TW201341304A - Preparation method for graphene composite material - Google Patents
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本發明係涉及一種複合材料的製備方法，更具體而言，係關於一種石墨烯複合材料的製備方法。The present invention relates to a method for preparing a composite material, and more particularly to a method for preparing a graphene composite material.
單層石墨，又稱為石墨烯(graphene)，是一種由單層碳原子以石墨鍵(sp2)緊密堆積成二維蜂窩狀的晶格結構，因此僅有一個碳原子的厚度，石墨鍵為共價鍵與金屬鍵的複合鍵，可說是絕緣體與導電體的天作之合。2004年英國曼徹斯特大學Andre Geim與Konstantin Novoselov成功利用膠帶剝離石墨的方式，證實可得到單層之石墨烯，並獲得2010年之諾貝爾物理獎。Single-layer graphite, also known as graphene, is a lattice structure in which a single layer of carbon atoms is closely packed into a two-dimensional honeycomb with graphite bonds (sp 2 ), so there is only one carbon atom thickness, graphite bond. The composite bond between the covalent bond and the metal bond can be said to be the natural fit of the insulator and the conductor. In 2004, Andre Geim and Konstantin Novoselov of the University of Manchester in the United Kingdom successfully used tape to strip graphite, which confirmed that a single layer of graphene could be obtained and won the 2010 Nobel Prize in Physics.
石墨烯是目前世界上最薄也是最堅硬的材料，導熱係數高於奈米碳管與金剛石，常溫下其電子遷移率亦比奈米碳管或矽晶體高，電阻率比銅或銀更低，是目前世界上電阻率最小的材料，這些獨特的電荷機械性質使得加入石墨烯的複合材料更多功能化，不但表現出優異的力學及電學性能，還具有優良的加工性能，為複合材料提供了更廣闊的應用領域。但是結構完整的石墨烯是由不含任何不穩定鍵的苯六元環組合而成的二維晶體，化學穩定性高，其表面呈惰性狀態，與其他介質(如溶劑等)相互作用較弱，且石墨烯的片與片之間存在較強的凡得瓦力，容易產生團聚，使其難溶於水以及其他常用的有機溶劑，因而限制了石墨烯的進一步研究與應用。Graphene is currently the thinnest and hardest material in the world. Its thermal conductivity is higher than that of carbon nanotubes and diamond. Its electron mobility is higher than that of carbon nanotubes or germanium crystals at room temperature, and its resistivity is lower than that of copper or silver. It is the world's smallest resistivity material. These unique charge mechanical properties make graphene-added composites more functional, not only exhibit excellent mechanical and electrical properties, but also have excellent processing properties, providing composite materials. A broader application area. However, the structurally intact graphene is a two-dimensional crystal composed of a benzene six-membered ring containing no unstable bonds. It has high chemical stability, its surface is inert, and its interaction with other media (such as solvents) is weak. Moreover, there is a strong van der Waals force between the sheet and the sheet of graphene, which is prone to agglomeration, making it difficult to dissolve in water and other commonly used organic solvents, thus limiting the further research and application of graphene.
中國專利CN10181219A號報導了一種石墨烯基阻隔複合材料及其製作方法，該製備方法包括：用增強材料的界面性能的一種塑膠添加劑對氧化石墨烯的表面進行修飾，使其表面接上活性官能基，然後再將修飾後的氧化石墨烯還原成石墨烯；經修飾後的石墨烯採用機械分散的方式分散到聚烯烴溶液中，在起始劑作用下使聚烯烴交聯結合，得到奈米複合材料。但該方法採用的石墨烯在製作石墨烯複合材料的過程中容易團聚，且採用機械分散的方式很難將修飾後的石墨烯均勻分散在聚烯烴基體中，因而使製備的石墨烯複合材料力學性質提高不明顯。Chinese patent CN10181219A reports a graphene-based barrier composite material and a preparation method thereof, the preparation method comprising: modifying a surface of graphene oxide with a plastic additive of a reinforcing material interfacial property, and attaching a reactive functional group to the surface thereof Then, the modified graphene oxide is reduced to graphene; the modified graphene is dispersed into the polyolefin solution by mechanical dispersion, and the polyolefin is cross-linked and combined under the action of the initiator to obtain a nano composite. material. However, the graphene used in the method is easy to agglomerate in the process of fabricating the graphene composite material, and it is difficult to uniformly disperse the modified graphene in the polyolefin matrix by mechanical dispersion, thereby making the prepared graphene composite material mechanics The improvement in nature is not obvious.
中國專利CN101781459A號公開了一種石墨烯/聚苯胺導電複合材料及其製備方法，由以下步驟製備而得：將氧化石墨加到醇類分散劑中以超音波分散，形成均勻分散的氧化石墨烯混合液；再加入苯胺進行分散；低溫下，於混合液中滴加氧化劑與無機酸的溶液，攪拌聚合；離心、洗滌後得到氧化石墨烯/聚苯胺複合材料；向上述產物的水懸浮液中加入高濃度的鹼液，加熱攪拌，分離後將得到的複合材料浸泡在酸性溶液中，分離乾燥得到石墨烯/聚苯胺導電複合材料。Chinese Patent No. CN101781459A discloses a graphene/polyaniline conductive composite material and a preparation method thereof, which are prepared by the following steps: adding graphite oxide to an alcohol dispersant to disperse ultrasonically to form a uniformly dispersed graphene oxide mixture. Liquid; further adding aniline for dispersion; at low temperature, adding a solution of oxidizing agent and inorganic acid to the mixed solution, stirring and polymerizing; centrifuging, washing to obtain graphene oxide/polyaniline composite material; adding to the aqueous suspension of the above product The high concentration alkali solution is heated and stirred, and the obtained composite material is immersed in an acidic solution after separation, and is separated and dried to obtain a graphene/polyaniline conductive composite material.
