TWI554470B - Preparation of composite materials for supercapacitors - Google Patents
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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
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Description
本創作關於一種用於超級電容之複合材料的製備方法。 This work relates to a method of preparing a composite material for a supercapacitor.
現代社會對於石化能源的依賴與日俱增，但過度使用石化能源將導致能源枯竭、環境污染和氣候變化等問題；近年隨環保意識抬頭，取代石化能源之再生能源如太陽能、風力、水力、地熱、潮汐及生質能等的相關技術也隨之蓬勃發展。 Modern society's dependence on petrochemical energy is increasing day by day. However, excessive use of petrochemical energy will lead to problems such as energy depletion, environmental pollution and climate change. In recent years, with the awareness of environmental protection, renewable energy such as solar energy, wind power, hydropower, geothermal heat and tides have been replaced by petrochemical energy. Related technologies such as biomass and energy have also flourished.
然，由於氣候的變化難以掌握，常使得再生能源的使用上受限於空間和天候的因素；為了有效的將再生能源分配使用，儲能元件的開發也因應而生。 However, due to the difficulty of climate change, the use of renewable energy is often limited by space and weather factors; in order to effectively allocate and use renewable energy, the development of energy storage components has also emerged.
而超級電容(super capacitor)之高電容值、高能量密度、高功率密度以及高循環壽命，使得其成為極具潛力之儲電元件；又超級電容之電容值、能量密度與功率密度均受到超級電容中選用之電極材料的影響，因此尋找適合應用於超級電容之電極材料係為業界積極發展的目標。 The high capacitance value, high energy density, high power density and high cycle life of the super capacitor make it a potential storage element; the capacitance value, energy density and power density of the super capacitor are all super The influence of the electrode material selected in the capacitor, so finding an electrode material suitable for use in a super capacitor is an actively developed target of the industry.
本創作之目的在於提供一種適合應用於超級電容之電極材料。 The purpose of this creation is to provide an electrode material suitable for use in supercapacitors.
本創作提供一種用於超級電容之複合材料的 製備方法，其包含：齊備氧化石墨烯溶液，氧化石墨烯溶液包含氧化石墨烯；齊備二氧化鈦溶液，二氧化鈦溶液包含二氧化鈦；混合氧化石墨烯溶液與二氧化鈦溶液，以得混合溶液，混合溶液包含氧化石墨烯與二氧化鈦，氧化石墨烯與二氧化鈦之重量比為1：1至1：2.5；以紫外光照射該混合溶液，以得複合材料溶液，複合材料溶液包含還原石墨烯與二氧化鈦；乾燥複合材料溶液，以得複合材料，複合材料包含還原石墨烯與二氧化鈦。 This creation provides a composite material for supercapacitors The preparation method comprises: preparing a graphene oxide solution, the graphene oxide solution comprises graphene oxide; preparing a titania solution, the titania solution comprises titanium dioxide; mixing the graphene oxide solution with the titania solution to obtain a mixed solution, and the mixed solution comprises graphene oxide And titanium dioxide, the weight ratio of graphene oxide to titanium dioxide is 1:1 to 1:2.5; irradiating the mixed solution with ultraviolet light to obtain a composite solution, the composite solution containing reduced graphene and titanium dioxide; drying the composite solution to A composite material comprising reduced graphene and titanium dioxide.
本創作所製備出的複合材料包含還原石墨烯，藉由還原石墨烯的二維平面結構、比表面積大、良好的化學穩定性以及導電、導熱性質等特性，使得本創作所製備出的複合材料可應用於超級電容。 The composite material prepared by the present invention comprises reduced graphene, and the composite material prepared by the present invention is obtained by reducing the two-dimensional planar structure of graphene, large specific surface area, good chemical stability, and electrical and thermal conductivity properties. Can be applied to super capacitors.
較佳的是，其中混合氧化石墨烯溶液與二氧化鈦溶液，以得混合溶液的步驟更包含：混合氧化石墨烯溶液與二氧化鈦溶液，並以氧化石墨烯溶液與二氧化鈦溶液之總重為基準，再加入5wt%的聚乙二醇，以得混合溶液，該混合溶液包含氧化石墨烯、二氧化鈦與聚乙二醇。 Preferably, the step of mixing the graphene oxide solution with the titania solution to obtain the mixed solution further comprises: mixing the graphene oxide solution and the titania solution, and adding the total weight of the graphene oxide solution and the titania solution, and then adding 5 wt% of polyethylene glycol to obtain a mixed solution containing graphene oxide, titanium oxide and polyethylene glycol.
較佳的是，聚乙二醇的分子量為20000。 Preferably, the polyethylene glycol has a molecular weight of 20,000.
