TWI667198B - Method for manufacturing graphene composite material - Google Patents
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- TWI667198B TWI667198B TW106146293A TW106146293A TWI667198B TW I667198 B TWI667198 B TW I667198B TW 106146293 A TW106146293 A TW 106146293A TW 106146293 A TW106146293 A TW 106146293A TW I667198 B TWI667198 B TW I667198B
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Abstract
一種石墨烯複合材料的製備方法，其包括以下步驟。對石墨材料與前驅物進行高能量球磨處理，使得前驅物中的元素摻雜至石墨材料中，以形成經摻雜石墨烯。A method for preparing a graphene composite material, comprising the following steps. The graphite material and the precursor are subjected to a high energy ball milling treatment such that elements in the precursor are doped into the graphite material to form doped graphene.
Description
本發明是有關於一種複合材料，且特別是有關於一種石墨烯複合材料。This invention relates to a composite material, and more particularly to a graphene composite.
由於石墨烯（Graphene）具有高電流承載力，且高可撓性以及高透光等特性，因此被業界視為最有潛力的材料，進而將石墨烯更廣泛運用在各個領域，如光電、能源儲存、綠能發電、環境生醫感測或功能性複合材料等。Because graphene has high current carrying capacity, high flexibility and high light transmission, it is regarded as the most promising material in the industry, and it is widely used in various fields such as photovoltaic and energy. Storage, green energy generation, environmental biomedical sensing or functional composites.
傳統的石墨烯製造方法是使用化學氣相沉積法、超聲波法、溶劑熱法、熱解法等，但傳統的製造方法的製程步驟繁雜且製造時間長，造成低產率的問題。此外，由於石墨烯不具有能帶隙，所以難以調整石墨烯的導電性。因此，改善上述石墨烯的缺點仍然是業界亟待研究的課題之一。The conventional graphene manufacturing method uses a chemical vapor deposition method, an ultrasonic method, a solvothermal method, a pyrolysis method, etc., but the conventional manufacturing method has a complicated process and a long manufacturing time, resulting in a problem of low yield. Further, since graphene does not have an energy band gap, it is difficult to adjust the conductivity of graphene. Therefore, the improvement of the above-mentioned disadvantages of graphene is still one of the topics to be studied in the industry.
本發明提供一種石墨烯複合材料的製備方法，其具有製備簡單、產率高以及大量製造的優點。另外，以上述方法所製備的石墨烯複合材料具有良好的導電性。The invention provides a preparation method of a graphene composite material, which has the advantages of simple preparation, high yield and mass production. In addition, the graphene composite material prepared by the above method has good electrical conductivity.
本發明的石墨烯複合材料的製備方法，其包括以下步驟。對石墨材料與前驅物進行高能量球磨處理，使得前驅物中的元素摻雜至石墨材料中，以形成經摻雜石墨烯。A method for producing a graphene composite material of the present invention, which comprises the following steps. The graphite material and the precursor are subjected to a high energy ball milling treatment such that elements in the precursor are doped into the graphite material to form doped graphene.
在本發明的一實施例中，上述的高能量球磨處理的時間例如是5小時至10小時，且高能量球磨處理的轉速例如是300 rpm至900 rpm。In an embodiment of the invention, the high energy ball milling treatment time is, for example, 5 hours to 10 hours, and the high energy ball milling treatment speed is, for example, 300 rpm to 900 rpm.
在本發明的一實施例中，上述的高能量球磨處理的球磨能量例如是8 GJ/g至440 GJ/g。In an embodiment of the invention, the ball milling energy of the high energy ball milling process described above is, for example, from 8 GJ/g to 440 GJ/g.
在本發明的一實施例中，上述的石墨材料的形式與前驅物的形式例如是固體形式，而石墨材料的形式與前驅物的形式不包括液體形式或氣體形式。In an embodiment of the invention, the form of the graphite material described above and the form of the precursor are, for example, a solid form, and the form of the graphite material and the form of the precursor do not include a liquid form or a gaseous form.
在本發明的一實施例中，上述的前驅物中的元素例如是氮、磷、硫、硼或其組合。In an embodiment of the invention, the element in the precursor is, for example, nitrogen, phosphorus, sulfur, boron or a combination thereof.
在本發明的一實施例中，上述的前驅物例如是三聚氰胺、三苯基膦、二苄基二硫、三氧化二硼或其組合。In an embodiment of the invention, the precursor is, for example, melamine, triphenylphosphine, dibenzyl disulfide, boron trioxide or a combination thereof.
在本發明的一實施例中，上述的前驅物與石墨材料的質量比例如是1：2至22：1。In an embodiment of the invention, the mass ratio of the precursor to the graphite material is, for example, 1:2 to 22:1.
在本發明的一實施例中，以上述的經摻雜石墨烯為總數計，經摻雜石墨烯中的元素的含量為0.1原子%至13.2原子%。In an embodiment of the invention, the content of the element in the doped graphene is 0.1 atom% to 13.2 atom% based on the total of the doped graphene described above.
在本發明的一實施例中，所述方法更包括：對所述經摻雜石墨烯直接進行純化處理；以及在所述純化處理之後，將經摻雜石墨烯製作成導電紙。In an embodiment of the invention, the method further comprises: directly purifying the doped graphene; and after the purifying treatment, forming the doped graphene into a conductive paper.
在本發明的一實施例中，在上述的高能量球磨處理的過程中，高能量球磨處理提供機械力剝離石墨材料並使得石墨材料產生缺陷，藉此使得前驅物中的元素取代石墨材料中的碳元素。In an embodiment of the invention, during the high energy ball milling process described above, the high energy ball milling process provides mechanical force to strip the graphite material and cause defects in the graphite material, thereby replacing the elements in the precursor with the graphite material. carbon element.