世界專利WO2011/045269 A1號係一種藉由鹼金屬鹽製備石墨烯溶液及石墨烯複合材料之方法，其中石墨係在極性有機溶劑中以鹼金屬鹽還原。該方法包括以下步驟：先將聚芳族化合物隨著攪拌而溶於極性有機溶劑中；之後，將鹼金屬(還原劑)較佳以稍微化學計量過量，供應至該溶液中；然後隨著攪拌將石墨加入還原劑中，進行此步驟直到獲得一安定石墨烯溶液；再將10 g鋁粉(300 mesh)加入所製得的石墨烯溶液中並藉由攪拌均化之；之後，令此溶液暴露於氧中並燒結之，以獲得2%石墨烯/鋁複合材料。World Patent No. WO 2011/045269 A1 is a method for preparing a graphene solution and a graphene composite by an alkali metal salt, wherein the graphite is reduced with an alkali metal salt in a polar organic solvent. The method comprises the steps of first dissolving the polyaromatic compound in a polar organic solvent with stirring; thereafter, the alkali metal (reducing agent) is preferably supplied to the solution in a slight stoichiometric excess; Adding graphite to the reducing agent, performing this step until a stable graphene solution is obtained; 10 g of aluminum powder (300 mesh) is added to the prepared graphene solution and homogenized by stirring; after that, the solution is made Exposure to oxygen and sintering to obtain a 2% graphene/aluminum composite.
美國專利US2010081057號製備一種石墨烯材料結合的金屬氧化物的奈米複合材料。該方法包括以下步驟：在第一懸浮液中提供石墨烯；用表面活性劑分散該石墨烯；在該經分散的石墨烯溶液中添加金屬氧化物前驅物以形成第二懸浮液，從該第二懸浮液中將金屬氧化物沉澱在經分散的石墨烯表面上，形成奈米複合材料。該奈米複合材料在超過約10 C的充電/放電速率時，具有為沒有石墨烯的金屬氧化物材料至少兩倍的比容量。U.S. Patent No. 2010081057 produces a nanocomposite of graphene material bonded metal oxide. The method comprises the steps of: providing graphene in a first suspension; dispersing the graphene with a surfactant; adding a metal oxide precursor to the dispersed graphene solution to form a second suspension, from the A metal oxide is precipitated on the surface of the dispersed graphene in the second suspension to form a nanocomposite. The nanocomposite has a specific capacity of at least twice the metal oxide material without graphene at a charge/discharge rate of more than about 10 C.
中國專利CN 102000590號係一種燃料電池用石墨烯/FePt奈米催化劑的製備方法，屬於奈米複合材料製備領域。主要步驟是以天然鱗片石墨為原料，用Hummers法將其氧化得到氧化石墨，將氧化石墨、等物質的量的氯鉑酸(H2PtCl6‧(H2O)6)與硝酸鐵一起溶解於去離子水中，再加入聯胺並用氨水調節溶液pH值為10~10.5，於120℃下以油浴加熱，在氮氣保護下回流反應2.5~3小時，收集沉澱並洗滌、乾燥後得到石墨烯/FePt奈米催化劑。此專利宣稱可減少燃料電池催化劑中貴金屬鉑的負載量，從而降低燃料電池的生產成本。Chinese patent CN 102000590 is a preparation method of graphene/FePt nano catalyst for fuel cell, and belongs to the field of preparation of nano composite materials. The main step is to use natural flake graphite as raw material, oxidize it by Hummers method to obtain graphite oxide, and dissolve the amount of chloroplatinic acid (H 2 PtCl 6 ‧(H 2 O) 6 ) with iron nitrate. In deionized water, add hydrazine and adjust the pH of the solution to 10~10.5 with ammonia water, heat in an oil bath at 120 °C, reflux under nitrogen for 2.5~3 hours, collect the precipitate, wash and dry to obtain graphene. /FePt nanocatalyst. This patent claims to reduce the loading of precious metal platinum in fuel cell catalysts, thereby reducing the production cost of fuel cells.
綜上所述，為避免因為石墨烯非常容易聚集堆疊進而影響產物特性，多數的先前技術均使用氧化石墨作為前軀物先行製備奈米複合材料，再將氧化石墨還原為石墨烯形成石墨烯複合材料，此一方式將限制石墨烯的取得來源，且石墨經氧化再於複合材料中還原會有還原程度不足的問題，影響其性能。In summary, in order to avoid the fact that graphene is very easy to aggregate and affect product characteristics, most of the prior art uses graphite oxide as a precursor to prepare nano composites, and then reduces graphite oxide to graphene to form graphene composite. The material, this way will limit the source of graphene, and the reduction of graphite by oxidation and then the reduction of the composite will have the problem of insufficient reduction and affect its performance.