聚乙二醇可進一步提升氧化石墨烯與二氧化鈦混合的顆粒分散程度，進而提高還原石墨烯之產率。 Polyethylene glycol can further increase the degree of particle dispersion of graphene oxide mixed with titanium dioxide, thereby increasing the yield of reduced graphene.
較佳的是，其中混合氧化石墨烯溶液與二氧化 鈦溶液，以得混合溶液的步驟包含：混合氧化石墨烯溶液與二氧化鈦溶液後再以超音波震盪，以得混合溶液。 Preferably, the mixed graphene oxide solution and the dioxide are mixed therein The titanium solution to obtain a mixed solution comprises: mixing the graphene oxide solution with the titanium dioxide solution, and then oscillating with ultrasonic waves to obtain a mixed solution.
更佳的是，混合氧化石墨烯溶液與二氧化鈦溶液後再以超音波震盪，以得混合溶液的步驟包含：混合氧化石墨烯溶液與二氧化鈦溶液後再以超音波震盪1小時至2小時，以得混合溶液。 More preferably, the mixture of the graphene oxide solution and the titanium dioxide solution is ultrasonically oscillated to obtain a mixed solution comprising: mixing the graphene oxide solution with the titanium dioxide solution, and then oscillating with ultrasonic waves for 1 hour to 2 hours. mixture.
較佳的是，以紫外光照射該混合溶液，以得複合材料溶液的步驟中包含：於30℃至50℃的溫度下以紫外光照射該混合溶液，以得複合材料溶液。本創作利用紫外光照射混合溶液，並得於低溫(30℃至50℃)的條件下使得氧化石墨烯還原形成還原石墨烯，所需耗費的能量較少，係可降低生產還原石墨烯的成本。 Preferably, the step of irradiating the mixed solution with ultraviolet light to obtain a composite solution comprises: irradiating the mixed solution with ultraviolet light at a temperature of 30 ° C to 50 ° C to obtain a composite solution. The present invention utilizes ultraviolet light to illuminate the mixed solution, and at a low temperature (30 ° C to 50 ° C), the reduction of graphene oxide to form reduced graphene requires less energy and reduces the cost of producing reduced graphene. .
更佳的是，於30℃至50℃的溫度下以紫外光照射該混合溶液，以得複合材料溶液的步驟包含：於30℃至50℃的溫度下以波長254奈米的紫外光照射該混合溶液，以得複合材料溶液。 More preferably, the mixed solution is irradiated with ultraviolet light at a temperature of 30 ° C to 50 ° C to obtain a composite solution comprising: irradiating the ultraviolet light having a wavelength of 254 nm at a temperature of 30 ° C to 50 ° C. The solution is mixed to obtain a composite solution.
再更佳的是，於30℃至50℃的溫度下以波長254奈米的紫外光照射該混合溶液，以得複合材料溶液的步驟更包含：於30℃至50℃的溫度下以18W、波長254奈米的紫外光照射該混合溶液，以得複合材料溶液。本創作僅需使用18W之紫外光照射混合溶液，即可使得氧化石墨烯還原形成還原石墨烯，所需耗費的能量較少，係可降低生產還 原石墨烯的成本。 More preferably, the mixed solution is irradiated with ultraviolet light having a wavelength of 254 nm at a temperature of 30 ° C to 50 ° C to obtain a composite solution, which further comprises: 18 W at a temperature of 30 ° C to 50 ° C, The mixed solution was irradiated with ultraviolet light having a wavelength of 254 nm to obtain a composite solution. This creation only needs to use 18W ultraviolet light to illuminate the mixed solution, which can reduce the reduction of graphene oxide to form reduced graphene, which requires less energy and can reduce production. The cost of the original graphene.
較佳的是，所齊備之氧化石墨烯溶液的酸鹼值介於pH 7至pH 9。 Preferably, the prepared graphene oxide solution has a pH between pH 7 and pH 9.
較佳的是，齊備氧化石墨烯溶液之步驟包含：將石墨片加入一硫酸磷酸混合液中，以得石墨片溶液，石墨片溶液包含石墨片，該硫酸磷酸混合液係由磷酸水溶液與硫酸水溶液混合而成；令過錳酸鉀與該石墨片溶液中於35℃至40℃下混合，以得第一混合溶液，其中過錳酸鉀與石墨片之重量比為1：4；將該第一混合溶液於45℃至50℃的溫度下反應，以得經加熱之第一混合溶液；混合冰塊、雙氧水與該經加熱之第一混合溶液中，以得第二混合溶液；將第二混合溶液離心並水洗，以得氧化石墨烯溶液。 Preferably, the step of preparing the graphene oxide solution comprises: adding the graphite sheet to the mixed solution of sulfuric acid phosphoric acid to obtain a graphite sheet solution, wherein the graphite sheet solution comprises a graphite sheet, and the sulfuric acid phosphoric acid mixed solution is composed of an aqueous solution of phosphoric acid and an aqueous solution of sulfuric acid. Mixing; mixing potassium permanganate with the graphite sheet solution at 35 ° C to 40 ° C to obtain a first mixed solution, wherein the weight ratio of potassium permanganate to graphite sheet is 1:4; a mixed solution is reacted at a temperature of 45 ° C to 50 ° C to obtain a heated first mixed solution; mixed ice cubes, hydrogen peroxide and the heated first mixed solution to obtain a second mixed solution; The mixed solution was centrifuged and washed with water to obtain a graphene oxide solution.
