keysight； 8.    旋轉塗覆機：PM-490，購自Synrex； 9.    微量移液器：Acura 825, 835，購自Socorex； 10.場發式掃描式電子顯微鏡：JSM-6701F，購自JEOL； 11.穿透式電子顯微鏡：JEM-1400，購自JEOL； 12.X射線衍射儀：MiniFlex II，購自Rigaku； 13.拉曼分析儀：RMS-iHR550，購自Jobin Yvon HORIBA S.A.A； 14.紫外光-可見光分光光度計：Lambda 850，購自Perkin Elmer precisely； 15.比表面積分析儀：ASAP 2060，購自Micromeritics； 16.太陽光模擬器：MFS-PV-Basic，購自HMT； 17.電化學阻抗譜：SP-150，購自BioLogic；以及 18.光電轉換效率分析儀：QE-R3011，購自Enlitech Inc.。 Models of instruments used in the following examples: 1. Ultrasonic oscillator: DC600H, purchased from DELTA; 2. pH meter: Sension3, purchased from HACH; 3. Freeze dryer: FD-series, purchased from PAMCHUM; 4. High-voltage power supply consumables: MATSUSADA, purchased from Precision Inc.; 5. Injection pump: Fusion 200, purchased from Chemyx Inc.; 6. Desktop industrial furnace: FD1545M, purchased from Clarkson Laboratory & Supply Inc.; 7. Multifunctional tester: HP 34401A, purchased from Keysight; 8. Rotary coating machine: PM-490, purchased from Synrex; 9. Micropipette: Acura 825, 835, purchased from Socorex; 10. Field emission scanning electron microscope: JSM-6701F, purchased from JEOL; 11. Penetrating electron microscope: JEM-1400, purchased from JEOL; 12. X-ray diffractometer: MiniFlex II, purchased from Rigaku; 13. Raman analyzer: RMS-iHR550, purchased from Jobin Yvon HORIBA S.A.A; 14. Ultraviolet-visible light spectrophotometer: Lambda 850, purchased from Perkin Elmer precisely; 15. Specific surface area analyzer: ASAP 2060, purchased from Micromeritics; 16. Sunlight simulator: MFS-PV-Basic, purchased from HMT; 17. Electrochemical impedance spectroscopy: SP-150, purchased from BioLogic; and 18. Photoelectric conversion efficiency analyzer: QE-R3011, purchased from Enlitech Inc.

以下實施例所使用的原料： 19.石墨粉末：購自Enerage Inc.； 20.乙醯丙酮(acetylacetone，C 5H 8O 2)：購自Sigma-Aldrich Co.； 21.酞菁(phthalocyanine，C 32H 18N 8)：購自Sigma-Aldrich Co.； 22.碘化鋰：購自Sigma-Aldrich Co.； 23.硝酸鈉：購自Sigma-Aldrich Co.； 24.硫酸：購自Nihon Shiyak Industries Ltd.； 25.鹽酸：購自Nihon Shiyak Industries Ltd.； 26.過錳酸鉀(potassium permanganate，KMnO 4)：購自Merck； 27.過氧化氫：購自景明化工股份有限公司； 28.乙酸：購自Sigma-Aldrich Co.； 29.氟摻雜氧化錫玻璃：購自Hartford Glass Co.； 30.無水乙醇：購自Sigma-Aldrich Co.及Katayama Chemical； 31.異丙醇鈦：購自Sigma-Aldrich Co.； 32.聚乙烯吡咯烷酮：購自Sigma-Aldrich Co.； 33.二氧化鈦粉末：P25，購自UniRegion Bio-Tech； 34.釕-N719(N719，C 58H 86N 8O 8RuS 2)：購自UniRegion Bio-Tech； 35.碘(iodine puriss)：購自Riedel-de Haėn；以及 36.曲拉通X-100(triton X-100)：購自PRS。 The raw materials used in the following examples: 19. Graphite powder: purchased from Enerage Inc.; 20. Acetylacetone (C 5 H 8 O 2 ): purchased from Sigma-Aldrich Co.; 21. Phthalocyanine (phthalocyanine, C 32 H 18 N 8 ): purchased from Sigma-Aldrich Co.; 22. Lithium iodide: purchased from Sigma-Aldrich Co.; 23. Sodium nitrate: purchased from Sigma-Aldrich Co.; 24. Sulfuric acid: purchased from Nihon Shiyak Industries Ltd.; 25. Hydrochloric acid: purchased from Nihon Shiyak Industries Ltd.; 26. Potassium permanganate (KMnO 4 ): purchased from Merck; 27. Hydrogen peroxide: purchased from Jingming Chemical Co., Ltd.; 28 Acetic acid: purchased from Sigma-Aldrich Co.; 29. Fluorine-doped tin oxide glass: purchased from Hartford Glass Co.; 30. Absolute ethanol: purchased from Sigma-Aldrich Co. and Katayama Chemical; 31. Titanium isopropoxide: Purchased from Sigma-Aldrich Co.; 32. Polyvinylpyrrolidone: purchased from Sigma-Aldrich Co.; 33. Titanium dioxide powder: P25, purchased from UniRegion Bio-Tech; 34. Ruthenium-N719 (N719, C 58 H 86 N 8 O 8 RuS 2 ): purchased from UniRegion Bio-Tech; 35. iodine puriss: purchased from Riedel-de Haėn; and 36. triton X-100 (triton X-100): purchased from PRS.

參考例Reference example 11 之二氧化鈦奈米顆粒Titanium dioxide nanoparticles

參考例1之二氧化鈦奈米顆粒係購自商用二氧化鈦粉末。The titanium dioxide nanoparticles of Reference Example 1 were purchased from commercial titanium dioxide powder.

參考例Reference example 22 之二氧化鈦奈米纖維Titanium dioxide nanofiber

於製程中，以滴加方式加入6毫升(milliliter，mL)的異丙醇鈦至8 mL的乙酸中，以得到溶液A。接著，將2克(gram，g)的聚乙烯吡咯烷酮加入18 g的無水乙醇溶液中，以得到溶液B。最後，將溶液A及溶液B混合均勻，再靜置24小時，以得到二氧化鈦溶膠-凝膠溶液。In the process, 6 milliliters (mL) of titanium isopropoxide was added dropwise to 8 mL of acetic acid to obtain solution A. Next, 2 grams (gram, g) of polyvinylpyrrolidone was added to 18 g of absolute ethanol solution to obtain solution B. Finally, the solution A and the solution B are mixed uniformly and allowed to stand for 24 hours to obtain a titanium dioxide sol-gel solution.

接著，將前述二氧化鈦溶膠-凝膠溶液注入靜電紡絲設備的注射器中，並利用注射幫浦將其注射流量控制在0.043 mL/min，電壓設定在17 kV、不銹鋼針的針尖及滾筒收集器之間的距離固定為約12至13公分，於室溫下進行靜電紡絲製作步驟，於滾筒收集器(轉速設定為1000 rpm)上收集得到靜電紡絲。Next, the aforementioned titanium dioxide sol-gel solution was injected into the syringe of the electrospinning device, and the injection flow rate was controlled at 0.043 mL/min using an injection pump, the voltage was set at 17 kV, the tip of the stainless steel needle and the roller collector The distance between them is fixed at about 12 to 13 cm, and the electrospinning process is carried out at room temperature, and the electrospinning is collected on a drum collector (the rotation speed is set to 1000 rpm).

最後，將前述所製得之靜電紡絲在500°C下持溫鍛燒1小時，即完成參考例2之二氧化鈦奈米纖維之製備。Finally, the above-prepared electrospinning was calcined at 500° C. for 1 hour to complete the preparation of the titanium dioxide nanofiber of Reference Example 2.