本發明之主要目的在於提供一種石墨烯的製備方法，包括一懸浮步驟，將一石墨烯片加入一溶劑中，該石墨烯片懸浮於該溶劑中，以獲得一石墨懸浮液，其中該石墨烯片係多層堆疊之石墨烯材料；一剝離步驟，使用一機械力量將該石墨懸浮液中的該石墨烯片剝離成為多個單層石墨烯材料，懸浮於該溶劑中，而獲得一石墨烯懸浮液，該石墨烯懸浮液中包括該等單層石墨烯材料及少部分未被剝離的該石墨烯片；一分離步驟，將該石墨烯懸浮液中的該等單層石墨烯材料與少部分未被剝離的該石墨烯片分離，去除少部分未被剝離的該石墨烯片後，獲得一石墨烯分散液，該石墨烯分散液中包括該等單層石墨烯材料均勻分散於其中；以及一活性物質添加步驟，加入一活性物質至該石墨烯分散液中，該活性物質與該石墨烯分散液中的該等單層石墨烯結合成為一石墨烯複合材料，而獲得一石墨烯複合材料分散液。The main object of the present invention is to provide a method for preparing graphene, comprising a suspension step of adding a graphene sheet to a solvent, the graphene sheet being suspended in the solvent to obtain a graphite suspension, wherein the graphene a multi-layer stacked graphene material; a stripping step, using a mechanical force to strip the graphene sheet in the graphite suspension into a plurality of single-layer graphene materials, suspended in the solvent to obtain a graphene suspension a liquid, the graphene suspension comprising the single-layer graphene material and a small portion of the graphene sheet not stripped; a separation step of the single-layer graphene material in the graphene suspension with a small portion Separating the graphene sheet that has not been peeled off, and removing a small portion of the graphene sheet that has not been peeled off, to obtain a graphene dispersion liquid, wherein the graphene dispersion layer includes the single-layer graphene material uniformly dispersed therein; An active material addition step of adding an active material to the graphene dispersion, the active material being combined with the single layer graphene in the graphene dispersion to form a stone Alkenyl composite, to obtain a dispersion of graphene composite material.
所述之石墨烯複合材料的製備方法，其中該溶劑的表面張力係大於35 mJ/m2且小於55 mJ/m2。The method for preparing a graphene composite material, wherein the solvent has a surface tension of more than 35 mJ/m 2 and less than 55 mJ/m 2 .
所述之石墨烯複合材料的製備方法，其中該溶劑與該石墨烯片的一接觸角係小於80度。The method for preparing a graphene composite material, wherein a contact angle of the solvent with the graphene sheet is less than 80 degrees.
所述之石墨烯複合材料的製備方法，其中該溶劑係選自苯甲酸芐酯(benzyl benzoate)、N-甲基吡咯烷酮(1-Methyl-2-pyrrolidinone)、γ-丁內酯(γ-Butyrolactone)、N,N-二甲基乙醯胺(N,N-Dimethylacetamide)、1,3-二甲基-2-咪唑啉酮(1,3-Dimethyl-2-Imidazolidinone)、N-乙烯基吡咯烷酮(1-Vinyl-2-pyrrolidone)、N,N-二甲基甲醯胺(N,N-Dimethylformamide)、二甲基亞碸(dimethyl sulfoxide)、N-辛基吡咯烷酮(1-Octyl-2-pyrrolidone)、苯胺(aniline)、苯甲醇(benzyl alcohol)、二甘醇(Diethylene glycol)、聚乙二醇(Polyethylene glycol)以及松油醇(terpineol)的至少其中之一。The method for preparing a graphene composite material, wherein the solvent is selected from the group consisting of benzyl benzoate, N-methylpyrrolidone, and γ-butyrolactone. , N,N-Dimethylacetamide, 1,3-Dimethyl-2-Imidazolidinone, N-vinylpyrrolidone (1-Vinyl-2-pyrrolidone), N,N-Dimethylformamide, dimethyl sulfoxide, N-octylpyrrolidone (1-Octyl-2- At least one of pyrrolidone), aniline, benzyl alcohol, diethylene glycol, polyethylene glycol, and terpineol.
所述之石墨烯複合材料的製備方法，其中該溶劑進一步包括一界面活性劑。該界面活性劑係聚乙烯吡咯烷酮(polyvinyl pyrrolidone)。The method for preparing a graphene composite material, wherein the solvent further comprises a surfactant. The surfactant is polyvinyl pyrrolidone.
所述之石墨烯複合材料的製備方法，其中該石墨懸浮液的濃度係小於5 g/L。The method for preparing a graphene composite material, wherein the concentration of the graphite suspension is less than 5 g/L.
所述之石墨烯複合材料的製備方法，其中該剝離步驟中的該機械力量係使用超音波震盪。The method for preparing a graphene composite material, wherein the mechanical force in the stripping step is ultrasonic shock.
所述之石墨烯複合材料的製備方法，其中該分離步驟係使用離心分離。The method for preparing a graphene composite material, wherein the separating step is performed by centrifugation.
所述之石墨烯複合材料的製備方法，其中該活性物質係選自高分子聚合物、陶瓷粉體、金屬粉體、碳粉及石墨粉的至少其中之一。The method for preparing a graphene composite material, wherein the active material is selected from at least one of a high molecular polymer, a ceramic powder, a metal powder, a carbon powder, and a graphite powder.
所述之石墨烯複合材料的製備方法，其中進一步包括一乾燥步驟，緊接於該活性物質添加步驟之後，用以乾燥該石墨烯複合材料分散液，得到一石墨烯複合材料粉體。The method for preparing a graphene composite material further comprises a drying step of drying the graphene composite dispersion liquid immediately after the active material addition step to obtain a graphene composite material powder.