若過錳酸鉀與石墨片溶液之溫度超過40℃則會導致過錳酸鉀與石墨片的反應過於劇烈，且若第一混合溶液之反應溫度超過50℃更將形成難溶之錳氧化物(副產物)，進而影響後續形成之氧化石墨烯的品質，故本創作將該第一混合溶液依序以不同溫度條件進行漸進式的加熱反應可有利於確保後續形成之氧化石墨烯的品質。 If the temperature of the potassium permanganate and the graphite sheet solution exceeds 40 ° C, the reaction between potassium permanganate and the graphite sheet is too severe, and if the reaction temperature of the first mixed solution exceeds 50 ° C, the insoluble manganese oxide is formed. (by-product), which in turn affects the quality of the subsequently formed graphene oxide. Therefore, the stepwise heating reaction of the first mixed solution in different temperature conditions in order to ensure the quality of the subsequently formed graphene oxide.
較佳的是，冰塊與雙氧水的體積比例為40：1，雙氧水與該經加熱之第一混合溶液之體積比例為1：20。 Preferably, the volume ratio of ice cubes to hydrogen peroxide is 40:1, and the volume ratio of hydrogen peroxide to the heated first mixed solution is 1:20.
圖1為樣品1-5至1-9與對照組的X光繞射分析圖。 Figure 1 is a graph of X-ray diffraction analysis of samples 1-5 to 1-9 and a control group.
圖2為氧化石墨烯的SEM影像。 2 is an SEM image of graphene oxide.
圖3為樣品1-6的SEM影像。 Figure 3 is an SEM image of Samples 1-6.
圖4為樣品1-7的SEM影像。 Figure 4 is an SEM image of samples 1-7.
圖5為樣品2-2的SEM影像。 Figure 5 is an SEM image of Sample 2-2.
圖6為樣品2-3的SEM影像。 Figure 6 is an SEM image of Sample 2-3.
圖7為樣品1-7的TEM影像。 Figure 7 is a TEM image of samples 1-7.
圖8為樣品3-1、3-2以及樣品4-2、4-3之循環伏安圖。 Figure 8 is a cyclic voltammogram of samples 3-1, 3-2 and samples 4-2, 4-3.
圖9為樣品4-3、樣品4-4與樣品4-5的循環伏安圖。 Figure 9 is a cyclic voltammogram of Sample 4-3, Sample 4-4, and Sample 4-5.
圖10為樣品3-1以及樣品5-1的循環伏安圖。 Figure 10 is a cyclic voltammogram of Sample 3-1 and Sample 5-1.
圖11為樣品3-1、樣品5-1以及樣品6-1的循環伏安圖。 Figure 11 is a cyclic voltammogram of Sample 3-1, Sample 5-1, and Sample 6-1.