實施例Examples 11 之Of 複合奈米纖維Composite nanofiber

於製程中，以滴加方式加入6 mL的異丙醇鈦至8 mL的乙酸中，以得到溶液A。接著，將3 g的石墨粉末及3 g的硝酸鈉放入1 L的玻璃反應器中，加入138 mL的硫酸後進行超音波振盪5分鐘。接著，邊攪拌邊緩慢加入9 g的過錳酸鉀在前述玻璃反應器中，於室溫下持續攪拌1小時。接著，將前述玻璃反應器浸泡於0°C至4°C的冰浴槽中，再持續攪拌24小時。接著，緩慢加入150 mL的去離子水進行酸鹼中和，再接續加入350 mL的去離子水。接者，緩慢加入30 mL的過氧化氫，持續攪拌30分鐘，以終止氧化反應，再靜置24小時使溶液產生沉澱物。接著，去除沉澱物，以得到氧化石墨烯前驅物。接著，以1 L的鹽酸溶液（鹽酸：去離子水=1：10）清洗氧化石墨烯前驅物，再以去離子水清洗氧化石墨烯前驅物至清洗廢液的pH值為7。接者，使用冷凍乾燥機去除水分，以得到氧化石墨烯粉末，將氧化石墨烯粉末加入去離子水混合均勻(氧化石墨烯粉末：去離子水=10mg：20mL)，以得到溶液C。接著，將溶液A和溶液C混合均勻，持續攪拌1小時，以得到溶液D。接著，將溶液D在60°C於超音波震盪之下持溫加熱1小時，以得到摻雜氧化石墨烯的二氧化鈦溶膠-凝膠溶液。In the process, 6 mL of titanium isopropoxide was added to 8 mL of acetic acid in a dropwise manner to obtain solution A. Next, 3 g of graphite powder and 3 g of sodium nitrate were placed in a 1 L glass reactor, and 138 mL of sulfuric acid was added, followed by ultrasonic vibration for 5 minutes. Next, 9 g of potassium permanganate was slowly added to the aforementioned glass reactor while stirring, and stirring was continued at room temperature for 1 hour. Next, the aforementioned glass reactor was immersed in an ice bath of 0°C to 4°C, and stirring was continued for 24 hours. Next, slowly add 150 mL of deionized water for acid-base neutralization, and then add 350 mL of deionized water. Then, slowly add 30 mL of hydrogen peroxide, and continue to stir for 30 minutes to stop the oxidation reaction, and then stand for 24 hours to produce a precipitate in the solution. Next, the precipitate is removed to obtain a graphene oxide precursor. Next, the graphene oxide precursor was washed with 1 L of hydrochloric acid solution (hydrochloric acid: deionized water=1:10), and then the graphene oxide precursor was washed with deionized water until the pH value of the cleaning waste liquid was 7. Then, the moisture was removed using a freeze dryer to obtain graphene oxide powder. The graphene oxide powder was added to deionized water and mixed uniformly (graphene oxide powder: deionized water = 10 mg: 20 mL) to obtain solution C. Next, the solution A and the solution C are mixed uniformly, and stirring is continued for 1 hour to obtain the solution D. Next, the solution D was heated at 60°C under ultrasonic vibration for 1 hour at a temperature to obtain a titanium dioxide sol-gel solution doped with graphene oxide.

接著，將前述摻雜氧化石墨烯的二氧化鈦溶膠-凝膠溶液注入靜電紡絲設備的注射器中，並利用注射幫浦將其注射流量控制在0.043 mL/min，電壓設定在17 kV、不銹鋼針的針尖及滾筒收集器之間的距離固定為約12至13公分，於室溫下進行靜電紡絲製作步驟，於滾筒收集器(轉速設定為1000 rpm)上收集得到靜電紡絲。Next, the aforementioned graphene oxide-doped titanium dioxide sol-gel solution was injected into the syringe of the electrospinning device, and its injection flow rate was controlled to 0.043 mL/min using an injection pump, the voltage was set at 17 kV, and the stainless steel needle The distance between the needle tip and the roller collector is fixed at about 12 to 13 cm, and the electrospinning process is performed at room temperature, and the electrospinning is collected on the roller collector (the rotation speed is set to 1000 rpm).

最後，將前述所製得之靜電紡絲在500°C下持溫鍛燒1小時，即完成實施例1之複合奈米纖維之製備，藉此令實施例1之複合奈米纖維中摻雜約0.016重量百分比的氧化石墨烯。Finally, the above-prepared electrospinning was calcined at 500°C for 1 hour to complete the preparation of the composite nanofiber of Example 1, thereby doping the composite nanofiber of Example 1 About 0.016 weight percent graphene oxide.

實施例Examples 22 至to 66 之Of 複合奈米纖維Composite nanofiber

實施例2至6之複合奈米纖維所採用的方法及製備實施例1之複合奈米纖維的方法相似，其差異在於：The methods used for the composite nanofibers of Examples 2 to 6 and the method for preparing the composite nanofibers of Example 1 are similar, but the differences are as follows:

於摻雜複合改質材料的步驟及前述步驟相同，其差異在於，在摻雜氧化石墨烯的二氧化鈦溶膠-凝膠溶液中再分別加入8 mg、16 mg、32 mg、48 mg及64 mg的硝酸銀及10 mg的酞菁，持續攪拌1小時，以得到溶液F。接著，將溶液F在60°C於超音波震盪之下持溫加熱1小時，再靜置24小時，以得到摻雜不同比例之銀及氧化石墨烯的二氧化鈦溶膠-凝膠溶液。The steps for doping the composite modified material are the same as the previous steps, the difference is that 8 mg, 16 mg, 32 mg, 48 mg and 64 mg are added to the graphene oxide-doped titanium dioxide sol-gel solution, respectively. Silver nitrate and 10 mg of phthalocyanine were continuously stirred for 1 hour to obtain solution F. Next, the solution F was heated at 60°C under ultrasonic vibration for 1 hour and then allowed to stand for 24 hours to obtain a titanium dioxide sol-gel solution doped with silver and graphene oxide in different proportions.

於進行靜電紡絲製作步驟及鍛燒步驟與前述步驟相同，即完成實施例2至6之複合奈米纖維之製備。其中實施例2至6之複合奈米纖維中依序摻雜0.24重量百分比、0.47重量百分比、0.94重量百分比、1.40重量百分比及1.86重量百分比的銀。The steps of making electrospinning and calcining are the same as the previous steps, that is, the preparation of the composite nanofibers of Examples 2 to 6 is completed. The composite nanofibers of Examples 2 to 6 were doped with 0.24 weight percent, 0.47 weight percent, 0.94 weight percent, 1.40 weight percent, and 1.86 weight percent silver in sequence.

參考例Reference example 1A1A 及實施例And examples 1A1A 至實施例To the embodiment 6A6A 之Of 染料敏化太陽能電池Dye-sensitized solar cell

依序採用參考例1之二氧化鈦奈米顆粒、實施例1至實施例6之複合奈米纖維，依以下相同的配製條件製備光陽極。The titanium dioxide nanoparticles of Reference Example 1 and the composite nanofibers of Example 1 to Example 6 were used in this order, and the photoanode was prepared according to the same formulation conditions below.

首先，將3 g的二氧化鈦奈米顆粒及4.0 mL的去離子水均勻混合，再加入0.15 mL的曲拉通X-100及0.05 mL的乙酸，使用磁力攪拌持續混合24小時，得到含有二氧化鈦奈米顆粒的膠體，將前述二氧化鈦奈米顆粒的膠體以旋轉塗覆法塗佈在氟摻雜氧化錫玻璃上，形成二氧化鈦層。First, uniformly mix 3 g of titanium dioxide nanoparticles and 4.0 mL of deionized water, then add 0.15 mL of Triton X-100 and 0.05 mL of acetic acid, and continue mixing for 24 hours using magnetic stirring to obtain nanoparticles containing titanium dioxide The colloid of the particles is coated on the fluorine-doped tin oxide glass by the spin coating method to form the titanium dioxide layer.

接著，將2 g的二氧化鈦奈米顆粒或前述複合奈米纖維、4.0 mL的去離子水均勻混合，再加入0.4 mL的無水乙醇，使用磁力攪拌持續混合24小時，形成含有二氧化鈦奈米顆粒或含有前述複合奈米纖維的膠體，將前述含有二氧化鈦奈米顆粒或含有前述複合奈米纖維的膠體分別以刮刀法塗佈在前述二氧化鈦層之上，形成具有兩層修飾的光陽極。接著，將前述光陽極以鋁箔包覆，在450°C燒結30分鐘，以分別得到各工作電極。最後，再將前述各工作電極浸泡在3×10 -4M的釕-N719染料中24小時。 Next, uniformly mix 2 g of titanium dioxide nanoparticles or the aforementioned composite nanofibers, 4.0 mL of deionized water, then add 0.4 mL of absolute ethanol, and continue mixing for 24 hours using magnetic stirring to form nanoparticles containing titanium dioxide or containing For the colloid of the composite nanofiber, the colloid containing the nanoparticles of titanium dioxide or the colloid containing the composite nanofibers are respectively applied on the titanium dioxide layer by a doctor blade method to form a photoanode with two-layer modification. Next, the aforementioned photoanode was covered with aluminum foil and sintered at 450°C for 30 minutes to obtain each working electrode. Finally, immerse the aforementioned working electrodes in 3×10 -4 M ruthenium-N719 dye for 24 hours.