基於上述，本發明藉由對石墨材料與前驅物進行高能量球磨處理，使得所述前驅物中的元素摻雜至所述石墨材料中，以形成經摻雜石墨烯。相較於未摻雜的石墨烯，本發明的經摻雜石墨烯具有較佳的導電性。此外，由於本發明的石墨烯複合材料的製備方法具有步驟簡單與產率高的優點，其適用於大量生產，進而提升商業競爭力。Based on the above, the present invention allows doping of elements in the precursor into the graphite material by high energy ball milling of the graphite material and the precursor to form doped graphene. The doped graphene of the present invention has better conductivity than undoped graphene. In addition, since the method for preparing the graphene composite material of the present invention has the advantages of simple steps and high yield, it is suitable for mass production, thereby improving commercial competitiveness.
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。The above described features and advantages of the invention will be apparent from the following description.
圖1為本發明之一實施例的一種石墨烯複合材料的製造流程圖。圖2為本發明之一實施例的一種藉由球磨處理來形成石墨烯複合材料的流程示意圖。1 is a flow chart showing the manufacture of a graphene composite material according to an embodiment of the present invention. 2 is a schematic flow chart of forming a graphene composite material by ball milling treatment according to an embodiment of the present invention.
本發明之一實施例提供一種石墨烯複合材料的製備方法10，其步驟如下。請參照圖1與圖2，進行步驟S100，對石墨材料102與前驅物104進行高能量球磨處理106，使得前驅物104中的元素103摻雜至石墨材料102中，以形成經摻雜石墨烯100。在此情況下，經摻雜石墨烯100可視為一種石墨烯複合材料。One embodiment of the present invention provides a method 10 for preparing a graphene composite material, the steps of which are as follows. Referring to FIG. 1 and FIG. 2, step S100 is performed to perform high energy ball milling process 106 on the graphite material 102 and the precursor 104 such that the element 103 in the precursor 104 is doped into the graphite material 102 to form doped graphene. 100. In this case, the doped graphene 100 can be regarded as a graphene composite material.
具體來說，如圖2所示，高能量球磨處理106例如是使用具有球型的研磨體108的球磨機110。在一實施例中，可將石墨材料102、前驅物104以及研磨體108同時放置球磨機110中進行混合與反應。但本發明不以此為限，在其他實施例中，亦可將石墨材料102與前驅物104先行混合後，再與研磨體108一起放置球磨機110中進行反應。球磨機110具有處理量大、設備安裝簡易、操作容易、生產效率高以及成本低的優點，因此，本實施例的製造方法可適用於大量生產。在一實施例中，研磨體108例如是不銹鋼球、氧化鋯顆粒或其組合。研磨體108的直徑愈小，則所形成的經摻雜石墨烯100的層數愈少。在一實施例中，經摻雜石墨烯100的層數可例如是10層或10層以下。Specifically, as shown in FIG. 2, the high energy ball milling process 106 is, for example, a ball mill 110 using a spherical abrasive body 108. In one embodiment, the graphite material 102, the precursor 104, and the abrasive body 108 can be simultaneously placed in the ball mill 110 for mixing and reaction. However, the present invention is not limited thereto. In other embodiments, the graphite material 102 may be first mixed with the precursor 104, and then placed in the ball mill 110 together with the polishing body 108 for reaction. The ball mill 110 has an advantage of a large amount of processing, simple equipment installation, easy operation, high production efficiency, and low cost. Therefore, the manufacturing method of the present embodiment can be applied to mass production. In an embodiment, the abrasive body 108 is, for example, a stainless steel ball, a zirconia particle, or a combination thereof. The smaller the diameter of the abrasive body 108, the less the number of layers of the doped graphene 100 formed. In an embodiment, the number of layers of the doped graphene 100 may be, for example, 10 layers or less.
值得注意的是，在高能量球磨處理106的過程中，高能量球磨處理106可提供機械力（例如是剪應力）剝離石墨材料102並使得石墨材料102產生缺陷，藉此使得前驅物104中的元素103取代石墨材料102中的碳元素。也就是說，高能量球磨處理106可提供球磨能量。所述球磨能量不僅能讓石墨材料102剝離，還能夠在石墨材料102中製造缺陷，以將前驅物104中的元素103摻雜到石墨材料102的缺陷中。在一實施例中，石墨材料102的所述缺陷包括邊緣缺陷、平面缺陷或其組合。某種程度上來說，高能量球磨處理106不僅能將石墨材料102與前驅物104均勻混合，還能夠使得石墨材料102與前驅物104進行取代反應，以將前驅物104中的元素103更容易地取代石墨材料102中的碳元素。Notably, during the high energy ball milling process 106, the high energy ball milling process 106 can provide mechanical force (eg, shear stress) to strip the graphite material 102 and cause the graphite material 102 to create defects, thereby causing the precursor 104 to Element 103 replaces the carbon element in graphite material 102. That is, the high energy ball milling process 106 can provide ball milling energy. The ball milling energy not only allows the graphite material 102 to be peeled off, but also can create defects in the graphite material 102 to dope the elements 103 in the precursor 104 into the defects of the graphite material 102. In an embodiment, the defects of the graphite material 102 include edge defects, planar defects, or a combination thereof. To some extent, the high energy ball milling process 106 not only uniformly mixes the graphite material 102 with the precursor 104, but also enables the graphite material 102 to undergo a substitution reaction with the precursor 104 to more easily mate the element 103 in the precursor 104. The carbon element in the graphite material 102 is replaced.