製備例：氧化石墨烯之製備Preparation: Preparation of graphene oxide
將硫酸水溶液與磷酸水溶液以體積比例9：1混合並加入石墨片，以得石墨片溶液，其中硫酸水溶液之濃度為98%，磷酸水溶液之濃度為85%，該石墨片溶液中包含石墨片；再加入過錳酸鉀於該石墨片溶液中並於37℃的溫度下以600rpm攪拌2小時，以第一混合溶液，其中過錳酸鉀與石墨片之重量比為4：1；接著將該第一混合溶液於50℃的溫度下以500rpm攪拌12小時，以得經加熱之第一混合溶液；然後將該經加熱之第一混合溶液於室溫下靜置冷卻並加入冰塊與雙氧水，以得第二混合溶液，其中該第二混合溶液中包含氧化石墨烯，該經加熱之第一混合溶液、冰塊與雙氧水之體積比例為20：40：1；再將該 第二混合溶液離心(轉速6000rpm)並以30%鹽酸酸洗，以得第三混合溶液；接著將該第三混合溶液離心(轉速6000rpm)並水洗，以得氧化石墨烯溶液，該氧化石墨烯溶液之酸鹼值為pH 7；最後將該氧化石墨烯溶液於50℃的溫度下真空乾燥24小時，以得呈固態之氧化石墨烯。 The sulfuric acid aqueous solution and the phosphoric acid aqueous solution are mixed in a volume ratio of 9:1 and added to the graphite sheet to obtain a graphite sheet solution, wherein the concentration of the aqueous sulfuric acid solution is 98%, and the concentration of the aqueous phosphoric acid solution is 85%, and the graphite sheet solution contains graphite sheets; Adding potassium permanganate to the graphite sheet solution and stirring at 600 rpm for 2 hours at a temperature of 37 ° C to obtain a first mixed solution, wherein the weight ratio of potassium permanganate to graphite sheet is 4:1; The first mixed solution was stirred at 500 rpm for 12 hours at a temperature of 50 ° C to obtain a heated first mixed solution; then the heated first mixed solution was allowed to stand at room temperature and cooled, and ice cubes and hydrogen peroxide were added. Taking a second mixed solution, wherein the second mixed solution contains graphene oxide, the heated first mixed solution, the volume ratio of ice cubes to hydrogen peroxide is 20:40:1; The second mixed solution was centrifuged (speed: 6000 rpm) and pickled with 30% hydrochloric acid to obtain a third mixed solution; then the third mixed solution was centrifuged (speed: 6000 rpm) and washed with water to obtain a graphene oxide solution, the graphene oxide. The pH value of the solution was pH 7; finally, the graphene oxide solution was vacuum dried at a temperature of 50 ° C for 24 hours to obtain a solid graphene oxide.
實施例1：第一複合材料的製備Example 1: Preparation of a first composite material
將製備例1所製得之氧化石墨烯溶於去離子水中，以得氧化石墨烯溶液；將二氧化鈦溶於無水乙醇中，以得二氧化鈦溶液；接著混合氧化石墨烯溶液與二氧化鈦溶液，並超音波震盪1小時，以得第四混合溶液，其中氧化石墨烯溶液與二氧化鈦溶液之體積比為1：1，樣品1-1至樣品1-9中第四混合溶液中的二氧化鈦與氧化石墨烯之重量比列於表1；再於氮氣環境持續混合該第四混合溶液1小時，並接著於40℃的溫度下以18W、波長254奈米之紫外光照射該第四混合溶液，藉此還原氧化石墨烯，以得第五混合溶液，樣品1-1至樣品1-9中第四混合溶液被紫外光照射之時間列於表1。 The graphene oxide prepared in Preparation Example 1 is dissolved in deionized water to obtain a graphene oxide solution; the titanium dioxide is dissolved in absolute ethanol to obtain a titania solution; then the graphene oxide solution and the titania solution are mixed, and the ultrasonic wave is obtained. Shake for 1 hour to obtain a fourth mixed solution in which the volume ratio of the graphene oxide solution to the titania solution is 1:1, and the weight of the titanium dioxide and graphene oxide in the fourth mixed solution in the sample 1-1 to the sample 1-9 The ratio is shown in Table 1; the fourth mixed solution was continuously mixed for 1 hour in a nitrogen atmosphere, and then the fourth mixed solution was irradiated with ultraviolet light of 18 W and a wavelength of 254 nm at a temperature of 40 ° C, thereby reducing graphite oxide. The olefin was used to obtain the fifth mixed solution, and the time when the fourth mixed solution of the sample 1-1 to the sample 1-9 was irradiated with ultraviolet light was listed in Table 1.
最後將該第五混合溶液的全體於80℃的溫度下真空乾燥12小時，可得第一複合材料(樣品1-1與樣品1-2)。 Finally, the entire fifth mixed solution was vacuum dried at a temperature of 80 ° C for 12 hours to obtain a first composite material (sample 1-1 and sample 1-2).
另亦可僅取樣(使用藥匙撈出)該第五混合溶液之懸浮部分，並於80℃的溫度下真空乾燥該第五混合溶液之懸浮部分12小時，可得懸浮部分之第一複合材料(樣品1-3至樣品1-9)。 Alternatively, only the suspended portion of the fifth mixed solution may be sampled (using a spoon), and the suspended portion of the fifth mixed solution may be vacuum dried at a temperature of 80 ° C for 12 hours to obtain a suspended composite portion of the first composite material. (Sample 1-3 to Sample 1-9).
該第一複合材料包含還原石墨烯與二氧化 鈦；該懸浮部分之第一複合材料包含還原石墨烯與二氧化鈦。 The first composite material comprises reduced graphene and dioxide Titanium; the first composite of the suspended portion comprises reduced graphene and titanium dioxide.
