TWI781777B - Three dimension crumpled graphene, producing method thereof and apparatus for producing the same - Google Patents

Three dimension crumpled graphene, producing method thereof and apparatus for producing the same Download PDF

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TWI781777B
TWI781777B TW110136329A TW110136329A TWI781777B TW I781777 B TWI781777 B TW I781777B TW 110136329 A TW110136329 A TW 110136329A TW 110136329 A TW110136329 A TW 110136329A TW I781777 B TWI781777 B TW I781777B
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graphene
reaction element
dimensional
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wrinkled
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TW202313460A (en
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陳軍互
劉昀佩
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國立中山大學
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The present invention relates to a three dimension crumpled graphene, a producing method thereof and an apparatus for producing the same. In the method of the application, graphene droplets are cooled by a low temperature environment, thereby producing the three dimension crumpled graphene. The three dimension crumpled graphene has excellent thermal conducting properties and pressure resistance.

Description

三維皺褶石墨烯、其製作方法，以及製備三維皺褶石墨烯的設備Three-dimensional wrinkled graphene, its production method, and equipment for preparing three-dimensional wrinkled graphene

本發明係有關一種石墨烯材料，特別是提供一種三維皺褶石墨烯與其製作方法，以及製備此三維皺褶石墨烯的設備。The present invention relates to a graphene material, and in particular provides a three-dimensional wrinkled graphene and its manufacturing method, as well as equipment for preparing the three-dimensional wrinkled graphene.

石墨烯材料係由碳原子所構成之二維的平面材料。由於石墨烯材料具有良好之熱傳導性質，故石墨烯材料常用以製作散熱元件。然而，礙於結構之限制，相較於x-y平面，石墨烯材料於z軸方向不具有優異之熱傳導性質，而難以進一步提升其性質。另外，平面之石墨烯材料亦容易受到分子間之吸引力，而彼此堆疊，因此石墨烯材料具有較差之分散性。Graphene material is a two-dimensional planar material composed of carbon atoms. Because graphene materials have good thermal conductivity properties, graphene materials are often used to make heat dissipation elements. However, due to structural limitations, compared with the x-y plane, graphene materials do not have excellent thermal conductivity properties in the z-axis direction, and it is difficult to further improve their properties. In addition, planar graphene materials are also easily attracted by intermolecular forces to stack each other, so the graphene materials have poor dispersion.

有鑑於此，亟須提供一種皺褶石墨烯、其製作方法，以及製備皺褶石墨烯的設備，以進一步提升石墨烯材料之熱傳導性質，並解決習知石墨烯材料分散性較差的缺陷。In view of this, there is an urgent need to provide a wrinkled graphene, its manufacturing method, and equipment for preparing the wrinkled graphene, so as to further improve the thermal conductivity of the graphene material and solve the defect of poor dispersion of the conventional graphene material.

因此，本發明之一態樣是在提供一種三維皺褶石墨烯的製作方法，其藉由噴灑石墨烯液滴至低溫氣相環境中，以形成皺褶石墨烯。Therefore, one aspect of the present invention is to provide a method for manufacturing three-dimensional wrinkled graphene, which forms the wrinkled graphene by spraying graphene droplets into a low-temperature gas phase environment.

本發明之另一態樣是在提供一種三維皺褶石墨烯，其是利用前述之製作方法所製成。Another aspect of the present invention is to provide a three-dimensional wrinkled graphene, which is made by the aforementioned manufacturing method.

本發明之又一態樣是在提供一種製備三維皺褶石墨烯的設備，其利用冷卻媒介來降低反應槽內之氣體溫度，而可凝固石墨烯液滴中之液體，進而製得三維皺褶石墨烯。Another aspect of the present invention is to provide a device for preparing three-dimensional wrinkled graphene, which uses a cooling medium to reduce the temperature of the gas in the reaction tank, so that the liquid in the graphene droplets can be solidified, and then the three-dimensional wrinkled graphene can be produced Graphene.