在一實施例中，石墨材料102包括天然石墨、人造石墨、介相碳微粒（mesophase carbon microbeads，MCMB）或其組合。在一實施例中，前驅物104包括三聚氰胺（Melamine）、三苯基膦（Triphenylphosphine）、二苄基二硫（Dibenzyl disulfide）、三氧化二硼（Boric Anhydride）或其組合。在替代實施例中，前驅物104中的元素103可例如是氮、磷、硫、硼或其組合，也就是說，經摻雜石墨烯100中所摻雜的元素103包括氮、磷、硫、硼或其組合。但本發明不以此為限，在其他實施例中，只要是能摻雜到經摻雜石墨烯100中且改善經摻雜石墨烯100的導電性的元素即為本發明的範疇。In an embodiment, the graphite material 102 comprises natural graphite, artificial graphite, mesophase carbon microbeads (MCMB), or a combination thereof. In one embodiment, the precursor 104 comprises Melamine, Triphenylphosphine, Dibenzyl disulfide, Boric Anhydride, or a combination thereof. In an alternate embodiment, the element 103 in the precursor 104 can be, for example, nitrogen, phosphorus, sulfur, boron, or a combination thereof, that is, the element 103 doped in the doped graphene 100 includes nitrogen, phosphorus, sulfur. Boron or a combination thereof. However, the present invention is not limited thereto, and in other embodiments, an element which can be doped into the doped graphene 100 and improve the conductivity of the doped graphene 100 is within the scope of the present invention.
在本實施例中，前驅物104與石墨材料102的質量比可例如是1：2至22：1。在本實施例中，石墨材料102的形式與前驅物104的形式包括粉末、片狀或其組合，而不包括溶液或氣體。也就是說，在進行高能量球磨處理106的過程中，球磨機110中的石墨材料102、前驅物104以及研磨體108皆為固體形式，而非液體或是氣體形式。因此，在製備經摻雜石墨烯100的過程中，不需要接觸到強酸、強鹼或是氧化還原劑，也不需要處於高溫或高壓的環境下。換言之，本實施例之經摻雜石墨烯100可藉由單一步驟（亦即一道高能量球磨處理106）來形成，其製備步驟簡單且可達到綠能環保的目的。In the present embodiment, the mass ratio of the precursor 104 to the graphite material 102 may be, for example, 1:2 to 22:1. In the present embodiment, the form of the graphite material 102 and the form of the precursor 104 include powder, flakes, or a combination thereof, and do not include a solution or a gas. That is, during the high energy ball milling process 106, the graphite material 102, the precursor 104, and the abrasive body 108 in the ball mill 110 are all in solid form, rather than in liquid or gaseous form. Therefore, in the process of preparing the doped graphene 100, it is not necessary to be exposed to a strong acid, a strong alkali or a redox agent, and it is not required to be in a high temperature or high pressure environment. In other words, the doped graphene 100 of the present embodiment can be formed by a single step (that is, a high-energy ball milling process 106), and the preparation steps are simple and can achieve the purpose of green energy conservation.
在一實施例中，高能量球磨處理106的時間例如是5小時至10小時，而高能量球磨處理106的轉速例如是300 rpm至900 rpm。值得注意的是，當高能量球磨處理106的時間與轉速增加時，高能量球磨處理106的球磨能量也會隨之增加。當高能量球磨處理106的球磨能量大於一預定值（例如是8 GJ/g）時，石墨材料102才會產生缺陷，使得前驅物104中的元素103能夠取代石墨材料102中的碳元素，進而達到較佳的導電性。在一實施例中，當高能量球磨處理106的球磨能量愈大，石墨材料102中的缺陷愈多，則經摻雜石墨烯100中的所摻雜的元素103的摻雜量也愈多。因此，本實施例可藉由調整高能量球磨處理106的球磨能量（或是時間與轉速）來改變經摻雜石墨烯100中的所摻雜的元素103的摻雜量，進而改善經摻雜石墨烯100的導電性。在一實施例中，高能量球磨處理106的球磨能量例如是8 GJ/g至440 GJ/g。In one embodiment, the high energy ball milling process 106 is, for example, 5 hours to 10 hours, and the high energy ball milling process 106 is, for example, 300 rpm to 900 rpm. It is worth noting that as the time and speed of the high energy ball milling process 106 increases, the ball milling energy of the high energy ball milling process 106 also increases. When the ball milling energy of the high energy ball milling process 106 is greater than a predetermined value (eg, 8 GJ/g), the graphite material 102 will produce defects such that the element 103 in the precursor 104 can replace the carbon element in the graphite material 102, thereby Achieve better conductivity. In one embodiment, the greater the ball milling energy of the high energy ball milling process 106, the more defects in the graphite material 102, the more doping of the doped element 103 in the doped graphene 100. Therefore, the present embodiment can improve the doping amount of the doped element 103 in the doped graphene 100 by adjusting the ball milling energy (or time and rotation speed) of the high energy ball milling process 106, thereby improving the doping. The electrical conductivity of graphene 100. In one embodiment, the ball milling energy of the high energy ball milling process 106 is, for example, from 8 GJ/g to 440 GJ/g.
在經過步驟S100之後，以經摻雜石墨烯100為總數計，經摻雜石墨烯100中所摻雜的前驅物104的元素103的含量例如是0.1原子%至13.2原子%。相較於未經摻雜石墨烯，本實施例的經摻雜石墨烯100可具有較低的電阻值，亦即具有較佳的導電性。After the passage of step S100, the content of the element 103 of the precursor 104 doped in the doped graphene 100 is, for example, 0.1 atom% to 13.2 atom%, based on the total of the doped graphene 100. The doped graphene 100 of the present embodiment can have a lower resistance value, that is, has better conductivity than undoped graphene.
接著，如圖1所示，可選擇性地進行步驟S200，對經摻雜石墨烯100直接進行純化處理。更詳細地說，所述純化處理例如是先使用溶劑與經摻雜石墨烯100進行混合。在進行混合時，所述溶劑會溶解經摻雜石墨烯100以外的雜質，例如殘餘的前驅物、有機汙染物等雜質。在一些實施例中，所述溶劑包括水或丙酮。所述純化處理的溫度例如是介於50℃至90℃。Next, as shown in FIG. 1, step S200 can be selectively performed, and the doped graphene 100 is directly subjected to purification treatment. In more detail, the purification treatment is, for example, first mixing with the doped graphene 100 using a solvent. When mixing is performed, the solvent dissolves impurities other than the doped graphene 100, such as impurities such as residual precursors, organic contaminants, and the like. In some embodiments, the solvent comprises water or acetone. The temperature of the purification treatment is, for example, from 50 ° C to 90 ° C.