實施例2：第二複合材料的製備Example 2: Preparation of a second composite material
將製備例1所製得之氧化石墨烯溶於去離子水中，以得氧化石墨烯溶液；將二氧化鈦溶於無水乙醇中，以得二氧化鈦溶液；接著混合氧化石墨烯溶液與二氧化鈦溶液，並超音波震盪1小時，以得第四混合溶液，其中氧化石墨烯溶液與二氧化鈦溶液之體積比為1：1，樣品2-1至樣品2-3中第四混合溶液中的二氧化鈦與氧化石墨烯之重量比列於表1；再以該第四混合溶液的總重為基準，於 該第四混合溶液加入5wt%聚乙二醇，以得第六混合溶液，聚乙二醇的分子量為20000；接著於於氮氣環境持續混合該第六混合溶液1小時並再於40℃的溫度下以18W、波長254奈米之紫外光照射該第六混合溶液，藉此還原氧化石墨烯，以得第七混合溶液，樣品2-1至樣品2-3中第六混合溶液被紫外光照射之時間列於表1。 The graphene oxide prepared in Preparation Example 1 is dissolved in deionized water to obtain a graphene oxide solution; the titanium dioxide is dissolved in absolute ethanol to obtain a titania solution; then the graphene oxide solution and the titania solution are mixed, and the ultrasonic wave is obtained. Shake for 1 hour to obtain a fourth mixed solution in which the volume ratio of the graphene oxide solution to the titania solution is 1:1, and the weight of the titanium dioxide and graphene oxide in the fourth mixed solution in the sample 2-1 to the sample 2-3 The ratio is listed in Table 1; based on the total weight of the fourth mixed solution, The fourth mixed solution was added with 5 wt% polyethylene glycol to obtain a sixth mixed solution, and the molecular weight of the polyethylene glycol was 20000; then the sixth mixed solution was continuously mixed in a nitrogen atmosphere for 1 hour and then at a temperature of 40 ° C. The sixth mixed solution is irradiated with ultraviolet light of 18 W and a wavelength of 254 nm, thereby reducing graphene oxide to obtain a seventh mixed solution, and the sixth mixed solution of the sample 2-1 to the sample 2-3 is irradiated with ultraviolet light. The time is listed in Table 1.
最後將該第七混合溶液的全體於80℃的溫度下真空乾燥12小時，可得第二複合材料(樣品2-1與2-2)。 Finally, the entire seventh mixed solution was vacuum dried at a temperature of 80 ° C for 12 hours to obtain a second composite material (samples 2-1 and 2-2).
另亦可僅取樣該第七混合溶液之懸浮部分，並於80℃的溫度下真空乾燥該第七混合溶液之懸浮部分12小時，可得懸浮部分之第二複合材料(樣品2-3)。 Alternatively, only the suspended portion of the seventh mixed solution may be sampled, and the suspended portion of the seventh mixed solution may be vacuum dried at a temperature of 80 ° C for 12 hours to obtain a suspended second composite (sample 2-3).
該第二複合材料包含還原石墨烯、二氧化鈦與聚乙二醇；該懸浮部分之第二複合材料包含還原石墨烯、二氧化鈦與聚乙二醇。 The second composite material comprises reduced graphene, titanium dioxide and polyethylene glycol; the second composite material of the suspension portion comprises reduced graphene, titanium dioxide and polyethylene glycol.
實施例3：第一石墨紙基板的製備Example 3: Preparation of a first graphite paper substrate
本實施例係採用如下列所述之方法製得樣品3-1與樣品3-2之第一石墨紙基板。 In the present embodiment, the first graphite paper substrate of Sample 3-1 and Sample 3-2 was obtained by the method described below.
依序以規格AA800和AA1000的粗砂紙研磨一石墨紙(1公分x1公分)之表面，可得一光滑石墨紙；再浸泡該光滑石墨紙於0.05M硫酸溶液並置於100℃的溫度下真空乾燥，以得一去油脂石墨紙；接著於無水乙醇中加入樣品1-1或樣品1-2之第一複合材料、碳黑與聚四氟乙烯，以得第一複合材料稠狀液，其中第一複合材料、碳黑與聚四氟乙烯之重量比為8：1：1；最後將該第一複合材料稠狀液滴至該去油脂石墨紙之表面，並於100℃的溫度下真 空乾燥，以得第一石墨紙基板(樣品3-1與樣品3-2)。 Grinding a graphite paper (1 cm x 1 cm) on a coarse sandpaper of AA800 and AA1000 in size to obtain a smooth graphite paper; then immersing the smooth graphite paper in a 0.05 M sulfuric acid solution and drying it at a temperature of 100 ° C under vacuum To obtain a grease graphite paper; then add the first composite material of sample 1-1 or sample 1-2, carbon black and polytetrafluoroethylene in absolute ethanol to obtain a first composite thick liquid, wherein a composite material, the weight ratio of carbon black to polytetrafluoroethylene is 8:1:1; finally, the first composite material is thickly dropped onto the surface of the degreased graphite paper, and is true at a temperature of 100 ° C. The air was dried to obtain a first graphite paper substrate (sample 3-1 and sample 3-2).