接著，將前述工作電極及一鉑電極組裝成一典型的三明治型電池，並注入電解質(碘、碘化鋰)，即完成參考例1A及實施例1A至實施例6A之染料敏化太陽能電池。Next, the aforementioned working electrode and a platinum electrode are assembled into a typical sandwich type battery, and electrolytes (iodine, lithium iodide) are injected to complete the dye-sensitized solar cells of Reference Example 1A and Example 1A to Example 6A.

試驗例Test example 11 ：形貌及含量分析: Analysis of appearance and content

所述參考例1之二氧化鈦顆粒、參考例2之二氧化鈦奈米纖維及實施例1至6之複合奈米纖維使用場發式掃描式電子顯微鏡(field-emission scanning electron microscope，FE-SEM)觀察上述二氧化鈦奈米纖維及複合奈米纖維的型貌。The titanium dioxide particles of Reference Example 1, the titanium dioxide nanofibers of Reference Example 2, and the composite nanofibers of Examples 1 to 6 were observed using a field-emission scanning electron microscope (FE-SEM). The appearance of titanium dioxide nanofibers and composite nanofibers.

由圖1A可以發現，參考例1之二氧化鈦顆粒具有不規則的奈米顆粒狀結構。由圖1B至圖1H可以發現，參考例2之二氧化鈦奈米纖維及實施例1至6之複合奈米纖維在鍛燒後皆具有連續性的結構，其形貌特徵皆為無序排列的絲狀。進一步比對，相較於參考例2之二氧化鈦奈米纖維及實施例1之複合奈米纖維的纖維排列方向皆較為複雜，實施例2至實施例6之複合奈米纖維的纖維排列方向則皆較為平整。由此可見，藉由摻雜銀於複合奈米纖維中能有效提升複合奈米纖維的導電率，可使其在靜電紡絲步驟及鍛燒步驟後能具有較為平整的結構。It can be found from FIG. 1A that the titanium dioxide particles of Reference Example 1 have an irregular nano-particle structure. It can be found from FIGS. 1B to 1H that the titanium dioxide nanofibers of Reference Example 2 and the composite nanofibers of Examples 1 to 6 have a continuous structure after calcination, and their morphological features are randomly arranged filaments shape. For further comparison, the fiber arrangement directions of the titanium dioxide nanofibers of Reference Example 2 and the composite nanofibers of Example 1 are more complicated, and the fiber arrangement directions of the composite nanofibers of Examples 2 to 6 are all Relatively flat. It can be seen that by doping silver in the composite nanofibers, the conductivity of the composite nanofibers can be effectively improved, which can make it have a relatively flat structure after the electrospinning step and the calcination step.

此外，再使用Image J軟體分析參考例2之二氧化鈦奈米纖維及實施例1至6之複合奈米纖維在鍛燒後的直徑。相較於參考例2之二氧化鈦奈米纖維在鍛燒後的直徑為330.52 ± 8.29奈米，實施例1至6之複合奈米纖維皆具有更小的直徑，分別為316.36 ± 5.79奈米、304.62 ± 5.74奈米、283.42 ± 11.61奈米、248.62 ± 14.52奈米、224.70 ± 6.60奈米及203.16 ± 6.16奈米。由此可見，藉由摻雜銀於複合奈米纖維中，可使所製得之複合奈米纖維具有較小的直徑，從而提供較佳的電子傳輸路徑，且其直徑隨銀摻雜量提升而降低，兩者之間呈現負相關。In addition, the diameter of the titanium dioxide nanofibers of Reference Example 2 and the composite nanofibers of Examples 1 to 6 after calcination was analyzed using Image J software. Compared with the diameter of the titanium dioxide nanofibers of Reference Example 2 after calcination is 330.52 ± 8.29 nm, the composite nanofibers of Examples 1 to 6 all have smaller diameters, respectively 316.36 ± 5.79 nm, 304.62 ± 5.74 nm, 283.42 ± 11.61 nm, 248.62 ± 14.52 nm, 224.70 ± 6.60 nm, and 203.16 ± 6.16 nm. It can be seen that by doping silver in the composite nanofibers, the composite nanofibers can be made to have a smaller diameter, thereby providing a better electron transmission path, and its diameter increases with the amount of silver doping While decreasing, there is a negative correlation between the two.

此外，本說明書中另外觀察參考例2A之染料敏化太陽能電池之光陽極中二氧化鈦層及塗佈於其上的二氧化鈦奈米纖維層的厚度。由圖1G可以發現，參考例2A之染料敏化太陽能電池之光陽極中二氧化鈦層的厚度僅為19微米；由圖1H可以發現，參考例2A之染料敏化太陽能電池之光陽極中二氧化鈦奈米纖維層的厚度僅有7微米。由此可見，本創作藉由控制靜電紡絲法條件及鍛燒條件，所製得之複合奈米纖維應用於染料敏化太陽能電池之光陽極能具有良好的緻密性。In addition, the thickness of the titanium dioxide layer and the titanium dioxide nanofiber layer coated thereon in the photoanode of the dye-sensitized solar cell of Reference Example 2A were additionally observed in this specification. It can be found from FIG. 1G that the thickness of the titanium dioxide layer in the photoanode of the dye-sensitized solar cell of Reference Example 2A is only 19 microns; from FIG. 1H, it can be found that the titanium dioxide nanometer in the photoanode of the dye-sensitized solar cell of Reference Example 2A The thickness of the fiber layer is only 7 microns. It can be seen from this that by controlling the conditions of electrospinning and calcination, the composite nanofibers obtained in the application can be used in the photoanode of dye-sensitized solar cells to have good compactness.

進一步地，使用掃描式電子顯微鏡能量色散X射線光譜(scanning electron microscope-energy dispersive X-ray spectroscopy，SEM-EDS)分析參考例2之二氧化鈦奈米纖維、實施例1及實施例6之複合奈米纖維的組成。由圖2A可以發現，參考例2之二氧化鈦奈米纖維係由12.56重量百分比的鈦、45.23重量百分比的碳及42.21重量百分比的氧所組成。由圖2B可以發現，實施例1之複合奈米纖維係由10.65重量百分比的鈦、43.21重量百分比的碳、46.14重量百分比的氧所組成。由圖2C可以發現，實施例6之複合奈米纖維係由22.12重量百分比的鈦、15.24重量百分比的碳、61.92重量百分比的氧及0.72重量百分比的銀所組成。由此可見，實施例6之複合奈米纖維中確實含有銀的組成。Further, scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS) was used to analyze the titanium dioxide nanofibers of Reference Example 2, the composite nanoparticles of Example 1 and Example 6 Composition of fibers. It can be found from FIG. 2A that the titanium dioxide nanofiber of Reference Example 2 is composed of 12.56% by weight of titanium, 45.23% by weight of carbon, and 42.21% by weight of oxygen. It can be found from FIG. 2B that the composite nanofiber of Example 1 is composed of 10.65% by weight of titanium, 43.21% by weight of carbon, and 46.14% by weight of oxygen. It can be found from FIG. 2C that the composite nanofiber of Example 6 is composed of 22.12% by weight of titanium, 15.24% by weight of carbon, 61.92% by weight of oxygen, and 0.72% by weight of silver. This shows that the composite nanofiber of Example 6 does contain silver.

更進一步地，使用穿透式電子顯微鏡(transmission electron microscope，TEM)觀察參考例2之二氧化鈦奈米纖維、實施例1及實施例6之複合奈米纖維的表面型貌。由圖3A至圖3D皆可以發現，參考例2之二氧化鈦奈米纖維、實施例1及實施例6之複合奈米纖維的表面皆存在許多奈米顆粒狀結構，此結果顯示本創作藉由控制靜電紡絲法條件及鍛燒條件，所製得之上述複合奈米纖維皆具有較高的比表面積。再由圖3C可以發現，實施例1之複合奈米纖維的結構內部有呈現不規則的突起，此結果顯示實施例1之複合奈米纖維中確實含有氧化石墨烯的組成。再由圖3A及3D可以發現，實施例6之複合奈米纖維的表面有球形或半球形的突起，此結果顯示實施例6之複合奈米纖維中確實含有銀的組成。Furthermore, the surface morphology of the titanium dioxide nanofibers of Reference Example 2 and the composite nanofibers of Example 1 and Example 6 was observed using a transmission electron microscope (TEM). It can be found from FIGS. 3A to 3D that the titanium dioxide nanofibers of Reference Example 2 and the composite nanofibers of Example 1 and Example 6 all have many nano-granular structures on their surfaces. This result shows that this creation is controlled by The conditions of the electrospinning method and the conditions of calcination make the above-mentioned composite nanofibers have a higher specific surface area. 3C, it can be found that the structure of the composite nanofiber of Example 1 has irregular protrusions. This result shows that the composite nanofiber of Example 1 does contain graphene oxide. 3A and 3D, it can be found that the surface of the composite nanofiber of Example 6 has spherical or hemispherical protrusions. This result shows that the composite nanofiber of Example 6 does contain silver.