在將經摻雜石墨烯100與溶劑混合之後，利用抽氣過濾將經摻雜石墨烯100以外的雜質過濾掉，使得經純化處理後的經摻雜石墨烯100具有更高純度，以達到更佳的導電性。After the doped graphene 100 is mixed with the solvent, impurities other than the doped graphene 100 are filtered by suction filtration, so that the purified doped graphene 100 has higher purity to achieve more Good conductivity.
在一實施例中，步驟S200包括進行一次以上的純化處理，例如是二次、三次或更多次的純化處理，但本發明不以此為限，可依照需求調整純化處理的次數來得到所欲純度的石墨烯複合材料。In an embodiment, the step S200 includes performing one or more purification treatments, for example, two, three or more purification treatments, but the invention is not limited thereto, and the number of purification treatments may be adjusted according to requirements to obtain A graphene composite of purity.
此外，在一實施例中，在所述純化處理之後，將經摻雜石墨烯100製作成導電紙。在此情況下，所述導電紙可視為另一種石墨烯複合材料。具體來說，所述導電紙的形成步驟包括將經摻雜石墨烯100與溶劑（例如是去離子水）混合，以形成混合溶液。在本實施例中，所述混合方式可例如是利用均質機震盪，但本發明不以此為限。接著，對所述混合溶液抽氣過濾並烘乾，藉此形成導電紙。Further, in an embodiment, after the purification treatment, the doped graphene 100 is made into a conductive paper. In this case, the conductive paper can be regarded as another graphene composite material. Specifically, the step of forming the conductive paper includes mixing the doped graphene 100 with a solvent such as deionized water to form a mixed solution. In this embodiment, the mixing mode may be oscillated by using a homogenizer, for example, but the invention is not limited thereto. Next, the mixed solution was suction-filtered and dried, thereby forming conductive paper.
為了證明本發明的可實現性，以下列舉多個實例來對本發明之石墨烯複合材料做更進一步地說明。雖然描述了以下實驗，但是在不逾越本發明範疇的情況下，可適當改變所用材料、其量及比率、處理細節以及處理流程等等。因此，不應根據下文所述的實驗對本發明作出限制性的解釋。In order to demonstrate the achievability of the present invention, a plurality of examples are exemplified below to further illustrate the graphene composite of the present invention. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.
實驗例Experimental example 11
在實驗例1中，將質量比為1 g：2 g的三聚氰胺粉末（購買自友和貿易股份有限公司）與石墨塊材（購買自Lanka Graphite Ltd公司）置入球磨機中。接著，依照下表1所示的轉速與時間來進行高能量球磨處理，以形成氮摻雜石墨烯粉體。值得注意的是，由表1中的不同轉速與不同時間所計算出來的球磨能量介於8 GJ/g至440 GJ/g之間。In Experimental Example 1, melamine powder (purchased from Ziyou and Trading Co., Ltd.) and graphite bulk (purchased from Lanka Graphite Ltd) in a mass ratio of 1 g: 2 g were placed in a ball mill. Next, high energy ball milling treatment was performed in accordance with the number of revolutions and time shown in Table 1 below to form nitrogen-doped graphene powder. It is worth noting that the ball milling energy calculated from the different rotational speeds and different times in Table 1 is between 8 GJ/g and 440 GJ/g.
接著，進行3次純化處理，純化處理的步驟如下。將實驗例1的氮摻雜石墨烯粉體與80℃的水進行混合，以將氮摻雜石墨烯粉體以外的雜質溶於80℃的水中。然後，利用抽氣過濾將氮摻雜石墨烯粉體以外的雜質過濾掉，並經過烘乾後，以形成經純化處理後的氮摻雜石墨烯（以下稱之為實驗例1的氮摻雜石墨烯）。Next, the purification treatment was carried out three times, and the purification treatment was carried out as follows. The nitrogen-doped graphene powder of Experimental Example 1 was mixed with water at 80 ° C to dissolve impurities other than the nitrogen-doped graphene powder in water at 80 ° C. Then, impurities other than the nitrogen-doped graphene powder are filtered by suction filtration, and dried to form a purified nitrogen-doped graphene (hereinafter referred to as nitrogen doping of Experimental Example 1). Graphene).
表1 摻雜元素 質量比 (前驅物:石墨) 轉速 (rpm) 時間 (分鐘) 缺陷程度 (ID/IG比) 2D帶位置(cm-1) N摻雜比例(原子%) N 1:2 300 300 0.1675 2693.07 2.37 N 1:2 300 600 0.1785 2691.34 2.63 N 1:2 600 300 0.3384 2686.62 3.83 N 1:2 600 600 0.5377 2682.91 4.82 N 1:2 900 300 0.7900 2679.49 4.51 N 1:2 900 600 1.4029 2676.04 6.63 Table 1 Doping element mass ratio (precursor: graphite) Rotational speed (rpm) Time (minutes) Defect degree (ID/IG ratio) 2D band position (cm-1) N doping ratio (atomic %) N 1:2 300 300 0.1675 2693.07 2.37 N 1:2 300 600 0.1785 2691.34 2.63 N 1:2 600 300 0.3384 2686.62 3.83 N 1:2 600 600 0.5377 2682.91 4.82 N 1:2 900 300 0.7900 2679.49 4.51 N 1:2 900 600 1.4029 2676.04 6.63
實驗例Experimental example 22
在實驗例2中，分別將質量比為5.464 g：0.25 g的三苯基膦粉末（購買自友和貿易股份有限公司）與石墨塊材（購買自Lanka Graphite Ltd公司）置入球磨機中。接著，依照下表2所示的轉速與時間來進行高能量球磨處理，形成磷摻雜石墨烯粉體。值得注意的是，由表2中的不同轉速與不同時間所計算出來的球磨能量介於8 GJ/g至440 GJ/g之間。In Experimental Example 2, triphenylphosphine powder (purchased from Ziyouhe Trading Co., Ltd.) and graphite bulk (purchased from Lanka Graphite Ltd.) having a mass ratio of 5.464 g: 0.25 g were placed in a ball mill, respectively. Next, high-energy ball milling treatment was performed in accordance with the number of revolutions and time shown in Table 2 below to form a phosphorus-doped graphene powder. It is worth noting that the ball milling energy calculated from the different rotational speeds and different times in Table 2 is between 8 GJ/g and 440 GJ/g.