實施例4：第二石墨紙基板的製備Example 4: Preparation of a second graphite paper substrate
本實施例係採用如下列所述之方法製得樣品4-1至樣品4-5之第二石墨紙基板。 In this example, a second graphite paper substrate of Sample 4-1 to Sample 4-5 was obtained by the method described below.
本實施例之第二石墨紙基板與實施例3之第一石墨紙基板的製作方法類似，其不同之處在於，分別於無水乙醇中加入樣品1-5至樣品1-9的懸浮部分之第一複合材料、碳黑與聚四氟乙烯，以得懸浮部分之第一複合材料稠狀液，其中懸浮部分之第一複合材料、碳黑與聚四氟乙烯之重量比為8：1：1；最後將該懸浮部分之第一複合材料稠狀液滴至該去油脂石墨紙之表面，並於100℃的溫度下真空乾燥，以得第二石墨紙基板(樣品4-1至樣品4-5)。 The second graphite paper substrate of the present embodiment is similar to the first graphite paper substrate of the third embodiment, except that the suspension portion of the sample 1-5 to the sample 1-9 is added to the absolute ethanol, respectively. a composite material, carbon black and polytetrafluoroethylene, to obtain a suspension of the first composite material thick liquid, wherein the suspended portion of the first composite material, the ratio of carbon black to polytetrafluoroethylene is 8:1:1 Finally, the first composite material of the suspended portion is thickly dropped onto the surface of the degreased graphite paper, and vacuum dried at a temperature of 100 ° C to obtain a second graphite paper substrate (sample 4-1 to sample 4 5).
實施例5：第三石墨紙基板的製備Example 5: Preparation of a third graphite paper substrate
本實施例係採用如下列所述之方法製得樣品5-2之第三石墨紙基板。 In this example, a third graphite paper substrate of Sample 5-2 was obtained by the method described below.
本實施例之第三石墨紙基板與實施例3之第一石墨紙基板的製作方法類似，其不同之處在於，於無水乙醇中加入樣品2-2之第二複合材料、碳黑與聚四氟乙烯，以得第二複合材料稠狀液，其中第二複合材料、碳黑與聚四氟乙烯之重量比為8：1：1；最後將該第二複合材料稠狀液滴至該去油脂石墨紙之表面，並於100℃的溫度下真空乾燥，以得第三石墨紙基板(樣品5-1)。 The third graphite paper substrate of the present embodiment is similar to the first graphite paper substrate of the third embodiment, except that the second composite material of sample 2-2, carbon black and poly 4 are added to absolute ethanol. Fluorine to obtain a second composite thick liquid, wherein the weight ratio of the second composite material, carbon black to polytetrafluoroethylene is 8:1:1; finally, the second composite material is thickly dropped to the The surface of the grease graphite paper was vacuum dried at a temperature of 100 ° C to obtain a third graphite paper substrate (Sample 5-1).
實施例6：第四石墨紙基板的製備Example 6: Preparation of a fourth graphite paper substrate
本實施例係採用如下列所述之方法製得樣品6-1之第三石墨紙基板。 In this example, a third graphite paper substrate of Sample 6-1 was obtained by the method described below.
本實施例之第四石墨紙基板與實施例3之第一 石墨紙基板的製作方法類似，其不同之處在於，於無水乙醇中加入樣品2-3之懸浮部分之第二複合材料、碳黑與聚四氟乙烯，以得懸浮部分之第二複合材料稠狀液，其中懸浮部分之第二複合材料、碳黑與聚四氟乙烯之重量比為8：1：1；最後將該懸浮部分之第二複合材料稠狀液滴至該去油脂石墨紙之表面，並於100℃的溫度下真空乾燥，以得第四石墨紙基板(樣品6-1)。 The fourth graphite paper substrate of the embodiment is the first of the third embodiment The graphite paper substrate is produced in a similar manner, except that the second composite material of the suspended portion of the sample 2-3, carbon black and polytetrafluoroethylene is added to the anhydrous ethanol to obtain a second composite material having a suspended portion. a liquid, wherein the second composite material of the suspension portion, the weight ratio of carbon black to polytetrafluoroethylene is 8:1:1; finally, the second composite material of the suspension portion is thickly dropped to the degreased graphite paper. The surface was vacuum dried at a temperature of 100 ° C to obtain a fourth graphite paper substrate (sample 6-1).