以下配合圖式及元件符號對本發明之實施方式做更詳細的說明，俾使熟習該項技藝者在研讀本說明書後能據以實施。The embodiments of the present invention will be described in more detail below with reference to the drawings and the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;
參閱第一圖，本發明之石墨烯複合材料的製備方法之流程圖。本發明之石墨烯的製備方法S1包括以下步驟：Referring to the first figure, a flow chart of a method for preparing a graphene composite material of the present invention. The method S1 for preparing graphene of the present invention comprises the following steps:
步驟S11懸浮步驟，將石墨烯片加入溶劑中，使石墨烯片懸浮於該溶劑中，以獲得石墨懸浮液，其中石墨烯片係多層堆疊的石墨烯材料。步驟S13剝離步驟，使用機械力量將石墨懸浮液中的石墨烯片剝離成為多個單層石墨烯材料，懸浮於溶劑中，而獲得石墨烯懸浮液，石墨烯懸浮液中包括單層石墨烯材料及少部分未被剝離的石墨烯片。步驟S15分離步驟，將石墨烯懸浮液中的單層石墨烯材料與少部分未被剝離的石墨烯片分離，去除少部分未被剝離的石墨烯片後，獲得石墨烯分散液，石墨烯分散液中包括單層石墨烯材料均勻分散於其中。步驟S17活性物質添加步驟，加入活性物質至石墨烯分散液中，活性物質與石墨烯分散液中的單層石墨烯結合成為石墨烯複合材料，而獲得石墨烯複合材料分散液。In step S11, the graphene sheet is added to the solvent to suspend the graphene sheet in the solvent to obtain a graphite suspension, wherein the graphene sheet is a multi-layer stacked graphene material. Step S13 is a stripping step of using a mechanical force to peel the graphene sheet in the graphite suspension into a plurality of single-layer graphene materials, suspending in a solvent to obtain a graphene suspension, and the graphene suspension includes a single-layer graphene material. And a small portion of the graphene sheets that are not stripped. Step S15 is a separation step of separating a single-layer graphene material in the graphene suspension from a small portion of the unexfoliated graphene sheet, and removing a small portion of the unexfoliated graphene sheet to obtain a graphene dispersion, and graphene dispersion. The liquid includes a single layer of graphene material uniformly dispersed therein. In step S17, the active material is added, the active material is added to the graphene dispersion, and the active material is combined with the single-layer graphene in the graphene dispersion to form a graphene composite material, thereby obtaining a graphene composite material dispersion.
步驟S11懸浮步驟中的石墨烯片可以各種製備法製得，但石墨烯片由於凡得瓦力的緣故非常容易形成聚集，難以直接用機械力量將其再分離，當石墨烯材料置入表面張力相近的溶劑中時，再輔以機械力量會較容易分離聚集的石墨烯。石墨的表面張力約為54 mJ/m2，石墨烯的表面張力則約為47 mJ/m2，因此步驟S11中所使用的溶劑表面張力應大於35 mJ/m2並小於55 mJ/m2，而溶劑與石墨烯片的接觸角係小於80度。The graphene sheet in the suspension step of step S11 can be prepared by various preparation methods, but the graphene sheet is very easy to form and aggregate due to van der Waals force, and it is difficult to directly separate it by mechanical force, when the graphene material is placed in a similar surface tension. In the solvent, it is easier to separate the aggregated graphene by mechanical force. The surface tension of graphite is about 54 mJ/m 2 , and the surface tension of graphene is about 47 mJ/m 2 , so the surface tension of the solvent used in step S11 should be greater than 35 mJ/m 2 and less than 55 mJ/m 2 . And the contact angle of the solvent with the graphene sheet is less than 80 degrees.
上述溶劑係選自苯甲酸芐酯(benzyl benzoate)、N-甲基吡咯烷酮(1-Methyl-2-pyrrolidinone)、γ-丁內酯(γ-Butyrolactone)、N,N-二甲基乙醯胺(N,N-Dimethylacetamide)、1,3-二甲基-2-咪唑啉酮(1,3-Dimethyl-2-Imidazolidinone)、N-乙烯基吡咯烷酮(1-Vinyl-2-pyrrolidone)、N,N-二甲基甲醯胺(N,N-Dimethylformamide)、二甲基亞碸(dimethylsulfoxide)、N-辛基吡咯烷酮(1-Octyl-2-pyrrolidone)、苯胺(aniline)、苯甲醇(benzyl alcohol)、二甘醇(Diethylene glycol)、聚乙二醇(Polyethylene glycol)以及松油醇(terpineol)的至少其中之一。步驟S11懸浮步驟中所得之石墨懸浮液的濃度係小於5 g/L。The above solvent is selected from the group consisting of benzyl benzoate, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide. (N,N-Dimethylacetamide), 1,3-Dimethyl-2-Imidazolidinone, N-vinylpyrrolidone, N, N,N-Dimethylformamide, dimethylsulfoxide, N-octyl-2-pyrrolidone, aniline, benzyl alcohol At least one of Diethylene glycol, Polyethylene glycol, and terpineol. The concentration of the graphite suspension obtained in the suspension step of step S11 is less than 5 g/L.
步驟S13剝離步驟係使用機械力量的方式將石墨烯片於表面張力相近的溶劑中進行進一步的剝離。一般而言，機械力量係使用超音波震盪的效果為最佳。若於溶劑中進一步加入一界面活性劑，則當石墨烯片藉由機械力量被剝離成為多個單層石墨烯材料之後，界面活性劑可迅速吸附於單層石墨烯材料的表面，防止其再次聚集。該界面活性劑係聚乙烯吡咯烷酮(polyvinyl pyrrolidone)。而單層石墨烯材料的厚度係小於3 nm。The stripping step of step S13 is to further peel off the graphene sheets in a solvent having a similar surface tension by mechanical force. In general, mechanical power is best used with ultrasonic vibration. If a surfactant is further added to the solvent, when the graphene sheet is peeled off into a plurality of single-layer graphene materials by mechanical force, the surfactant can be quickly adsorbed on the surface of the single-layer graphene material to prevent it from being again Gather. The surfactant is polyvinyl pyrrolidone. The thickness of the single-layer graphene material is less than 3 nm.
步驟S15分離步驟係將石墨烯懸浮液中少部分仍無法剝離為單層石墨烯材料的石墨烯片進行分離，去除這少部分的石墨烯片後，即獲得完全由單層石墨烯材料均勻分散其中的石墨烯分散液。一般而言，上述的分離方法係使用離心分離的效果最佳。The separating step of step S15 separates a small portion of the graphene suspension which cannot be peeled off into a single-layer graphene material, and after removing a small portion of the graphene sheet, the uniform dispersion of the single-layer graphene material is obtained. Among them is a graphene dispersion. In general, the separation method described above works best with centrifugal separation.