接著，進行3次純化處理，純化處理的步驟如下。將磷摻雜石墨烯粉體與60℃的丙酮進行混合，以將磷摻雜石墨烯粉體以外的雜質溶於60℃的丙酮中。然後，利用抽氣過濾將磷摻雜石墨烯粉體以外的雜質過濾掉，並經過烘乾後，以形成經純化處理後的磷摻雜石墨烯（以下稱之為實驗例2的磷摻雜石墨烯）。Next, the purification treatment was carried out three times, and the purification treatment was carried out as follows. The phosphorus-doped graphene powder was mixed with acetone at 60 ° C to dissolve impurities other than the phosphorus-doped graphene powder in acetone at 60 ° C. Then, impurities other than the phosphorus-doped graphene powder are filtered by suction filtration, and dried to form a purified phosphorus-doped graphene (hereinafter referred to as phosphorus doping of Experimental Example 2). Graphene).
表2 摻雜元素 質量比 (前驅物:石墨) 轉速 (rpm) 時間 (分鐘) 缺陷程度 (ID/IG比) 2D帶位置(cm-1) P摻雜比例(原子%) P 22:1 300 300 0.1826 2709.97 0.32 P 22:1 300 600 0.3274 2709.97 0.29 P 22:1 600 300 0.1946 2703.04 0.59 P 22:1 600 600 0.7845 2697.56 0.42 P 22:1 900 300 0.5445 2702.02 0.54 P 22:1 900 600 1.0551 2694.83 0.70 Table 2 Doping element mass ratio (precursor: graphite) Rotational speed (rpm) Time (minutes) Degree of defect (ID/IG ratio) 2D band position (cm-1) P doping ratio (atomic %) P 22:1 300 300 0.1826 2709.97 0.32 P 22:1 300 600 0.3274 2709.97 0.29 P 22:1 600 300 0.1946 2703.04 0.59 P 22:1 600 600 0.7845 2697.56 0.42 P 22:1 900 300 0.5445 2702.02 0.54 P 22:1 900 600 1.0551 2694.83 0.70
實驗例Experimental example 33
在實驗例3中，分別將質量比為3.626 g：0.25 g的三氧化二硼粉末（購買自友和貿易股份有限公司）與石墨塊材（購買自Lanka Graphite Ltd公司）置入球磨機中。接著，依照下表3所示的轉速與時間來進行高能量球磨處理，形成硼摻雜石墨烯粉體。值得注意的是，由表3中的不同轉速與不同時間所計算出來的球磨能量介於8 GJ/g至440 GJ/g之間。In Experimental Example 3, boron trioxide powder (purchased from Ziyouhe Trading Co., Ltd.) and graphite bulk (purchased from Lanka Graphite Ltd) were placed in a ball mill at a mass ratio of 3.626 g: 0.25 g, respectively. Next, high-energy ball milling treatment was performed in accordance with the number of revolutions and time shown in Table 3 below to form a boron-doped graphene powder. It is worth noting that the ball milling energy calculated from the different rotational speeds and different times in Table 3 is between 8 GJ/g and 440 GJ/g.
接著，進行3次純化處理，純化處理的步驟如下。將硼摻雜石墨烯粉體與80℃的水進行混合，以將硼摻雜石墨烯粉體以外的雜質溶於80℃的水中。然後，利用抽氣過濾將硼摻雜石墨烯粉體以外的雜質過濾掉，並經過烘乾後，以形成經純化處理後的硼摻雜石墨烯（以下稱之為實驗例3的硼摻雜石墨烯）。Next, the purification treatment was carried out three times, and the purification treatment was carried out as follows. The boron-doped graphene powder was mixed with water at 80 ° C to dissolve impurities other than the boron-doped graphene powder in water at 80 ° C. Then, impurities other than the boron-doped graphene powder are filtered by suction filtration, and dried to form a boron-doped graphene after purification treatment (hereinafter referred to as boron doping of Experimental Example 3). Graphene).