最後，再使用比表面積分析儀分析參考例2之二氧化鈦奈米纖維、實施例1至實施例6之複合奈米纖維的比表面積。相較於參考例2之二氧化鈦奈米纖維的比表面積僅有40.16 m 2/g，實施例1之複合奈米纖維具有較高的比表面積為75.58 m 2/g，實施例2至實施例6之複合奈米纖維皆具有更高的比表面積分別為98.45 m 2/g、98.73 m 2/g、99.21 m 2/g、99.69 m 2/g、100.16 m 2/g。由此可見，藉由摻雜氧化石墨烯及銀於複合奈米纖維中，可使複合奈米纖維具有較大的比表面積，從而有助於吸附更多的染料，故使更多的電子因此被激發，且其比表面積隨銀摻雜量提升而提升，兩者之間呈現正相關。 Finally, the specific surface area of the titanium dioxide nanofibers of Reference Example 2 and the composite nanofibers of Examples 1 to 6 was analyzed using a specific surface area analyzer. Compared with the specific surface area of the titanium dioxide nanofibers of Reference Example 2 is only 40.16 m 2 /g, the composite nanofibers of Example 1 have a higher specific surface area of 75.58 m 2 /g, and Examples 2 to 6 the nanofiber composite having a higher specific surface area are respectively 98.45 m 2 /g,98.73 m 2 /g,99.21 m 2 /g,99.69 m 2 /g,100.16 m 2 / g. It can be seen that by doping graphene oxide and silver in the composite nanofibers, the composite nanofibers can have a larger specific surface area, which helps to adsorb more dyes, so that more electrons are therefore Excited, and its specific surface area increases with the amount of silver doping, there is a positive correlation between the two.

試驗例Test example 22 ：: 晶相Crystal phase 分析analysis

所述參考例1之二氧化鈦奈米顆粒、實施例1及實施例6之複合奈米纖維使用X射線衍射儀(X-ray diffractometer，XRD)分析上述二氧化鈦奈米顆粒及複合奈米纖維的晶相結構。根據Joint Committee on Powder Diffraction Standards(JCPDS)標準圖21-1272，當2θ為25.281°、37.800°、48.049°、53.890°及55.060°之衍射峰代表銳鈦礦的結晶面，當2θ為24.9°之衍射峰代表氧化石墨烯的結晶面。The crystal phases of the titanium dioxide nanoparticles of Reference Example 1 and the composite nanofibers of Example 1 and Example 6 were analyzed by X-ray diffractometer (XRD). structure. According to the Joint Committee on Powder Diffraction Standards (JCPDS) standard figure 21-1272, when 2θ is 25.281°, 37.800°, 48.049°, 53.890° and 55.060°, the diffraction peaks represent the crystal surface of anatase, when 2θ is 24.9° The diffraction peak represents the crystal plane of graphene oxide.

由圖4可以發現，相較於參考例1之二氧化鈦奈米顆粒的XRD圖譜，實施例2及實施例6之複合奈米纖維的XRD圖譜中皆可以觀察到2θ為24.9°之衍射峰代表氧化石墨烯的結晶面。由此可見，實施例2及實施例6之複合奈米纖維中確實具有氧化石墨烯的組成。由圖4可以發現，根據JCPDS標準圖04-0783，實施例6之複合奈米纖維的XRD圖譜中可以同時觀察到2θ為38.110°、44.290°、64.430°之衍射峰代表銀的結晶面。由此可見，實施例6之複合奈米纖維中確實具有銀的組成。It can be found from FIG. 4 that, compared with the XRD patterns of the titanium dioxide nanoparticles of Reference Example 1, the XRD patterns of the composite nanofibers of Examples 2 and 6 can be observed with a diffraction peak of 2θ of 24.9° representing oxidation The crystal face of graphene. From this, it can be seen that the composite nanofibers of Examples 2 and 6 do have a composition of graphene oxide. It can be found from FIG. 4 that, according to the JCPDS standard diagram 04-0783, the XRD patterns of the composite nanofibers of Example 6 can be simultaneously observed that the diffraction peaks at 2θ of 38.110°, 44.290°, and 64.430° represent the crystal surface of silver. Thus, it can be seen that the composite nanofiber of Example 6 does have a silver composition.

此外，相較於參考例1之二氧化鈦奈米顆粒的XRD圖譜，實施例2及實施例6之複合奈米纖維的XRD圖譜中2θ為25.281°，37.800°，48.049°，53.890°及59.060°之衍射峰代表銳鈦礦的結晶面的相對強度皆較小。由此可見，藉由摻雜氧化石墨烯及銀於複合奈米纖維中，導致二氧化鈦的銳鈦礦的結晶面降低，從而使複合奈米纖維具有較佳的電子傳輸路徑。In addition, compared to the XRD patterns of the titanium dioxide nanoparticles of Reference Example 1, the XRD patterns of the composite nanofibers of Examples 2 and 6 are 25.281°, 37.800°, 48.049°, 53.890°, and 59.060° Diffraction peaks indicate that the relative intensity of the anatase crystal surface is relatively small. It can be seen that by doping graphene oxide and silver in the composite nanofiber, the crystal surface of the anatase of titanium dioxide is reduced, so that the composite nanofiber has a better electron transmission path.

試驗例Test example 33 ：: 化學結構Chemical structure 分析analysis

所述參考例1之二氧化鈦奈米顆粒、實施例1及實施例6之複合奈米纖維使用拉曼分析儀(Raman spectroscopy，Raman)分析上述二氧化鈦奈米顆粒及複合奈米纖維的化學結構。The chemical structures of the titanium dioxide nanoparticles of Reference Example 1 and the composite nanofibers of Example 1 and Example 6 were analyzed using a Raman spectroscopy (Raman).

由圖5可以發現，參考例1之二氧化鈦奈米顆粒、實施例1及實施例6之複合奈米纖維的拉曼分析圖譜中，可以同時觀察到在149 cm -1、199 cm -1、391 cm -1、509 cm -1及627 cm -1之衍射峰代表銳鈦礦的結晶面。此外，再由圖5可以發現，實施例1及實施例6之複合奈米纖維的拉曼分析圖譜中，可以同時觀察到在約1580 cm -1之衍射峰代表D帶，在約1350 cm -1之衍射峰代表G帶，此結果顯示實施例1及實施例6之複合奈米纖維中確實有氧化石墨烯的組成。 It can be found from FIG. 5 that in the Raman analysis patterns of the titanium dioxide nanoparticles of Reference Example 1 and the composite nanofibers of Example 1 and Example 6, it can be observed at 149 cm -1 , 199 cm -1 , 391 The diffraction peaks of cm -1 , 509 cm -1 and 627 cm -1 represent the crystal surface of anatase. In addition, it can be found from FIG. 5 that in the Raman analysis patterns of the composite nanofibers of Example 1 and Example 6, the diffraction peak at about 1580 cm -1 can be observed to represent the D band at about 1350 cm − The diffraction peak of 1 represents the G band. This result shows that the composite nanofibers of Example 1 and Example 6 do have a graphene oxide composition.