根據本發明之一態樣，提出一種三維皺褶石墨烯的製作方法。此製作方法係先提供反應元件，其中反應元件之反應槽包含封閉底部與頂部。然後，對此反應元件進行冷卻製程。接著，進行噴灑製程，以製得三維皺褶石墨烯。其中，噴灑製程係由反應元件之頂部噴入石墨烯溶液至反應元件中，且冷卻製程係使反應元件內之氣體溫度係不大於石墨烯溶液的溶劑之凝固點。According to an aspect of the present invention, a method for manufacturing three-dimensional wrinkled graphene is proposed. In this manufacturing method, a reaction element is firstly provided, wherein the reaction tank of the reaction element includes a closed bottom and a top. Then, a cooling process is performed on the reaction element. Next, a spraying process is performed to produce three-dimensional wrinkled graphene. Wherein, the spraying process is to spray the graphene solution into the reaction element from the top of the reaction element, and the cooling process is to make the temperature of the gas in the reaction element not greater than the freezing point of the solvent of the graphene solution.

依據本發明之一些實施例，前述之冷卻製程係將反應元件放置於冷卻媒介中。According to some embodiments of the present invention, the aforementioned cooling process is to place the reaction element in a cooling medium.

依據本發明之一些實施例，於進行前述之冷卻製程前，此製作方法可選擇性地放置一載材於封閉底部上。According to some embodiments of the present invention, before performing the aforementioned cooling process, the fabrication method may optionally place a carrier on the closed bottom.

依據本發明之一些實施例，於進行前述之冷卻製程前，此製作方法可選擇性地對反應元件進行減壓製程，以使反應槽內之氣體壓力係小於1 atm。According to some embodiments of the present invention, before performing the aforementioned cooling process, the manufacturing method may optionally perform a decompression process on the reaction element, so that the gas pressure in the reaction tank is less than 1 atm.

依據本發明之一些實施例，前述之石墨烯溶液包含氧化石墨烯。According to some embodiments of the present invention, the aforementioned graphene solution includes graphene oxide.

依據本發明之一些實施例，前述石墨烯溶液之濃度係不小於0.05 mg/mL。According to some embodiments of the present invention, the concentration of the aforementioned graphene solution is not less than 0.05 mg/mL.

根據本發明之另一態樣，提出一種三維皺褶石墨烯，其係利用前述之製作方法所製成。其中，三維皺褶石墨烯係球型的，且三維皺褶石墨烯之耐壓性係不小於400 kg/cm 2。 According to another aspect of the present invention, a three-dimensional wrinkled graphene is proposed, which is manufactured by the aforementioned manufacturing method. Among them, the three-dimensional wrinkled graphene is spherical, and the pressure resistance of the three-dimensional wrinkled graphene is not less than 400 kg/cm 2 .

根據本發明之又一態樣，提出一種製備三維皺褶石墨烯的設備。此設備包含槽體與反應元件，其中槽體係配置以容納冷卻媒介，且反應元件係放置於槽體中。反應元件包含反應槽與噴灑單元。反應槽包含封閉底部與頂部。頂部係相對於封閉底部，且頂部具有開孔，其中此開孔係高於冷卻媒介。噴灑單元係設於開孔，以使反應元件係氣密的。其中，噴灑單元之噴出孔係延伸至反應元件中，且噴灑單元係配置以經由噴出孔噴入石墨烯溶液至反應元件中。According to another aspect of the present invention, a device for preparing three-dimensional wrinkled graphene is proposed. The device includes a tank and a reaction element, wherein the tank system is configured to accommodate a cooling medium, and the reaction element is placed in the tank. The reaction element includes a reaction tank and a spray unit. The reaction tank has a closed bottom and a top. The top is opposite to the closed bottom, and the top has an opening, wherein the opening is higher than the cooling medium. The spraying unit is arranged in the opening so that the reaction element is airtight. Wherein, the spray hole of the spray unit extends into the reaction element, and the spray unit is configured to spray the graphene solution into the reaction element through the spray hole.

依據本發明之一些實施例，前述之反應槽係由一導熱材料所製成。According to some embodiments of the present invention, the aforementioned reaction tank is made of a heat-conducting material.

依據本發明之一些實施例，前述之反應槽可選擇性地包含減壓管，且此減壓管係設置於頂部。According to some embodiments of the present invention, the aforementioned reaction tank may optionally include a decompression pipe, and the decompression pipe is arranged at the top.