表3 摻雜元素 質量比 (前驅物:石墨) 轉速 (rpm) 時間 (分鐘) 缺陷程度 (ID/IG比) 2D帶位置(cm-1) B摻雜比例(原子%) B 15:1 300 300 0.389 2703.10 0.88 B 15:1 300 600 0.347 2716.02 0.10 B 15:1 600 300 0.802 2687.85 2.34 B 15:1 600 600 1.043 2690.50 0.19 B 15:1 900 300 0.831 2683.44 6.78 B 15:1 900 600 1.379 2681.70 13.20 table 3 Doping element mass ratio (precursor: graphite) Rotational speed (rpm) Time (minutes) Defect degree (ID/IG ratio) 2D band position (cm-1) B doping ratio (atomic %) B 15:1 300 300 0.389 2703.10 0.88 B 15:1 300 600 0.347 2716.02 0.10 B 15:1 600 300 0.802 2687.85 2.34 B 15:1 600 600 1.043 2690.50 0.19 B 15:1 900 300 0.831 2683.44 6.78 B 15:1 900 600 1.379 2681.70 13.20
實驗例Experimental example 44
在實驗例4中，分別將質量比為0.25 g：0.5 g的二硫化二卡基粉末（購買自友和貿易股份有限公司）與石墨塊材（購買自Lanka Graphite Ltd公司）置入球磨機中。接著，依照下表4所示的轉速與時間來進行高能量球磨處理，形成硫摻雜石墨烯粉體。值得注意的是，由表4中的不同轉速與不同時間所計算出來的球磨能量介於8 GJ/g至440 GJ/g之間。In Experimental Example 4, dicarbosulfide disulfide powder (purchased from Ziyouhe Trading Co., Ltd.) and graphite bulk (purchased from Lanka Graphite Ltd.) in a mass ratio of 0.25 g: 0.5 g were placed in a ball mill, respectively. Next, high-energy ball milling treatment was performed in accordance with the number of revolutions and time shown in Table 4 below to form a sulfur-doped graphene powder. It is worth noting that the ball milling energy calculated from the different rotational speeds and different times in Table 4 is between 8 GJ/g and 440 GJ/g.
接著，進行3次純化處理，純化處理的步驟如下。將硫摻雜石墨烯粉體與60℃的丙酮進行混合，以將硫摻雜石墨烯粉體以外的雜質溶於60℃的丙酮中。然後，利用抽氣過濾將硫摻雜石墨烯粉體以外的雜質過濾掉，並經過烘乾後，以形成經純化處理後的硫摻雜石墨烯（以下稱之為實驗例4的硫摻雜石墨烯）。Next, the purification treatment was carried out three times, and the purification treatment was carried out as follows. The sulfur-doped graphene powder was mixed with acetone at 60 ° C to dissolve impurities other than the sulfur-doped graphene powder in acetone at 60 ° C. Then, impurities other than the sulfur-doped graphene powder are filtered by suction filtration, and dried to form a sulfur-doped graphene after purification treatment (hereinafter referred to as sulfur doping of Experimental Example 4). Graphene).
表4 摻雜元素 質量比 (前驅物:石墨) 轉速 (rpm) 時間 (分鐘) 缺陷程度 (ID/IG比) 2D帶位置(cm-1) S摻雜比例(原子%) S 1:2 300 300 0.2926 2691.0 0.63 S 1:2 300 600 0.6334 2698.0 0.47 S 1:2 600 300 1.6109 2678.8 1.11 S 1:2 600 600 1.5591 2680.0 1.17 S 1:2 900 300 1.5287 2679.0 2.20 S 1:2 900 600 1.8892 2682.5 2.29 Table 4 Doping element mass ratio (precursor: graphite) Rotational speed (rpm) Time (minutes) Defect degree (ID/IG ratio) 2D band position (cm-1) S doping ratio (atomic %) S 1:2 300 300 0.2926 2691.0 0.63 S 1:2 300 600 0.6334 2698.0 0.47 S 1:2 600 300 1.6109 2678.8 1.11 S 1:2 600 600 1.5591 2680.0 1.17 S 1:2 900 300 1.5287 2679.0 2.20 S 1:2 900 600 1.8892 2682.5 2.29
缺陷程度量測Defect level measurement
量測實驗例1的氮摻雜石墨烯、實驗例2的磷摻雜石墨烯、實驗例3的硼摻雜石墨烯以及實驗例4的硫摻雜石墨烯的拉曼光譜，以獲得I D/I G值（其中，I D為D帶（D band）的強度，I G為G帶（G band）的強度），進而得知實驗例1-4的經摻雜石墨烯的缺陷程度。量測的結果如上表1-4所示。 The Raman spectra of the nitrogen-doped graphene of Experimental Example 1, the phosphorus-doped graphene of Experimental Example 2, the boron-doped graphene of Experimental Example 3, and the sulfur-doped graphene of Experimental Example 4 were measured to obtain I D . The value of /I G (where I D is the intensity of the D band, and I G is the intensity of the G band), and the degree of defect of the doped graphene of Experimental Example 1-4 was further known. The results of the measurements are shown in Table 1-4 above.
由上表1-4可知，在相同時間下，當高能量球磨處理的轉速增加，實驗例1的氮摻雜石墨烯、實驗例2的磷摻雜石墨烯、實驗例3的硼摻雜石墨烯以及實驗例4的硫摻雜石墨烯的缺陷程度也隨之增加，進而提升氮摻雜、磷摻雜、硼摻雜以及硫摻雜的比例。As can be seen from the above Tables 1-4, at the same time, when the rotational speed of the high-energy ball milling treatment is increased, the nitrogen-doped graphene of Experimental Example 1, the phosphorus-doped graphene of Experimental Example 2, and the boron-doped graphite of Experimental Example 3 are obtained. The degree of defects of the olefin and the sulfur-doped graphene of Experimental Example 4 also increased, thereby increasing the ratio of nitrogen doping, phosphorus doping, boron doping, and sulfur doping.
石墨烯層數量Number of graphene layers 測Measurement
另外，藉由上述拉曼光譜中2D帶（2D band）的位置，可推算實驗例1的氮摻雜石墨烯、實驗例2的磷摻雜石墨烯、實驗例3的硼摻雜石墨烯以及實驗例4的硫摻雜石墨烯的層數。由上表1-4可知，實驗例1的氮摻雜石墨烯、實驗例2的磷摻雜石墨烯、實驗例3的硼摻雜石墨烯以及實驗例4的硫摻雜石墨烯的2D帶的位置約為2720 cm -1，其層數約為10層或10層以下。 Further, the nitrogen-doped graphene of Experimental Example 1, the phosphorus-doped graphene of Experimental Example 2, the boron-doped graphene of Experimental Example 3, and the boron-doped graphene of Experimental Example 3 can be estimated by the position of the 2D band in the above Raman spectrum. The number of layers of sulfur-doped graphene in Experimental Example 4. As can be seen from the above Tables 1-4, the nitrogen-doped graphene of Experimental Example 1, the phosphorus-doped graphene of Experimental Example 2, the boron-doped graphene of Experimental Example 3, and the 2D band of the sulfur-doped graphene of Experimental Example 4 The position is about 2720 cm -1 and the number of layers is about 10 or less.