試驗例Test example 44 ：光伏特性分析: Analysis of photovoltaic characteristics

所述參考例1A及實施例1A至6A之染料敏化太陽能電池使用太陽光模擬器及光電轉換效率分析儀分析其光伏特性，其分析結果如圖6A至圖6D及下表1所示。 表1：參考例1A及實施例1A至6A之染料敏化太陽能電池的光伏特性試驗結果

Figure 108139351-A0305-0001
The dye-sensitized solar cells of Reference Example 1A and Examples 1A to 6A were analyzed for their photovoltaic characteristics using a solar simulator and a photoelectric conversion efficiency analyzer. The analysis results are shown in FIGS. 6A to 6D and Table 1 below. Table 1: Photovoltaic characteristic test results of dye-sensitized solar cells of Reference Example 1A and Examples 1A to 6A
Figure 108139351-A0305-0001

由圖6A至圖6D及上表1可以發現，相較於參考例1A之染料敏化太陽能電池的光伏效率僅為約4.03%，實施例1A至實施例6A之染料敏化太陽能電池皆具有較佳的光伏效率分別為約4.46%、4.74%、4.89%、5.07%、5.14%及5.40%。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，因氧化石墨烯及銀皆具有良好的導電性質，故能具體改善電子傳輸；同時，由試驗例1的結果可以發現，藉由在複合奈米纖維中摻雜銀的複合奈米纖維(實施例2至實施例6)在鍛燒後能提升其比表面積，從而有助於吸附更多的染料，故能提升被激發的電子數，進而能提升複合奈米纖維應用於染料敏化太陽能電池的光伏特性。It can be found from FIGS. 6A to 6D and Table 1 above that the photovoltaic efficiency of the dye-sensitized solar cell of Reference Example 1A is only about 4.03%, and the dye-sensitized solar cells of Example 1A to Example 6A have The best photovoltaic efficiency is about 4.46%, 4.74%, 4.89%, 5.07%, 5.14% and 5.40%, respectively. It can be seen that by doping graphene oxide and silver in the composite nanofiber, since both graphene oxide and silver have good conductive properties, they can specifically improve electron transmission; at the same time, it can be found from the results of Test Example 1 , The composite nanofibers (Examples 2 to 6) doped with silver in the composite nanofibers can increase the specific surface area after calcination, thereby helping to adsorb more dye, so it can enhance the The number of excited electrons can further improve the photovoltaic properties of composite nanofibers used in dye-sensitized solar cells.

試驗例Test example 55 ：光電轉換效率分析：Analysis of photoelectric conversion efficiency

所述參考例1A、實施例1A及實施例6A之染料敏化太陽能電池使用太陽光模擬器分析其光電轉換效率。The dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A were analyzed for their photoelectric conversion efficiency using a solar simulator.

由圖7可以發現，相較於參考例1A之染料敏化太陽能電池的光電轉換效率僅為36.00%，實施例1A之染料敏化太陽能電池具有較高的光電轉換效率為41.92%，實施例6A之染料敏化太陽能電池具有更高的光電轉換效率為55.67%。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，能有助於提升複合奈米纖維應用於染料敏化太陽能電池的光電轉換效率。It can be found from FIG. 7 that the photoelectric conversion efficiency of the dye-sensitized solar cell of Reference Example 1A is only 36.00%, and the dye-sensitized solar cell of Example 1A has a higher photoelectric conversion efficiency of 41.92%, and Example 6A The dye-sensitized solar cell has a higher photoelectric conversion efficiency of 55.67%. It can be seen that by doping graphene oxide and silver in the composite nanofibers, it can help to improve the photoelectric conversion efficiency of the composite nanofibers used in dye-sensitized solar cells.

試驗例Test example 66 ：吸收波長分析: Absorption wavelength analysis

所述參考例1A、實施例1A及實施例6A之染料敏化太陽能電池使用紫外光-可見光分光光度計分析其吸收波長範圍。The dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A were analyzed for their absorption wavelength range using an ultraviolet-visible light spectrophotometer.

由圖8可以發現，在350奈米及550奈米的可見光吸收波長範圍，相較於參考例1A之染料敏化太陽能電池的吸收值，實施例1A及實施例6A之染料敏化太陽能電池皆具有較高的吸收值；換句話說，實施例1A及實施例6A之染料敏化太陽能電池能吸收更多的可見光。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，可提升複合奈米纖維的比表面積(對應試驗例1的結果)，從而能使更多的染料被吸附，故可吸收更多的可見光，使更多的電子被激發，因此改善電流密度，進而提升染料敏化太陽能電池的光伏特性及光電轉換效率(對應試驗例4及試驗例5的結果)。It can be found from FIG. 8 that in the visible light absorption wavelength range of 350 nm and 550 nm, the dye-sensitized solar cells of Example 1A and Example 6A are both compared to the absorption values of the dye-sensitized solar cells of Reference Example 1A. It has a higher absorption value; in other words, the dye-sensitized solar cells of Example 1A and Example 6A can absorb more visible light. It can be seen that by doping graphene oxide and silver in the composite nanofiber, the specific surface area of the composite nanofiber (corresponding to the result of Test Example 1) can be increased, so that more dye can be adsorbed, so it is possible It absorbs more visible light and causes more electrons to be excited, thus improving the current density, thereby improving the photovoltaic characteristics and photoelectric conversion efficiency of the dye-sensitized solar cell (corresponding to the results of Test Examples 4 and 5).

試驗例Test example 77 ：: 電化學阻抗譜Electrochemical impedance spectroscopy 分析analysis

所述參考例1A、實施例1A及實施例6A之染料敏化太陽能電池使用電化學阻抗譜分析其電化學特性，其結果如圖9及下表2所示，其中R S代表氟摻雜氧化錫玻璃及半導體薄膜層之間的電阻，R 1代表鉑電極及電解質之間的電阻，R 2代表光陽極與染料及電解質之間的電阻。 表2：參考例1A、實施例1A及實施例6A之染料敏化太陽能電池的電化學阻抗譜試驗結果

Figure 108139351-A0305-0002
The dye-sensitized solar cells of Reference Example 1A, Example 1A and Example 6A were analyzed for their electrochemical characteristics using electrochemical impedance spectroscopy. The results are shown in FIG. 9 and Table 2 below, where R S represents fluorine-doped oxidation Resistance between tin glass and semiconductor thin film layer, R 1 represents resistance between platinum electrode and electrolyte, R 2 represents resistance between photoanode and dye and electrolyte. Table 2: Electrochemical impedance spectroscopy test results of the dye-sensitized solar cells of Reference Example 1A, Example 1A and Example 6A
Figure 108139351-A0305-0002

由圖9及上表2可以發現，相較於參考例1A之染料敏化太陽能電池的R 2值，實施例1A及實施例6A之染料敏化太陽能電池皆具有較高的R 2值分別為18.64 Ω、27.55 Ω。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，能促使介面(光陽極與染料及電解質之間)的阻抗提升，從而減少電子復合的情形，進而提升染料敏化太陽能電池的光伏特性及光電轉換效率(對應試驗例4及試驗例5的結果)。 It can be found from FIG. 9 and Table 2 above that, compared to the R 2 value of the dye-sensitized solar cell of Reference Example 1A, the dye-sensitized solar cells of Example 1A and Example 6A have higher R 2 values respectively: 18.64 Ω, 27.55 Ω. It can be seen that by doping graphene oxide and silver in the composite nanofiber, the impedance of the interface (between the photoanode and the dye and the electrolyte) can be increased, thereby reducing the situation of electronic recombination and further improving the dye-sensitized solar energy. The photovoltaic characteristics and photoelectric conversion efficiency of the battery (corresponding to the results of Test Example 4 and Test Example 5).

試驗例Test example 88 ：光照強度分析: Light intensity analysis

所述參考例1A、實施例1A及實施例6A之染料敏化太陽能電池使用太陽光模擬器及光電轉換效率分析儀在不同光照強度下分析其光伏特性，其結果如圖10A至10C及下表3所示。 表3：參考例1A、實施例1A及實施6A之染料敏化太陽能電池在不同光照強度下的光伏特性試驗結果

Figure 108139351-A0305-0003
The dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A were analyzed for their photovoltaic characteristics under different light intensities using a solar simulator and a photoelectric conversion efficiency analyzer. The results are shown in FIGS. 10A to 10C and the table below 3 shown. Table 3: Test results of the photovoltaic characteristics of the dye-sensitized solar cells of Reference Example 1A, Example 1A and Example 6A under different light intensities
Figure 108139351-A0305-0003

由圖10A至10C及上表3可以發現，相較於參考例1A之染料敏化太陽能電池在光照強度為100、80、50、30、10毫瓦特/平方公分(milliwatt/ square centimeter，mW/cm 2)時的光伏效率，實施例1A及實施例6A之染料敏化太陽能電池在光照強度為100、80、50、30、10 mW/cm 2時皆具有較高的光伏效率。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，可提升複合奈米纖維的比表面積(對應試驗例1的結果)，從而能使更多的染料被吸附，故可吸收更多的可見光，使更多的電子被激發，因此改善電流密度，進而提升染料敏化太陽能電池在不同光照強度下的光伏特性。 From FIGS. 10A to 10C and Table 3 above, it can be found that the dye-sensitized solar cell of Reference Example 1A has a light intensity of 100, 80, 50, 30, and 10 milliwatts/square centimeter (mW/ cm 2 ), the dye-sensitized solar cells of Example 1A and Example 6A have higher photovoltaic efficiency when the light intensity is 100, 80, 50, 30, 10 mW/cm 2 . It can be seen that by doping graphene oxide and silver in the composite nanofiber, the specific surface area of the composite nanofiber (corresponding to the result of Test Example 1) can be increased, so that more dye can be adsorbed, so it is possible Absorb more visible light and make more electrons excited, thus improving the current density, and thus improving the photovoltaic characteristics of dye-sensitized solar cells under different light intensities.