試驗例1：X光繞射分析Test Example 1: X-ray diffraction analysis
將樣品1-5至樣品1-9之懸浮部分之第一複合材料與作為對照組之氧化石墨烯分別利用X光繞射分析儀進行分析，所得結果如圖1所示。 The first composite material of the suspension portion of Samples 1-5 to 1-9 and the graphene oxide as a control group were respectively analyzed by an X-ray diffraction analyzer, and the results are shown in Fig. 1.
圖1中由下至上依序為對照組以及樣品1-5至樣品1-9，由圖1中可以看出，氧化石墨烯的主要繞射峰值(2θ=10°)的強度隨著二氧化鈦的比例增加而下降，表示二氧化鈦能夠有效的還原氧化石墨烯而形成還原石墨烯。 In Fig. 1, the bottom to the top are the control group and the samples 1-5 to 1-9. As can be seen from Fig. 1, the intensity of the main diffraction peak of the graphene oxide (2θ = 10°) follows the titanium dioxide. The decrease in proportion increases, indicating that titanium dioxide can effectively reduce graphene oxide to form reduced graphene.
試驗例2：掃描式電子顯微鏡分析Test Example 2: Scanning electron microscope analysis
將樣品1-6與1-7、樣品2-2與2-3以及作為對照組之氧化石墨烯分別利用掃描式電子顯微鏡(scanning electron microscope，SEM)拍攝SEM影像，結果係如圖2至圖6所示。 Samples 1-6 and 1-7, samples 2-2 and 2-3, and graphene oxide as a control group were respectively photographed by scanning electron microscope (SEM), and the results are shown in Fig. 2 to Fig. 2 6 is shown.
圖2為對照組之氧化石墨烯的SEM影像，可以看出氧化石墨烯並非緊密堆疊在一起，而是層與層之間的間距分明，且為皺褶狀。 2 is an SEM image of graphene oxide in a control group. It can be seen that graphene oxide is not closely packed together, but the layer-to-layer spacing is distinct and wrinkled.
再配合圖3至圖6，係分別為樣品1-6與1-7 以及樣品2-2與2-3的SEM影像，由上述SEM影像中可以看出不論是樣品1-6、1-7或樣品2-2、2-3，二氧化鈦皆插層於還原石墨烯之間，以避免還原石墨烯層與層間在還原過程中重新堆疊。使得後續可用於與電解液反應之潤濕面積增加。 3 to 6, together with samples 1-6 and 1-7 And the SEM images of samples 2-2 and 2-3, it can be seen from the above SEM images that whether the samples 1-6, 1-7 or the samples 2-2, 2-3, the titanium dioxide is intercalated into the reduced graphene To avoid re-stacking of the reduced graphene layer and the interlayer during the reduction process. The subsequent wetted area available for reaction with the electrolyte is increased.
再比較樣品1-6的懸浮部分之第一複合材料 (圖3)與樣品2-3的懸浮部分之第二複合材料(圖6)，加入聚乙二醇使得樣品2-3的懸浮部分之第二複合材料層與層之間的間距大於未加入聚乙二醇之樣品1-6的懸浮部分之第一複合材料，係使得樣品2-3的懸浮部分之第二複合材料後續可用於與電解液反應之潤濕面積增加。 Compare the first composite of the suspended portion of Samples 1-6 (Fig. 3) A second composite material (Fig. 6) with the suspension portion of sample 2-3, polyethylene glycol was added such that the distance between the second composite material layer and the layer of the suspended portion of sample 2-3 was greater than that of the non-addition The first composite of the suspended portion of Samples 1-6 of polyethylene glycol is such that the second composite of the suspended portion of Sample 2-3 is subsequently available for increased wetted area for reaction with the electrolyte.
試驗例3：穿透式電子顯微鏡分析Test Example 3: Analysis by Penetrating Electron Microscopy
將樣品1-7利用穿透式電子顯微鏡(transmission electron microscopy，TEM)拍攝TEM影像，其結果如圖7所示。 TEM images were taken using Sample 1-7 using a transmission electron microscopy (TEM), and the results are shown in FIG.
由圖7可以看出二氧化鈦(平均粒徑大小約27奈米)負載於還原石墨烯之表面(於TEM影像中具有明顯***之皺褶狀)，表示二氧化鈦確實插層於還原石墨烯之間，以避免在還原過程中各氧化石墨烯層之間重新堆疊，故能確保後續可用於與電解液反應之潤濕面積增加。 It can be seen from Fig. 7 that titanium dioxide (average particle size of about 27 nm) is supported on the surface of the reduced graphene (having a wrinkle in the TEM image), indicating that the titanium dioxide is intercalated between the reduced graphene. To avoid re-stacking between the graphene oxide layers during the reduction process, it is possible to ensure an increase in the wetted area that can be subsequently used to react with the electrolyte.