摻雜量檢測Doping amount detection
藉由X射線光電子光譜（X-ray photoelectron spectroscopy，XPS）可以分析出經摻雜石墨烯中所摻雜的元素的摻雜量，也能夠檢測出經摻雜石墨烯中的鍵結結構。The doping amount of the element doped in the doped graphene can be analyzed by X-ray photoelectron spectroscopy (XPS), and the bonding structure in the doped graphene can also be detected.
量測實驗例1的氮摻雜石墨烯的X射線光電子光譜，其結果如上表1所示。由上表1可知，隨著高能量球磨處理的轉速與時間增加，實驗例1的氮摻雜石墨烯的氮摻雜比例也隨之增加。X射線光電子光譜亦顯示實驗例1的氮摻雜石墨烯的鍵結結構包括吡啶型氮（Pyridinic N）結構、吡咯型氮（Pyrrolic N）結構、四元氮（Quaternary N）結構以及N-氧化吡啶（Oxides pyridinic N）結構。The X-ray photoelectron spectrum of the nitrogen-doped graphene of Experimental Example 1 was measured, and the results are shown in Table 1 above. As can be seen from the above Table 1, as the rotation speed and time of the high-energy ball milling treatment increased, the nitrogen doping ratio of the nitrogen-doped graphene of Experimental Example 1 also increased. X-ray photoelectron spectroscopy also showed that the nitrogen-doped graphene bonding structure of Experimental Example 1 includes a Pyridic N structure, a Pyrrolic N structure, a quaternary N structure, and N-oxidation. Oxides pyridinic N structure.
量測實驗例2的磷摻雜石墨烯的X射線光電子光譜，其結果如上表2所示。由上表2可知，在相同時間下，隨著高能量球磨處理的轉速增加，基本上實驗例2的磷摻雜石墨烯的磷摻雜比例也隨之增加。X射線光電子光譜亦顯示實驗例2的磷摻雜石墨烯的鍵結結構包括P-C鍵結與P-O鍵結。The X-ray photoelectron spectrum of the phosphorus-doped graphene of Experimental Example 2 was measured, and the results are shown in Table 2 above. As can be seen from the above Table 2, at the same time, as the rotational speed of the high-energy ball milling treatment increases, the phosphorus doping ratio of the phosphorus-doped graphene of Experimental Example 2 also increases. The X-ray photoelectron spectroscopy also showed that the bonding structure of the phosphorus-doped graphene of Experimental Example 2 included P-C bonding and P-O bonding.
量測實驗例3的硼摻雜石墨烯的X射線光電子光譜，其結果如上表3所示。由上表3可知，在相同時間下，隨著高能量球磨處理的轉速增加，基本上實驗例3的硼摻雜石墨烯的硼摻雜比例也隨之增加。X射線光電子光譜亦顯示實驗例3的硼摻雜石墨烯的鍵結結構包括B 4C鍵結、BC 3鍵結、BC 2O鍵結、BCO 2鍵結以及B 2O 3鍵結。 The X-ray photoelectron spectrum of the boron-doped graphene of Experimental Example 3 was measured, and the results are shown in Table 3 above. As can be seen from the above Table 3, at the same time, as the rotational speed of the high-energy ball milling treatment increases, the boron doping ratio of the boron-doped graphene of Experimental Example 3 also increases. The X-ray photoelectron spectroscopy also showed that the bonding structure of the boron-doped graphene of Experimental Example 3 included B 4 C bonding, BC 3 bonding, BC 2 O bonding, BCO 2 bonding, and B 2 O 3 bonding.
量測實驗例4的硫摻雜石墨烯的X射線光電子光譜，其結果如上表4所示。由上表4可知，在相同時間下，隨著高能量球磨處理的轉速增加，基本上實驗例4的硫摻雜石墨烯的硫摻雜比例也隨之增加。X射線光電子光譜亦顯示實驗例4的硫摻雜石墨烯的鍵結結構包括C-SO 2-C鍵結、C-SO 3-C鍵結以及C-SO 4-C鍵結。 The X-ray photoelectron spectrum of the sulfur-doped graphene of Experimental Example 4 was measured, and the results are shown in Table 4 above. As can be seen from the above Table 4, at the same time, as the rotational speed of the high-energy ball milling treatment increases, the sulfur doping ratio of the sulfur-doped graphene of Experimental Example 4 also increases. The X-ray photoelectron spectroscopy also showed that the bonding structure of the sulfur-doped graphene of Experimental Example 4 included a C-SO 2 -C bond, a C-SO 3 -C bond, and a C-SO 4 -C bond.
由上述的實驗結果可知，當高能量球磨處理的轉速與時間增加時，其可提供更多的球磨能量，使得石墨材料剝離並在石墨材料中製造更多的缺陷，進而將更多的摻雜元素摻雜到石墨材料的缺陷中。It can be seen from the above experimental results that when the rotation speed and time of the high-energy ball milling treatment increase, it can provide more ball milling energy, which causes the graphite material to peel off and make more defects in the graphite material, thereby further doping. The element is doped into the defects of the graphite material.
比較例Comparative example 11
在比較例1中，將2 g的石墨置入球磨機中。接著，依照上表1所示的不同轉速（亦即300 rpm、600 rpm以及900 rpm）與不同時間（亦即300分鐘與600分鐘）來進行高能量球磨處理，形成未經摻雜石墨烯粉體（以下稱之為比較例1的未經摻雜石墨烯）。In Comparative Example 1, 2 g of graphite was placed in a ball mill. Then, according to the different rotation speeds shown in Table 1 (ie, 300 rpm, 600 rpm, and 900 rpm) and different times (ie, 300 minutes and 600 minutes), high-energy ball milling treatment is performed to form undoped graphene powder. The body (hereinafter referred to as undoped graphene of Comparative Example 1).