應用本發明三維皺褶石墨烯、其製作方法，以及製備三維皺褶石墨烯的設備，其係利用冷卻媒介來冷卻反應槽內之氣體溫度，並將石墨烯溶液噴灑至此低溫氣相環境中。所噴出之石墨烯液滴中的液體可因低溫而凝固，而使平面之石墨烯產生三維之皺褶結構。其中，石墨烯之三維皺褶結構可自立(free-standing)存在，而係不須依靠外力來維持。據此，所形成之三維皺褶石墨烯具有較佳之熱傳導性質，且石墨烯間之分子吸引力(如凡得瓦爾力)減弱，故皺褶石墨烯具有較佳之分散性。另外，由於石墨烯液滴係於低溫氣相環境中凝固，故於凝固階段之液滴不易彼此再結合，且已凝固之液滴亦不易與未完全凝固之液滴再結合。因此，本發明製得之三維皺褶石墨烯具有均一之粒徑分布。The three-dimensional wrinkled graphene of the present invention, its manufacturing method, and the equipment for preparing three-dimensional wrinkled graphene use a cooling medium to cool the gas temperature in the reaction tank, and spray the graphene solution into the low-temperature gas-phase environment. The liquid in the ejected graphene droplets can be solidified due to low temperature, so that the planar graphene produces a three-dimensional wrinkled structure. Among them, the three-dimensional wrinkled structure of graphene can exist independently (free-standing), and does not need to rely on external force to maintain. Accordingly, the formed three-dimensional wrinkled graphene has better thermal conductivity, and the molecular attraction (such as van der Waals force) between graphenes is weakened, so the wrinkled graphene has better dispersion. In addition, since the graphene droplets are solidified in a low-temperature gas phase environment, the droplets in the solidification stage are not easy to recombine with each other, and the solidified droplets are also not easy to recombine with the incompletely solidified droplets. Therefore, the three-dimensional wrinkled graphene prepared by the present invention has a uniform particle size distribution.

以下仔細討論本發明實施例之製造和使用。然而，可以理解的是，實施例提供許多可應用的發明概念，其可實施於各式各樣的特定內容中。所討論之特定實施例僅供說明，並非用以限定本發明之範圍。The making and using of embodiments of the invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are illustrative only and do not limit the scope of the invention.

請同時參照圖1與圖2A，其中圖1係繪示依照本發明之一些實施例之三維皺褶石墨烯的製作方法之流程圖，且圖2A係繪示依照本發明之一些實施例之製備三維皺褶石墨烯的設備之剖視示意圖。方法100係先提供反應元件200a，並對反應元件200a進行冷卻製程，如操作110與操作120所示。Please refer to FIG. 1 and FIG. 2A at the same time, wherein FIG. 1 is a flowchart illustrating a method for manufacturing three-dimensional wrinkled graphene according to some embodiments of the present invention, and FIG. 2A is a flowchart illustrating the preparation according to some embodiments of the present invention Schematic cross-section of the device for 3D crumpled graphene. In the method 100, the reaction element 200a is firstly provided, and a cooling process is performed on the reaction element 200a, as shown in operation 110 and operation 120 .

反應元件200a可包含反應槽210與噴灑單元220，且反應槽210包含封閉底部211a與相對之頂部213a。其中，頂部213a包含開孔213b，且噴灑單元220係設置於開孔213b上。由於噴灑單元220之設置，反應槽210之內部空間210a可為氣密的。如圖2A所示，雖然反應槽210係圓管，但本發明不以此為限，在其他實施例中，反應槽210亦可為方管或其他適當之外型。噴灑單元220包含噴出孔221，且噴出孔221係經由開孔213b延伸至反應槽210的內部空間210a中。噴灑單元220係藉由噴出孔221朝反應槽210之內部空間210a噴出石墨烯溶液，以形成石墨烯液滴，進而可製得本發明之三維皺褶石墨烯。雖然圖2A未繪示，惟所屬技術領域具有通常知識者可清楚理解噴灑單元220可包含儲料桶、加壓泵浦、泵送管路與其他欲達成噴灑功效所需之組件與結構。The reaction element 200a may include a reaction tank 210 and a spray unit 220, and the reaction tank 210 includes a closed bottom 211a and an opposite top 213a. Wherein, the top 213a includes an opening 213b, and the spraying unit 220 is disposed on the opening 213b. Due to the arrangement of the spraying unit 220, the inner space 210a of the reaction tank 210 can be airtight. As shown in FIG. 2A , although the reaction tank 210 is a circular tube, the present invention is not limited thereto. In other embodiments, the reaction tank 210 can also be a square tube or other suitable shapes. The spray unit 220 includes a spray hole 221 , and the spray hole 221 extends into the inner space 210 a of the reaction tank 210 through the opening 213 b. The spraying unit 220 sprays the graphene solution toward the inner space 210 a of the reaction tank 210 through the spray hole 221 to form graphene droplets, thereby producing the three-dimensional wrinkled graphene of the present invention. Although not shown in FIG. 2A , those skilled in the art can clearly understand that the spraying unit 220 may include a storage tank, a pressurized pump, a pumping pipeline and other components and structures required to achieve the spraying effect.