步驟S17活性物質添加步驟係將一活性物質加入石墨烯分散液中，將活性物質與石墨烯分散液均勻混合，即可得到石墨烯複合材料分散液。所述活性物質係選自高分子聚合物、陶瓷粉體、金屬粉體、碳粉及石墨粉的至少其中之一。Step S17: The active material addition step is carried out by adding an active material to the graphene dispersion, and uniformly mixing the active material and the graphene dispersion to obtain a graphene composite dispersion. The active material is selected from at least one of a high molecular polymer, a ceramic powder, a metal powder, a carbon powder, and a graphite powder.
本發明之石墨烯複合材料的製備方法S1可進一步包括另一步驟(圖中未示)，即乾燥步驟，緊接於步驟S17活性物質添加步驟之後，用以乾燥石墨烯複合材料分散液，得到石墨烯複合材料粉體。The preparation method S1 of the graphene composite material of the present invention may further comprise a further step (not shown), that is, a drying step, which is used to dry the graphene composite material dispersion liquid immediately after the step of adding the active material in step S17. Graphene composite powder.
以下實驗示例1-實驗示例10係說明以石墨烯分散液結合活性材料應用於鋰電池、超級電容器、燃料電池電極之電化學應用及導熱複合材料與導電漿之應用。單層石墨烯材料之二維奈米片狀的結構，有利於形成連續的導電導熱網路，因此提升活性材料的電化學與熱傳導性能。The following Experimental Example 1 - Experimental Example 10 illustrates the application of a graphene dispersion in combination with an active material to electrochemical applications of lithium batteries, supercapacitors, fuel cell electrodes, and applications of thermally conductive composites and conductive pastes. The two-dimensional nano-sheet structure of the single-layer graphene material is favorable for forming a continuous conductive and heat-conducting network, thereby improving the electrochemical and thermal conduction properties of the active material.
實驗示例中所使用的石墨烯片係使用熱剝離還原方法製備。取石墨粉10 g置於230 mL的硫酸(H2SO4)中，在冰浴中緩慢加入30 g過錳酸鉀(KMnO4)持續攪拌，過程中將溶液維持於20℃以下，完成之後於35℃下持續攪拌至少40分鐘，再緩慢加入460 mL的去離子水於混合溶液中，保持水浴溫度35℃繼續攪拌至少20分鐘，待反應結束後，將1.4 L去離子水與100 mL雙氧水(H2O2)加入溶液中，靜止放置24小時，最後以5%鹽酸(HCl)清洗過濾，並於真空環境中乾燥，而得到石墨氧化物粉體。The graphene sheets used in the experimental examples were prepared using a thermal stripping reduction method. 10 g of graphite powder was placed in 230 mL of sulfuric acid (H 2 SO 4 ), and 30 g of potassium permanganate (KMnO 4 ) was slowly added in an ice bath and stirring was continued. The solution was maintained at 20 ° C or less after completion. Stir at 35 ° C for at least 40 minutes, then slowly add 460 mL of deionized water to the mixed solution, keep the water bath temperature at 35 ° C and continue to stir for at least 20 minutes. After the reaction is finished, 1.4 L of deionized water and 100 mL of hydrogen peroxide (H 2 O 2 ) was added to the solution, left to stand for 24 hours, finally filtered with 5% hydrochloric acid (HCl), and dried in a vacuum atmosphere to obtain a graphite oxide powder.
將所獲得的石墨氧化物粉體置於真空環境下瞬間接觸1100℃熱源1分鐘以進行剝離，形成預還原之石墨烯片，再將該石墨烯片置於1400℃的5%氫氣/95%氬氣中0.5小時，進行還原及熱處理，即可得到氧含量低於1.5 wt%的石墨烯片，其TEM顯微結構如附件一所示。The obtained graphite oxide powder was placed in a vacuum environment and contacted with a heat source of 1100 ° C for 1 minute to be peeled off to form a pre-reduced graphene sheet, and the graphene sheet was placed at 1400 ° C of 5% hydrogen / 95%. After reduction and heat treatment in argon for 0.5 hour, a graphene sheet having an oxygen content of less than 1.5 wt% can be obtained, and the TEM microstructure of the TEM is as shown in Annex 1.
做為此處實驗示例的石墨烯分散液，取上述石墨烯片0.5 g加入100 mL的N-甲基吡咯烷酮溶劑中，均勻攪拌形成石墨烯懸浮液，如附件二所示。其中N-甲基吡咯烷酮之表面張力約為42-47 mJ/m2，與石墨烯材料相近，可做為一有效分散之溶劑。As the graphene dispersion of the experimental example herein, 0.5 g of the above graphene sheet was added to 100 mL of N-methylpyrrolidone solvent, and uniformly stirred to form a graphene suspension, as shown in Annex 2. The surface tension of N-methylpyrrolidone is about 42-47 mJ/m 2 , which is similar to the graphene material and can be used as an effective dispersion solvent.
將石墨烯懸浮液放入超音波震盪中2小時，再以離心機以4000 rpm轉速離心1小時，將石墨烯懸浮液與離心沉澱之石墨烯片分離，即可得到具有單層石墨烯材料均勻分散其中的石墨烯分散液，其濃度小於0.5 mg/mL，如附件三所示。單層石墨烯材料之TEM顯微結構如附件四所示。單層石墨烯材料之厚度小於2 nm，如附件五之AFM影像所示。The graphene suspension was placed in an ultrasonic vibration for 2 hours, and then centrifuged at 4000 rpm for 1 hour in a centrifuge to separate the graphene suspension from the centrifugally precipitated graphene sheet to obtain a uniform single-layer graphene material. The graphene dispersion dispersed therein has a concentration of less than 0.5 mg/mL as shown in Annex III. The TEM microstructure of the single-layer graphene material is shown in Annex IV. The thickness of the single-layer graphene material is less than 2 nm, as shown in the AFM image of Annex V.