電阻值量測Resistance measurement
分別將實驗例1的氮摻雜石墨烯、實驗例2的磷摻雜石墨烯以及比較例1的未經摻雜石墨烯製作成導電紙，並且測量其電阻值（以下簡稱為實驗例1、實驗例2或比較例1的電阻值）。具體來說，是將5 mg的實驗例1的氮摻雜石墨烯、5 mg的實驗例2的磷摻雜石墨烯或5 mg的比較例1的未經摻雜石墨烯加入20 ml的去離子水中，接著，使用均質機震盪10分鐘。之後，經過抽氣過濾並在室溫（例如約為22℃至30℃）下烘乾24小時後，以形成實驗例1、實驗例2或比較例1的導電紙。The nitrogen-doped graphene of Experimental Example 1, the phosphorus-doped graphene of Experimental Example 2, and the undoped graphene of Comparative Example 1 were respectively made into conductive paper, and the resistance value thereof was measured (hereinafter referred to as Experimental Example 1). The resistance value of Experimental Example 2 or Comparative Example 1). Specifically, 5 mg of the nitrogen-doped graphene of Experimental Example 1, 5 mg of the phosphorus-doped graphene of Experimental Example 2 or 5 mg of the undoped graphene of Comparative Example 1 was added to 20 ml. In ionic water, it was then shaken for 10 minutes using a homogenizer. Thereafter, it is subjected to suction filtration and dried at room temperature (for example, about 22 ° C to 30 ° C) for 24 hours to form conductive paper of Experimental Example 1, Experimental Example 2 or Comparative Example 1.
圖3為實驗例1、2以及比較例1的電阻值（其為標準化（normalized）後的電阻值）與球磨能量的關係圖。3 is a graph showing the relationship between the resistance values (the resistance values after normalization) and the ball milling energy in Experimental Examples 1 and 2 and Comparative Example 1.
如圖3所示，隨著球磨能量增加，比較例1的電阻值大幅增加，反觀，實驗例1與實驗例2的電阻值僅微量增加。因此，實驗例1、2與比較例1的電阻值之間的差距愈大。也就是說，隨著球磨能量增加，實驗例1、2的導電紙的電阻值下降程度愈大。由此可知，相較於比較例1之未經摻雜石墨烯所製作成的導電紙，本發明之經摻雜石墨烯所製作成導電紙（如實驗例1、2所示）具有更佳的導電性。而且隨著球磨能量增加，經摻雜石墨烯中的摻雜元素的比例也隨之增加，進而改善經摻雜石墨烯中的導電性。As shown in FIG. 3, as the ball milling energy increased, the resistance value of Comparative Example 1 increased greatly, and in contrast, the resistance values of Experimental Example 1 and Experimental Example 2 increased only slightly. Therefore, the difference between the resistance values of Experimental Examples 1, 2 and Comparative Example 1 was larger. That is, as the ball milling energy increases, the resistance value of the conductive paper of Experimental Examples 1 and 2 decreases to a greater extent. It can be seen that the conductive paper prepared by the doped graphene of the present invention is more preferable than the conductive paper prepared by the undoped graphene of Comparative Example 1 (as shown in Experimental Examples 1 and 2). Conductivity. Moreover, as the ball milling energy increases, the proportion of doping elements in the doped graphene also increases, thereby improving the conductivity in the doped graphene.
基於上述，本發明藉由對石墨材料與前驅物進行高能量球磨處理，使得所述前驅物中的元素摻雜至所述石墨材料中，以形成經摻雜石墨烯。相較於未摻雜的石墨烯，本發明的經摻雜石墨烯具有較佳的導電性。另外，由於本發明的石墨烯複合材料的製備方法具有步驟簡單與產率高的優點，其適用於大量生產，進而提升商業競爭力。Based on the above, the present invention allows doping of elements in the precursor into the graphite material by high energy ball milling of the graphite material and the precursor to form doped graphene. The doped graphene of the present invention has better conductivity than undoped graphene. In addition, since the method for preparing the graphene composite material of the present invention has the advantages of simple steps and high yield, it is suitable for mass production, thereby improving commercial competitiveness.
此外，本發明的石墨烯複合材料因具有較佳的導電性，其可適用於透明導電薄膜、超級電容器、鋰離子電池、光感測器、高效能導熱片等相關應用，而極具商業價值。In addition, the graphene composite material of the invention has good conductivity, and can be applied to transparent conductive films, super capacitors, lithium ion batteries, photo sensors, high-performance thermal conductive sheets and the like, and has great commercial value. .
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.
10：製備方法 100：經摻雜石墨烯 102：石墨材料 103：元素 104：前驅物 106：高能量球磨處理 108：研磨體 110：球磨機 S100、S200：步驟10: Preparation method 100: Doped graphene 102: Graphite material 103: Element 104: Precursor 106: High energy ball milling treatment 108: Abrasive body 110: Ball mill S100, S200: Step
圖1為本發明之一實施例的一種石墨烯複合材料的製造流程圖。 圖2為本發明之一實施例的一種藉由球磨處理來形成石墨烯複合材料的流程示意圖。 圖3為實驗例1、2以及比較例1的電阻值與球磨能量的關係圖。1 is a flow chart showing the manufacture of a graphene composite material according to an embodiment of the present invention. 2 is a schematic flow chart of forming a graphene composite material by ball milling treatment according to an embodiment of the present invention. 3 is a graph showing the relationship between the resistance value and the ball milling energy of Experimental Examples 1, 2 and Comparative Example 1.
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