進一步地，由圖10A至10C及上表3可以發現，參考例1A、實施例1A及實施例6A之染料敏化太陽能電池在光照強度為30 mW/cm 2時皆具有最佳的光伏效率，且其光伏效率隨光照強度由30 mW/cm 2往上提升而降低，兩者之間呈現負相關；反之，其光伏效率隨光照強度由30 mW/cm 2往下降低而降低，兩者之間呈現正相關。由此可見，在低光照強度下，因光生電子的數量較少，故可減少電子復合的情形，進而提升染料敏化太陽能電池的光伏特性；然而，在過低的光照強度下，因光生電子的數量過少，反而降低染料敏化太陽能電池的光伏特性。 Further, from FIGS. 10A to 10C and Table 3 above, it can be found that the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A have the best photovoltaic efficiency when the light intensity is 30 mW/cm 2 , And its photovoltaic efficiency decreases as the light intensity increases from 30 mW/cm 2 upward, and there is a negative correlation between the two; on the contrary, its photovoltaic efficiency decreases as the light intensity decreases from 30 mW/cm 2 downward. Showed a positive correlation. It can be seen that under low light intensity, due to the small number of photo-generated electrons, the recombination of electrons can be reduced, thereby improving the photovoltaic characteristics of dye-sensitized solar cells; however, under too low light intensity, due to photo-generated electrons The number is too small, but instead reduces the photovoltaic characteristics of dye-sensitized solar cells.

更進一步地，所述參考例1A、實施例1A及實施例6A之染料敏化太陽能電池使用電化學阻抗譜分析其電化學特性，其結果如圖11A至11B及下表4所示，其中R S代表氟摻雜氧化錫玻璃及半導體薄膜層之間的電阻，R 1代表鉑電極及電解質之間的電阻，R 2代表光陽極與染料及電解質之間的電阻。 表4：參考例1A、實施例1A及實施例6A之染料敏化太陽能電池在不同光照強度下的電化學阻抗譜試驗結果

Figure 108139351-A0305-0004
Furthermore, the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A were analyzed for their electrochemical characteristics using electrochemical impedance spectroscopy. The results are shown in FIGS. 11A to 11B and Table 4 below, where R S represents the resistance between the fluorine-doped tin oxide glass and the semiconductor thin film layer, R 1 represents the resistance between the platinum electrode and the electrolyte, and R 2 represents the resistance between the photoanode and the dye and the electrolyte. Table 4: Electrochemical impedance spectroscopy test results of dye-sensitized solar cells of Reference Example 1A, Example 1A and Example 6A under different light intensities
Figure 108139351-A0305-0004

由圖11A至11B及上表4可以發現，相較於參考例1A之染料敏化太陽能電池在光照強度為100、80、50、30、10 mW/cm 2時的R 2值，實施例1A及實施例6A之染料敏化太陽能電池在光照強度為100、80、50、30、10 mW/cm 2時皆具有較高的R 2值。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，能在不同光照強度下促使介面(光陽極與染料及電解質之間)的阻抗提升，從而減少電子復合的情形，進而提升染料敏化太陽能電池的光伏特性。 From FIGS. 11A to 11B and Table 4 above, it can be found that the R 2 value of the dye-sensitized solar cell of Reference Example 1A when the light intensity is 100, 80, 50, 30, 10 mW/cm 2 , Example 1A And the dye-sensitized solar cell of Example 6A has a higher R 2 value when the light intensity is 100, 80, 50, 30, 10 mW/cm 2 . It can be seen that by doping graphene oxide and silver in the composite nanofiber, the impedance of the interface (between the photoanode and the dye and electrolyte) can be increased under different light intensities, thereby reducing the situation of electronic recombination, and Improve the photovoltaic characteristics of dye-sensitized solar cells.

此外，參考例1A、實施例1A及實施6A之染料敏化太陽能電池在光照強度為10 mW/cm 2時皆具有最高的R 2值，且其R 2值隨光照強度提升而降低，兩者之間呈現負相關。由此可見，在過低的光照強度下，因光生電子的數量過少，從而使介面(光陽極與染料及電解質之間)的阻抗過高，反而降低染料敏化太陽能電池的光伏特性。 In addition, the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Implementation 6A all have the highest R 2 value when the light intensity is 10 mW/cm 2 , and their R 2 value decreases as the light intensity increases, both Show a negative correlation. It can be seen that under too low light intensity, the number of photo-generated electrons is too small, so that the impedance of the interface (between the photoanode and the dye and electrolyte) is too high, but instead reduces the photovoltaic characteristics of the dye-sensitized solar cell.

試驗例Test example 99 ：螢光燈照射分析: Fluorescent lamp irradiation analysis

所述參考例1A、實施例1A及實施例6A之染料敏化太陽能電池使用T5螢光燈照明設備及光電轉換效率分析儀分析其光伏特性，其結果如圖12及下表5所示。 表5：參考例1A、實施例1A及實施例6A之染料敏化太陽能電池在不同螢光燈照射強度下的光伏特性試驗結果

Figure 108139351-A0305-0005
The dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A were analyzed for their photovoltaic characteristics using T5 fluorescent lamp lighting equipment and a photoelectric conversion efficiency analyzer. The results are shown in FIG. 12 and Table 5 below. Table 5: Photovoltaic characteristic test results of the dye-sensitized solar cells of Reference Example 1A, Example 1A and Example 6A under different fluorescent lamp irradiation intensity
Figure 108139351-A0305-0005

由圖12及上表5可以發現，相較於參考例1A之染料敏化太陽能電池在螢光燈照射強度為1.75、1.36、0.85、0.51、0.17 mW/cm 2時的光伏效率，實施例1A及實施例6A之染料敏化太陽能電池在螢光燈照射強度為1.75、1.36、0.85、0.51、0.17 mW/cm 2時皆具有較高的光伏效率。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，可提升複合奈米纖維的比表面積(對應試驗例1的結果)，從而能使更多的染料被吸附，故可吸收更多的螢光，使更多的電子被激發，因此改善電流密度，進而提升染料敏化太陽能電池在不同螢光燈照射強度下的光伏特性。進言之，本創作之染料敏化太陽能電池不僅得以應用於低太陽光照射之環境下，也得以應用於室內其他光源照射之環境下(例如：螢光燈)。 It can be found from FIG. 12 and Table 5 above that the photovoltaic efficiency of the dye-sensitized solar cell of Reference Example 1A when the irradiation intensity of the fluorescent lamp is 1.75, 1.36, 0.85, 0.51, 0.17 mW/cm 2 , Example 1A And the dye-sensitized solar cell of Example 6A has higher photovoltaic efficiency when the fluorescent lamp irradiation intensity is 1.75, 1.36, 0.85, 0.51, 0.17 mW/cm 2 . It can be seen that by doping graphene oxide and silver in the composite nanofiber, the specific surface area of the composite nanofiber (corresponding to the result of Test Example 1) can be increased, so that more dye can be adsorbed, so it is possible Absorb more fluorescent light, so that more electrons are excited, so improve the current density, and thus improve the photovoltaic characteristics of dye-sensitized solar cells under different fluorescent lamp irradiation intensity. In other words, the dye-sensitized solar cell of this creation can be used not only in the environment with low sunlight, but also in the environment with other light sources indoors (for example: fluorescent lamps).

此外，參考例1A、實施例1A及實施例6A之染料敏化太陽能電池在螢光燈照射強度為0.51 mW/cm 2時皆具有最佳的光伏效率，且其光伏效率隨螢光燈照射強度由0.51 mW/cm 2往上提升而降低，兩者之間呈現負相關；反之，其光伏效率隨螢光燈照射強度由0.51 mW/cm 2往下降低而降低，兩者之間呈現正相關。由此可見，在低螢光燈照射強度下，因光生電子的數量較少，故可減少電子復合的情形，進而提升染料敏化太陽能電池的光伏特性；然而，在過低的螢光燈照射強度下，因光生電子的數量過少，反而降低染料敏化太陽能電池的光伏特性。 In addition, the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A have the best photovoltaic efficiency when the fluorescent lamp irradiation intensity is 0.51 mW/cm 2 , and their photovoltaic efficiency varies with the fluorescent lamp irradiation intensity It increases from 0.51 mW/cm 2 upward and decreases, and there is a negative correlation between the two; on the contrary, its photovoltaic efficiency decreases as the fluorescent lamp irradiation intensity decreases from 0.51 mW/cm 2 downward, and there is a positive correlation between the two. . It can be seen that under low fluorescent lamp irradiation intensity, because the number of photo-generated electrons is small, the situation of electron recombination can be reduced, thereby improving the photovoltaic characteristics of dye-sensitized solar cells; however, under too low fluorescent lamp irradiation Under the intensity, because the number of photo-generated electrons is too small, the photovoltaic characteristics of the dye-sensitized solar cell are reduced.