實驗示例1-實驗示例3係說明將石墨烯分散液應用於鋰電池複合材料之製備，以提昇高速充放電的表現。分別取0.05 g、0.1 g、0.2 g的石墨烯片加入100 mL的N-甲基吡咯烷酮溶劑中，均勻攪拌形成石墨懸浮液，將石墨懸浮液放入超音波震盪中2小時，形成石墨烯懸浮液，再經過離心步驟得到石墨烯分散液，將該石墨烯分散液與17 g磷酸鋰鐵(LiFePO4)陶瓷粉末進行混合攪拌，再以烘箱加熱烘乾，即可得到均勻分散的複合材料粉體。所得之石墨烯/磷酸鋰鐵複合材料之SEM顯微結構如附件六所示。Experimental Example 1 - Experimental Example 3 illustrates the application of a graphene dispersion to the preparation of a lithium battery composite to improve the performance of high-speed charge and discharge. Add 0.05 g, 0.1 g, 0.2 g of graphene sheets to 100 mL of N-methylpyrrolidone solvent, stir evenly to form a graphite suspension, and place the graphite suspension in ultrasonic vibration for 2 hours to form graphene suspension. The liquid is further subjected to a centrifugation step to obtain a graphene dispersion, and the graphene dispersion is mixed with 17 g of lithium iron phosphate (LiFePO 4 ) ceramic powder, and then oven-dried to obtain a uniformly dispersed composite powder. body. The SEM microstructure of the obtained graphene/lithium iron phosphate composite material is shown in Annex 6.
取實驗示例1-實驗示例3所獲得之石墨烯/磷酸鋰鐵複合材料做為鋰電池正極材料，以鋰箔做為負極材料，電解液為六氟磷鋰，並按常規工藝組裝為鈕扣型電池後，進行1 C及10 C速率的充放電測試，其結果如表一所示，其連續充放電之結果如附件七所示。Taking the experimental example 1 - experiment example 3 obtained graphene / lithium iron phosphate composite material as a lithium battery cathode material, lithium foil as a negative electrode material, the electrolyte is hexafluorophosphorus lithium, and assembled into a button type according to a conventional process After the battery, the 1 C and 10 C rate charge and discharge tests were performed. The results are shown in Table 1. The results of continuous charge and discharge are shown in Annex VII.
結果顯示，與未使用複合材料的情況相比，石墨烯/磷酸鋰鐵複合材料的表面積、導電度及高速充放電的電容量均大幅提昇。The results show that the surface area, electrical conductivity, and high-speed charge and discharge capacity of the graphene/lithium iron phosphate composite material are greatly improved compared with the case where the composite material is not used.
實驗示例4係採用以石墨烯分散液結合活性炭製備超級電容材料。活性炭主要用於超級電容器，具有超大的比表面積、電化學性能好、電容量高等特點，但其孔洞大多為微孔，孔洞直徑小於2 nm，不利高速充放電時電解液離子的進出。本實驗示例即以石墨烯分散液結合活性炭製備超級電容材料，石墨烯的高表面積可提供高速充放電時的電容量，彌補傳統活性炭電容的不足。實施方式係取均勻分散的石墨烯分散液4 mL，再加入3 g活性炭進行混合攪拌，最後以烘箱加熱烘乾即可得到均勻分散的複合材料粉體。石墨烯/活性炭複合材料之SEM顯微結構如附件八所示。Experimental Example 4 uses a graphene dispersion in combination with activated carbon to prepare a supercapacitor material. Activated carbon is mainly used in supercapacitors, and has the characteristics of large specific surface area, good electrochemical performance and high electric capacity. However, most of the pores are micropores, and the pore diameter is less than 2 nm, which is unfavorable for the entry and exit of electrolyte ions during high-speed charge and discharge. In this experimental example, a supercapacitor material is prepared by using graphene dispersion combined with activated carbon. The high surface area of graphene can provide the capacity at high speed charge and discharge, and make up for the deficiency of traditional activated carbon capacitors. In the embodiment, 4 mL of the uniformly dispersed graphene dispersion is taken, and then 3 g of activated carbon is added for mixing and stirring, and finally heated and dried in an oven to obtain a uniformly dispersed composite powder. The SEM microstructure of the graphene/activated carbon composite is shown in Annex VIII.
將所獲得之石墨烯/活性炭複合材料按常規工藝組裝成為鈕扣型超級電容，其中以親水型不織布做為隔離膜，電解液則是選用氫氧化鉀，並進行不同電流密度的充放電測試及交流阻抗分析。石墨烯/活性炭複合材料之電化學如附件九所示。結果顯示，與未使用複合材料相比，石墨烯/活性炭複合材料高速充放電的電容量不但大幅提昇，同時也擁有較低的元件阻抗值。The obtained graphene/activated carbon composite material is assembled into a button type super capacitor according to a conventional process, wherein a hydrophilic type non-woven fabric is used as a separator, and an electrolyte is selected from potassium hydroxide, and subjected to charge and discharge tests and exchanges of different current densities. Impedance analysis. The electrochemistry of graphene/activated carbon composites is shown in Annex IX. The results show that the graphene/activated carbon composite material has a high capacity for high-speed charge and discharge compared to the unused composite material, and also has a low component resistance value.