試驗例4：循環伏安法分析Test Example 4: Cyclic voltammetry analysis
利用恆電流電位分析儀(購自CH Instruments，型號400 Series)分別對第一石墨基板(樣品3-1至樣品3-2)、第二石墨基板(樣品4-1至樣品4-5)、第三石墨基板(樣品5-1)以及第四石墨基板(樣品6-1)進行循環伏 安法分析(掃描速率0.01V/s)，以求得上述樣品之電容值，所得之循環伏安圖為圖8至圖11，而各樣品之電容值列於表2。 The first graphite substrate (sample 3-1 to sample 3-2) and the second graphite substrate (sample 4-1 to sample 4-5) were respectively subjected to a constant current potential analyzer (available from CH Instruments, model 400 Series), The third graphite substrate (sample 5-1) and the fourth graphite substrate (sample 6-1) were subjected to cyclic volts The amperometric analysis (scanning rate 0.01 V/s) was used to obtain the capacitance values of the above samples, and the obtained cyclic voltammograms are shown in Figs. 8 to 11, and the capacitance values of the respective samples are shown in Table 2.
圖8為樣品3-1、3-2以及樣品4-2、4-3之循 環伏安圖，可以看出第二石墨基板(樣品4-2、4-3)相較於第一石墨基板(樣品3-1、3-2)具有較大的電流密度面積，且第二石墨基板(樣品4-3)的電容值為226.45F/g亦大於第一石墨基板(樣品3-2)的電容值80.12F/g。 Figure 8 is a sample of samples 3-1, 3-2 and samples 4-2, 4-3. The ring voltammogram shows that the second graphite substrate (samples 4-2, 4-3) has a larger current density area than the first graphite substrate (samples 3-1, 3-2), and the second The capacitance value of the graphite substrate (sample 4-3) was also 226.45 F/g, which was also larger than the capacitance value of the first graphite substrate (sample 3-2) of 80.12 F/g.
圖9為樣品4-3至4-5的循環伏安圖，可以看 出樣品4-3(照光時間5小時)相較於樣品4-4(照光時間1小時)或樣品4-5(照光時間10小時)具有較大的電流密度面積。 Figure 9 is a cyclic voltammogram of samples 4-3 to 4-5, which can be seen Sample 4-3 (lighting time 5 hours) has a larger current density area than sample 4-4 (lighting time 1 hour) or sample 4-5 (lighting time 10 hours).
圖10為樣品3-1以及5-1的循環伏安圖，可以 看出添加聚乙二醇使得第三石墨基板(樣品5-1)的電容值(125F/g)相較於第一石墨基板(樣品3-1)的電容值(70F/g)來得高；圖11為樣品3-1、樣品5-1以及樣品6-1的循環 伏安圖，可以看出第四石墨基板(樣品6-1)的電容值(183F/g)相較於第三石墨基板(樣品5-1)的電容值(125F/g)來得高。 Figure 10 is a cyclic voltammogram of samples 3-1 and 5-1, which can It is seen that the addition of polyethylene glycol causes the capacitance value (125 F/g) of the third graphite substrate (sample 5-1) to be higher than the capacitance value (70 F/g) of the first graphite substrate (sample 3-1); Figure 11 shows the cycle of sample 3-1, sample 5-1, and sample 6-1. In the voltammogram, it can be seen that the capacitance value (183 F/g) of the fourth graphite substrate (sample 6-1) is higher than the capacitance value (125 F/g) of the third graphite substrate (sample 5-1).
由表2可以看出，各樣品之電容值均大於70F/g，均適合應用於超級電容。 It can be seen from Table 2 that the capacitance values of each sample are all greater than 70 F/g, which are suitable for use in super capacitors.
以上所述僅為說明本創作的例示，並非對本創作做任何形式上的限制，本創作所主張之權利範圍自應以申請專利範圍所述為準，而非僅限於上述實施例。任何所屬技術領域中具有通常知識者，在不脫離本創作技術方案的範圍內，當可利用上述揭示的技術內容做出些許更動或修飾為等同變化的等效實施例，但凡是未脫離本創作之技術方案的內容，依據本創作的技術實質對以上實施例作任何簡單修改、等同變化與修改，均仍屬於本創作技術方案的範圍內。 The above description is only illustrative of the present invention, and is not intended to limit the scope of the present invention. The scope of the present invention is defined by the scope of the patent application, and is not limited to the above embodiments. Any equivalents of the above-disclosed technical contents may be modified or modified to equivalent variations, without departing from the scope of the present invention. The content of the technical solution, any simple modification, equivalent change and modification of the above embodiment according to the technical essence of the present invention are still within the scope of the technical solution of the present invention.
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