更進一步地，所述參考例1A及實施例6A之染料敏化太陽能電池使用電化學阻抗譜分析其電化學特性，其結果如圖13A至13B及下表6所示，其中R S代表氟摻雜氧化錫玻璃及半導體薄膜層之間的電阻，R 1代表鉑電極及電解質之間的電阻，R 2代表光陽極與染料及電解質之間的電阻。 表6：參考例1A及實施例6A之染料敏化太陽能電池在不同螢光燈照射強度下的電化學阻抗譜試驗結果

Figure 108139351-A0305-0006
Furthermore, the dye-sensitized solar cells of Reference Example 1A and Example 6A were analyzed for their electrochemical characteristics using electrochemical impedance spectroscopy. The results are shown in FIGS. 13A to 13B and Table 6 below, where R S represents fluorine-doped The resistance between the tin oxide glass and the semiconductor thin film layer, R 1 represents the resistance between the platinum electrode and the electrolyte, and R 2 represents the resistance between the photoanode and the dye and the electrolyte. Table 6: Electrochemical impedance spectroscopy test results of the dye-sensitized solar cells of Reference Example 1A and Example 6A under different fluorescent lamp irradiation intensity
Figure 108139351-A0305-0006

由圖13A至13B及上表6可以發現，相較於參考例1A之染料敏化太陽能電池在螢光燈照射強度為100、80、50、30、10 mW/cm 2時的R 2值，實施例6A之染料敏化太陽能電池在螢光燈照射強度為100、80、50、30、10 mW/cm 2時皆具有較高的R 2值。由此可見，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，能在不同螢光燈照射強度下促使介面(光陽極與染料及電解質之間)的阻抗提升，從而減少電子復合的情形，進而提升染料敏化太陽能電池的光伏特性。 It can be found from FIGS. 13A to 13B and Table 6 above that the R 2 value of the dye-sensitized solar cell of Reference Example 1A when the irradiation intensity of the fluorescent lamp is 100, 80, 50, 30, 10 mW/cm 2 , The dye-sensitized solar cell of Example 6A has a higher R 2 value when the fluorescent lamp irradiation intensity is 100, 80, 50, 30, or 10 mW/cm 2 . It can be seen that by doping graphene oxide and silver in the composite nanofiber, the impedance of the interface (between the photoanode and the dye and the electrolyte) can be increased under different fluorescent lamp irradiation intensity, thereby reducing the electronic composite Situation, which in turn improves the photovoltaic characteristics of dye-sensitized solar cells.

此外，參考例1A及實施6A之染料敏化太陽能電池在螢光燈照射強度為10 mW/cm 2時皆具有最高的R 2值，且其R 2值隨螢光燈照射強度提升而降低，兩者之間呈現負相關。由此可見，在過低的螢光燈照射強度下，因光生電子的數量過少，從而使介面(光陽極與染料及電解質之間)的阻抗過高，反而降低染料敏化太陽能電池的光伏特性。 In addition, the dye-sensitized solar cells of Reference Example 1A and 6A have the highest R 2 value when the fluorescent lamp irradiation intensity is 10 mW/cm 2 , and the R 2 value decreases as the fluorescent lamp irradiation intensity increases. There is a negative correlation between the two. It can be seen that under too low the intensity of fluorescent lamp irradiation, the number of photo-generated electrons is too small, so that the impedance of the interface (between the photoanode and the dye and electrolyte) is too high, but instead reduces the photovoltaic characteristics of the dye-sensitized solar cell .

綜合上述試驗例1至試驗例9之分析結果均顯示，藉由在複合奈米纖維中摻雜氧化石墨烯及銀，其所製得之複合奈米纖維具有較大的比表面積、直徑較小等優點，從而使該複合奈米纖維應用於染料敏化太陽能電池之光陽極中能減少電子復合的情形，進而提升染料敏化太陽能電池之光伏特性及光電轉換效率。According to the analysis results of the above Test Example 1 to Test Example 9, the composite nanofibers prepared by doping graphene oxide and silver in the composite nanofibers have larger specific surface area and smaller diameter And other advantages, so that the use of the composite nanofiber in the photoanode of the dye-sensitized solar cell can reduce the situation of electronic recombination, thereby improving the photovoltaic characteristics and photoelectric conversion efficiency of the dye-sensitized solar cell.

上述之實施例僅係為說明書創作之例示，並非於任何方面限制本創作主張之權利範圍。本創作所主張之權利範圍自應以申請專利範圍所述為準，而非僅限於上述具體實施例。The above-mentioned embodiments are only examples of the creation of the specification, and do not limit the scope of the rights claimed by the creation in any way. The scope of the rights claimed in this creation should be subject to the scope of the patent application, and not limited to the above specific embodiments.

無。no.