實驗示例5-實驗示例6與實驗示例4的目的相同，均採用以石墨烯分散液結合活性炭製備超級電容材料；惟其實施方式是分別取石墨烯片0.1 g及0.2 g加入100 mL的N-甲基吡咯烷酮溶劑中，均勻攪拌形成石墨烯懸浮液，將該懸浮液放入超音波震盪2小時，即可得到均勻分散的石墨烯分散液。再加入16 g活性炭進行混合攪拌，最後以烘箱加熱烘乾即可得到一均勻分散的複合材料粉體。Experimental Example 5 - Experimental Example 6 The same purpose as Experimental Example 4 was to prepare a supercapacitor material by using a graphene dispersion in combination with activated carbon; however, the embodiment was to take a graphene sheet of 0.1 g and 0.2 g, respectively, and add 100 mL of N-A. In the pyrrolidone solvent, uniformly stirred to form a graphene suspension, and the suspension was subjected to ultrasonic vibration for 2 hours to obtain a uniformly dispersed graphene dispersion. Then add 16 g of activated carbon for mixing and stirring, and finally heat and dry in an oven to obtain a uniformly dispersed composite powder.
將所獲得之石墨烯/活性炭複合材料做為超級電容正負極材料，以聚丙烯多孔膜做為隔離膜，電解液為六氟磷鋰，並按常規工藝組裝為鈕扣型超級電容後，進行不同電流密度的充放電測試及交流阻抗分析。石墨烯/活性炭複合材料之電化學如表二所示。The obtained graphene/activated carbon composite material is used as a supercapacitor positive and negative electrode material, a polypropylene porous membrane is used as a separator, and the electrolyte is hexafluorophosphorus lithium, and is assembled into a button type super capacitor according to a conventional process, and then different Charge density test and AC impedance analysis of current density. The electrochemistry of graphene/activated carbon composites is shown in Table 2.
結果顯示，適當的石墨烯/活性炭複合材料量不但有助於提昇高速充放電的電容，同時也可降低的元件阻抗值。The results show that the appropriate amount of graphene/activated carbon composite material not only helps to increase the capacitance of high-speed charge and discharge, but also reduces the resistance value of the component.
實驗示例7係說明將石墨烯分散液應用於奈米金屬粒子複合材料，做為質子交換膜燃料電池之電極。取0.1 g氯化鉑(PtCl6)均勻分散於超純水中，再加入500 mL石墨烯分散液中均勻攪拌，形成石墨烯分散液，過濾該石墨烯分散液並乾燥後，放入高溫爐中，以700℃的5%氫氣/95%氬氣中進行還原熱處理1小時，即可得到鉑與石墨烯之複合材料，將石墨烯/鉑複合材料與Nafion溶液均勻混合配置成為一漿料，利用網版印刷塗佈於Nafion質子交換膜之兩側，乾燥後即可得到一質子交換膜電極組。Experimental Example 7 illustrates the application of a graphene dispersion to a nano metal particle composite as an electrode of a proton exchange membrane fuel cell. 0.1 g of platinum chloride (PtCl 6 ) was uniformly dispersed in ultrapure water, and then uniformly stirred with 500 mL of graphene dispersion to form a graphene dispersion. The graphene dispersion was filtered, dried, and placed in a high temperature furnace. In the reduction heat treatment at 700 ° C in 5% hydrogen / 95% argon for 1 hour, a composite of platinum and graphene can be obtained, and the graphene/platinum composite material and Nafion are obtained. The solution is uniformly mixed and configured into a slurry, which is applied to Nafion by screen printing. On both sides of the proton exchange membrane, a proton exchange membrane electrode group can be obtained after drying.
實驗示例8係說明將石墨烯分散液應用於高分子與陶瓷複合材料，改善其熱傳導表現，有利於半導體封裝材料之應用。取500 mL石墨烯分散液加入1 mL矽烷偶合劑(silane coupling agent,3-aminopropyltrithoxy silane)均勻攪拌，再依照5:1:0.1的比例分別加入環氧樹脂(cresol novolac epoxy)、硬化劑(phenol novolac)與硬化促進劑(triphenyl phosphine)均勻溶解，最後再加入與環氧樹脂相同體積之氮化鋁(aluminum nitride)粉體均勻攪拌3小時，將漿料放入真空烘箱中以80℃烘乾，烘乾之後的產物再研磨至40 mesh以下。將所得到之粉體放入模具中以175℃及50 Kg/cm3的條件熱壓5分鐘，即可得到一環氧樹脂複合材料。將環氧樹脂複合材料的試片進行熱傳導係數測試，與未使用石墨烯分散液的試片相比，使用石墨烯分散液的試片熱傳導值可由4 W/mK提升至5.5 W/mK。Experimental Example 8 illustrates the application of graphene dispersion to polymer and ceramic composites to improve their heat conduction performance and is beneficial to the application of semiconductor packaging materials. Add 500 mL of graphene dispersion to 1 mL of silane coupling agent (3-aminopropyltrithoxy silane) and stir evenly, then add cresol novolac epoxy and hardener according to the ratio of 5:1:0.1. Novolac) is uniformly dissolved with triphenyl phosphine. Finally, the same volume of aluminum nitride powder as the epoxy resin is added and uniformly stirred for 3 hours. The slurry is placed in a vacuum oven and dried at 80 ° C. The product after drying is further ground to below 40 mesh. The obtained powder was placed in a mold and heat-pressed at 175 ° C and 50 Kg/cm 3 for 5 minutes to obtain an epoxy resin composite. The test piece of the epoxy resin composite was subjected to a heat transfer coefficient test, and the heat transfer value of the test piece using the graphene dispersion was increased from 4 W/mK to 5.5 W/mK as compared with the test piece not using the graphene dispersion.
實驗示例9係說明將石墨烯分散液應用於導電複合材料製備為石墨烯導電漿，提昇導電漿之導電表現。取0.1 g石墨烯片加入100 mL松油醇中形成石墨懸浮液，再加入0.01 g聚乙烯吡咯烷酮，經超音波震盪3小時後，以1000 rpm轉速離心0.5小時，將石墨烯懸浮液與離心沉澱的石墨烯片分離，即可得到均勻分散之石墨烯分散液，在石墨烯分散液中加入黏結劑乙基纖維素10 wt%並滴入濕潤分散劑(BYK-190)與靜電助劑(BYK-ES80)，再加入25 g導電石墨均勻混合攪拌形成導電複合漿料，將該漿料利用刮刀塗佈於PET基材上，測得片電阻為70 Ω/sq。Experimental Example 9 shows that the graphene dispersion is applied to a conductive composite material to prepare a graphene conductive paste to enhance the conductive performance of the conductive paste. 0.1 g of graphene sheet was added to 100 mL of terpineol to form a graphite suspension, and then 0.01 g of polyvinylpyrrolidone was added. After ultrasonic vibration for 3 hours, it was centrifuged at 1000 rpm for 0.5 hour to precipitate the graphene suspension and centrifuge. The graphene sheet is separated to obtain a uniformly dispersed graphene dispersion, and 10 wt% of the binder ethyl cellulose is added to the graphene dispersion and the wet dispersant (BYK-190) and the electrostatic auxiliary agent (BYK) are added dropwise. -ES80), further adding 25 g of conductive graphite to uniformly mix and stir to form a conductive composite slurry, and the slurry was coated on a PET substrate by a doctor blade to measure a sheet resistance of 70 Ω/sq.
實驗示例10的步驟與實驗示例9完全相同，惟並無添加石墨烯片於松油醇溶劑中，該石墨漿料測得之片電阻為150 Ω/sq，與實驗示例9相較，顯示石墨烯片分散於松油醇溶劑中形成石墨烯分散液後，可有效提昇導電性。The procedure of Experimental Example 10 was identical to that of Experimental Example 9, except that no graphene sheet was added to the terpineol solvent, and the sheet resistance measured by the graphite slurry was 150 Ω/sq, which showed graphite as compared with Experimental Example 9. When the olefin sheet is dispersed in a terpineol solvent to form a graphene dispersion, the conductivity can be effectively improved.
本發明之石墨烯複合材料的製備方法，其主要特點在於，由於本方法不以石墨經氧化再於複合材料中還原的方式來製得石墨烯，因此不會有還原程度不足的問題。The main feature of the method for preparing the graphene composite material of the present invention is that since the method does not produce graphene by oxidation of graphite and then reduction in the composite material, there is no problem that the degree of reduction is insufficient.
本發明的另一特點在於，所製得的石墨烯複合材料具有高度之分散性，可充分發揮石墨烯之特性，有效提昇複合材料之性能。以本發明方法所製得的石墨烯複合材料的說明性用途係用於電池、電容器、燃料電池、油漆、其他塗料或觸媒。熟諳此技者知道可使用本發明之複合材料的其他應用。Another feature of the present invention is that the obtained graphene composite material has high dispersibility, can fully exert the characteristics of graphene, and effectively improve the performance of the composite material. Illustrative uses of the graphene composites produced by the process of the invention are for batteries, capacitors, fuel cells, paints, other coatings or catalysts. Those skilled in the art are aware of other applications in which the composite materials of the present invention can be used.
以上所述者僅為用以解釋本發明之較佳實施例，並非企圖據以對本發明做任何形式上之限制，是以，凡有在相同之發明精神下所作有關本發明之任何修飾或變更，皆仍應包括在本發明意圖保護之範疇。The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, and any modifications or alterations to the present invention made in the spirit of the same invention. All should still be included in the scope of the intention of the present invention.
S1．．．石墨烯複合材料的製備方法S1. . . Method for preparing graphene composite material
S11．．．懸浮步驟S11. . . Suspension step
S13．．．剝離步驟S13. . . Stripping step
S15．．．分離步驟S15. . . Separation step
S17．．．活性物質添加步驟S17. . . Active substance addition step
第一圖係本發明之石墨烯複合材料的製備方法之流程圖。The first figure is a flow chart of a method for preparing the graphene composite material of the present invention.
S1．．．石墨烯複合材料的製備方法S1. . . Method for preparing graphene composite material
S11．．．懸浮步驟S11. . . Suspension step
S13．．．剝離步驟S13. . . Stripping step
S15．．．分離步驟S15. . . Separation step
S17．．．活性物質添加步驟S17. . . Active substance addition step
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| CN105323949A (en) * | 2014-07-14 | 2016-02-10 | 安炬科技股份有限公司 | Graphene printed circuit structure |
| US10403888B2 (en) | 2015-12-30 | 2019-09-03 | Auo Crystal Corporation | Negative electrode material of lithium battery and method for manufacturing the same |
| CN111003706A (en) * | 2019-11-25 | 2020-04-14 | 苏州盈顺绝缘材料有限公司 | Preparation method of graphene heat conduction and dissipation material |
| TWI708801B (en) * | 2018-02-26 | 2020-11-01 | 謙華科技股份有限公司 | Manufacturing method of graphene composite film |
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| CN101671015B (en) * | 2009-10-13 | 2011-07-20 | 南昌航空大学 | Method of producing graphene |
| CN101973543B (en) * | 2010-10-21 | 2012-08-15 | 中国科学院上海应用物理研究所 | Preparation method of monolayer graphene |
| CN102299326B (en) * | 2011-08-04 | 2014-01-29 | 浙江工业大学 | Graphene modified lithium iron phosphate/carbon composite material and its application |
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| CN105323949A (en) * | 2014-07-14 | 2016-02-10 | 安炬科技股份有限公司 | Graphene printed circuit structure |
| US10403888B2 (en) | 2015-12-30 | 2019-09-03 | Auo Crystal Corporation | Negative electrode material of lithium battery and method for manufacturing the same |
| TWI708801B (en) * | 2018-02-26 | 2020-11-01 | 謙華科技股份有限公司 | Manufacturing method of graphene composite film |
| CN111003706A (en) * | 2019-11-25 | 2020-04-14 | 苏州盈顺绝缘材料有限公司 | Preparation method of graphene heat conduction and dissipation material |
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