圖1A係參考例1之二氧化鈦奈米顆粒的掃描式電子顯微鏡的照片，圖1B係參考例2之二氧化鈦奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1C係實施例1之複合奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1D係實施例2之複合奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1E係實施例3之複合奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1F係實施例4之複合奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1G係實施例5之複合奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1H係實施例6之複合奈米纖維在鍛燒後的掃描式電子顯微鏡的照片，圖1I係參考例2A之染料敏化太陽能電池之光陽極中二氧化鈦層的掃描式電子顯微鏡的照片，圖1J係參考例2A之染料敏化太陽能電池之光陽極中二氧化鈦奈米纖維層的掃描式電子顯微鏡的照片。 圖2A係參考例2之二氧化鈦奈米纖維的能量色散X射線光譜圖，圖2B係實施例1之複合奈米纖維的能量色散X射線光譜圖，圖2C係實施例6之複合奈米纖維的能量色散X射線光譜圖。 圖3A係實施例6之複合奈米纖維的穿透式電子顯微鏡的照片，圖3B係參考例2之二氧化鈦奈米纖維的穿透式電子顯微鏡的照片，圖3C係實施例1之複合奈米纖維的穿透式電子顯微鏡的照片，圖3D係實施例6之複合奈米纖維的穿透式電子顯微鏡的照片。 圖4由下至上分別係參考例1之二氧化鈦奈米顆粒、實施例1及實施例6之複合奈米纖維的X射線衍射儀圖譜。 圖5由下至上分別係參考例1之二氧化鈦奈米顆粒、實施例1及實施例6之複合奈米纖維的拉曼分析圖譜。 圖6A係參考例1A之染料敏化太陽能電池在光照射下的電流密度及電壓的關係圖，圖6B係參考例1A及實施例1A之染料敏化太陽能電池在光照射下的電流密度及電壓的關係圖，圖6C係實施例2A至實施例6A之染料敏化太陽能電池在光照射下的電流密度及電壓的關係圖，圖6D係參考例1A、實施例1A及實施例6A之染料敏化太陽能電池在光照射下的電流密度及電壓的關係圖。 圖7係參考例1A、實施例1A及實施例6A之染料敏化太陽能電池的光電轉換效率圖譜。 圖8係參考例1A、實施例1A及實施例6A之染料敏化太陽能電池的紫外光-可見光吸收光譜圖。 圖9係參考例1A、實施例1A及實施例6A之染料敏化太陽能電池的奈奎斯特圖。 圖10A係參考例1A之染料敏化太陽能電池在不同光照強度下的電流密度及電壓的關係圖，圖10B係實施例1A之染料敏化太陽能電池在不同光照強度下的電流密度及電壓的關係圖，圖10C係實施例6A之染料敏化太陽能電池在不同光照強度下的電流密度及電壓的關係圖。 圖11A係參考例1A之染料敏化太陽能電池在不同光照強度下的奈奎斯特圖，圖11B係實施例1A之染料敏化太陽能電池在不同光照強度下的奈奎斯特圖，圖11C係實施例6A之染料敏化太陽能電池在不同光照強度下的奈奎斯特圖。 圖12係實施例6A之染料敏化太陽能電池在不同螢光燈照射強度下的電流密度及電壓的關係圖。 圖13A係參考例1A之染料敏化太陽能電池在不同螢光燈照射強度下的奈奎斯特圖，圖13B係實施例6A之染料敏化太陽能電池在不同螢光燈照射強度下的奈奎斯特圖。 1A is a scanning electron microscope photograph of titanium dioxide nanoparticles of Reference Example 1, FIG. 1B is a scanning electron microscope photograph of titanium dioxide nanofibers of Reference Example 2 after calcination, and FIG. 1C is a composite of Example 1 Scanning electron microscope photographs of nanofibers after calcination, Figure 1D is a scanning electron microscope photograph of composite nanofibers of Example 2 and Figure 1E is composite nanofibers of Example 3 Scanning electron microscope photographs after calcination, Figure 1F is the scanning electron microscope photographs of the composite nanofibers of Example 4 after calcination, and Figure 1G is the composite nanofibers of Example 5 after calcination Scanning electron microscope photograph, Figure 1H is a scanning electron microscope photograph of the composite nanofiber of Example 6 after calcination, and Figure 1I is a scan of the titanium dioxide layer in the photoanode of the dye-sensitized solar cell of Reference Example 2A 1J is a scanning electron microscope photograph of the titanium dioxide nanofiber layer in the photoanode of the dye-sensitized solar cell of Reference Example 2A. 2A is the energy dispersive X-ray spectrum of the titanium dioxide nanofiber of Reference Example 2, FIG. 2B is the energy dispersive X-ray spectrum of the composite nanofiber of Example 1, and FIG. 2C is the composite nanofiber of Example 6 Energy dispersive X-ray spectrogram. 3A is a photograph of a transmission electron microscope of composite nanofibers of Example 6, FIG. 3B is a photograph of a transmission electron microscope of titanium dioxide nanofibers of Reference Example 2, and FIG. 3C is a composite nanometer of Example 1 The photograph of the transmission electron microscope of the fiber, FIG. 3D is the photograph of the transmission electron microscope of the composite nanofiber of Example 6. 4 is an X-ray diffractometer pattern of the titanium dioxide nanoparticles of Reference Example 1 and the composite nanofibers of Example 1 and Example 6 from bottom to top. 5 is the Raman analysis chart of the titanium dioxide nanoparticles of Reference Example 1, the composite nanofibers of Example 1 and Example 6 from bottom to top. FIG. 6A is a relation diagram of current density and voltage of the dye-sensitized solar cell of Reference Example 1A under light irradiation, and FIG. 6B is current density and voltage of the dye-sensitized solar cell of Reference Example 1A and Example 1A under light irradiation 6C is a graph of the current density and voltage of the dye-sensitized solar cells of Example 2A to Example 6A under light irradiation, and FIG. 6D is the dye-sensitivity of Reference Example 1A, Example 1A, and Example 6A The relationship between the current density and voltage of a solar cell under light irradiation. 7 is a graph of the photoelectric conversion efficiency of the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A. 8 is an ultraviolet-visible absorption spectrum chart of the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A. 9 is a Nyquist diagram of the dye-sensitized solar cells of Reference Example 1A, Example 1A, and Example 6A. FIG. 10A is a graph of the relationship between the current density and voltage of the dye-sensitized solar cell of Reference Example 1A under different light intensities, and FIG. 10B is a graph of the relationship between the current density and voltage of the dye-sensitized solar cell of Example 1A under different light intensities. 10C is a graph showing the relationship between the current density and voltage of the dye-sensitized solar cell of Example 6A under different light intensities. 11A is the Nyquist diagram of the dye-sensitized solar cell of Reference Example 1A under different light intensities, FIG. 11B is the Nyquist diagram of the dye-sensitized solar cell of Example 1A under different light intensities, FIG. 11C It is the Nyquist diagram of the dye-sensitized solar cell of Example 6A under different light intensities. 12 is a graph showing the relationship between the current density and voltage of the dye-sensitized solar cell of Example 6A under different fluorescent lamp irradiation intensities. 13A is the Nyquist diagram of the dye-sensitized solar cell of Reference Example 1A under different fluorescent lamp irradiation intensity, and FIG. 13B is the Nyquist of the dye-sensitized solar cell of Example 6A under different fluorescent lamp irradiation intensity Stertu.

無。no.

Claims (9)

一種複合奈米纖維，其包括一二氧化鈦奈米纖維及一氧化石墨烯；以該複合奈米纖維之總重為基準，該氧化石墨烯之含量大於0重量百分比且小於或等於0.016重量百分比；其中該複合奈米纖維的直徑大於或等於180奈米且小於或等於350奈米，複合奈米纖維的比表面積大於或等於70 m 2/g且小於或等於120 m 2/g。 A composite nanofiber including a titanium dioxide nanofiber and graphene oxide; based on the total weight of the composite nanofiber, the content of the graphene oxide is greater than 0 weight percent and less than or equal to 0.016 weight percent; wherein The diameter of the composite nanofiber is greater than or equal to 180 nanometers and less than or equal to 350 nanometers, and the specific surface area of the composite nanofiber is greater than or equal to 70 m 2 /g and less than or equal to 120 m 2 /g. 如請求項1所述之複合奈米纖維，其中該複合奈米纖維包含一銀。The composite nanofiber according to claim 1, wherein the composite nanofiber contains one silver. 如請求項2所述之複合奈米纖維，其中以該複合奈米纖維之總重為基準，該銀之含量大於0重量百分比且小於或等於1.9重量百分比，該氧化石墨烯及該銀之總含量大於或等於0.2重量百分比且小於或等於1.91重量百分比。The composite nanofiber according to claim 2, wherein based on the total weight of the composite nanofiber, the silver content is greater than 0 weight percent and less than or equal to 1.9 weight percent, the total of the graphene oxide and the silver The content is greater than or equal to 0.2 weight percent and less than or equal to 1.91 weight percent. 如請求項1所述之複合奈米纖維，其中該二氧化鈦奈米纖維的晶相含有鋭鈦礦、金紅石或其組合。The composite nanofiber according to claim 1, wherein the crystalline phase of the titanium dioxide nanofiber contains brookite, rutile, or a combination thereof. 一種複合奈米纖維之製法，其包括以下步驟： 步驟(a)：於一極性有機溶劑之存在下，令異丙醇鈦混合氧化石墨烯，以獲得一膠體溶液；以該膠體溶液之總重為基準，該氧化石墨烯之含量大於0重量百分比且小於或等於0.016重量百分比； 步驟(b)：令該膠體溶液進行靜電紡絲法，得到一靜電紡絲產物；以及 步驟(c)：令該靜電紡絲產物於大於或等於450°C且小於或等於600°C之溫度下，持續鍛燒1小時以上，以製得一複合奈米纖維。 A method for preparing composite nanofibers includes the following steps: Step (a): mixing titanium isopropoxide with graphene oxide in the presence of a polar organic solvent to obtain a colloidal solution; based on the total weight of the colloidal solution, the content of the graphene oxide is greater than 0 weight percent And less than or equal to 0.016 weight percent; Step (b): subject the colloidal solution to electrospinning to obtain an electrospinning product; and Step (c): The electrospinning product is continuously calcined at a temperature greater than or equal to 450°C and less than or equal to 600°C for more than 1 hour to obtain a composite nanofiber. 如請求項5所述之製法，其中該膠體溶液包含銀。The method according to claim 5, wherein the colloidal solution contains silver. 如請求項5所述之製法，其中以該膠體溶液之總重為基準，該銀之含量大於0重量百分比且小於或等於1.9重量百分比，該氧化石墨烯及該銀之總含量大於或等於0.2重量百分比且小於或等於1.91重量百分比。The manufacturing method according to claim 5, wherein the total content of the silver is greater than 0 weight percent and less than or equal to 1.9 weight percent based on the total weight of the colloidal solution, and the total content of the graphene oxide and the silver is greater than or equal to 0.2 Weight percent and less than or equal to 1.91 weight percent. 一種光陽極，其係包括如請求項1至4中任一項所述之複合奈米纖維以及一導電基板，該複合奈米纖維形成於該導電基板上。A photoanode comprising the composite nanofibers according to any one of claims 1 to 4 and a conductive substrate, the composite nanofibers formed on the conductive substrate. 一種染料敏化太陽能電池，其包括如請求項8所述之光陽極。A dye-sensitized solar cell comprising the photoanode described in claim 8.
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WO2009061685A1 (en) * 2007-11-05 2009-05-14 Nanotek Instruments, Inc. Nano graphene platelet-based composite anode compositions for lithium ion batteries
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