於進行冷卻製程時，反應槽210之內部空間210a的溫度可被降低。須說明的是，所稱之內部空間210a的溫度係指反應槽210之內部氣氛的溫度。換言之，內部空間210a的溫度係指反應槽210內之氣體溫度。在一些實施例中，冷卻製程係將反應元件200a放置於冷卻媒介203中，以降低反應槽210之內部空間210a的溫度。如圖2A所示，雖然冷卻媒介203係繪示為液相媒介，但本發明不以此為限，冷卻媒介203亦可為氣相媒介、固相媒介，或上述冷卻媒介之任意混合。可理解的，當使用固相媒介時，為提升冷卻效果，固相媒介可混合其他液態物質。在其他實施例中，冷卻製程亦可藉由其他適當之方法來冷卻反應元件。在此些實施例中，進行冷卻製程時，反應元件200a可置放於電致冷卻裝置中，而達到降低內部空間210a的溫度之效果。在一些具體例中，電致冷卻裝置可例如但不限於含有製冷壓縮機、熱電致冷晶片及/或其他適當之電致冷組件的裝置。During the cooling process, the temperature of the inner space 210 a of the reaction tank 210 can be lowered. It should be noted that the temperature of the inner space 210 a refers to the temperature of the inner atmosphere of the reaction tank 210 . In other words, the temperature of the inner space 210 a refers to the gas temperature in the reaction tank 210 . In some embodiments, the cooling process is to place the reaction element 200 a in the cooling medium 203 to reduce the temperature of the inner space 210 a of the reaction tank 210 . As shown in FIG. 2A , although the cooling medium 203 is shown as a liquid phase medium, the present invention is not limited thereto, and the cooling medium 203 can also be a gas phase medium, a solid phase medium, or any mixture of the above cooling mediums. Understandably, when a solid medium is used, in order to enhance the cooling effect, the solid medium can be mixed with other liquid substances. In other embodiments, the cooling process may also use other appropriate methods to cool the reaction element. In these embodiments, when the cooling process is performed, the reaction element 200a can be placed in an electric cooling device to reduce the temperature of the inner space 210a. In some embodiments, the electric cooling device may be, for example but not limited to, a device including a refrigeration compressor, a thermoelectric cooling chip, and/or other suitable electric cooling components.

請參照圖2A。於進行前述之冷卻製程時，反應元件200a可放置於槽體200中，其中槽體200可用以容納冷卻媒介203(如液態氮、乾冰、丙酮與乾冰之混合媒介、其他適當之冷卻媒介，或上述媒介之任意混合)。可理解的，若使用氣相媒介(如低溫氣體)來進行冷卻製程時，反應元件200a較佳係放置於可形成低溫密閉環境之裝置中，惟若內部空間210a的溫度可維持穩定，反應元件200a亦可放置於開放之低溫環境中。在一些實施例中，槽體200可利用絕熱材料所製成，以維持冷卻媒介203之溫度。為了有效地冷卻反應槽210之內部空間210a的溫度，反應槽210較佳係利用導熱材料所製成。於進行冷卻製程後，內部空間210a之溫度係不大於石墨烯溶液之溶劑的凝固點(T f)。若內部空間210a之溫度大於溶劑的凝固點時，於進行後續之噴灑製程時，經由噴灑單元220所噴出之石墨烯溶液將無法形成立體之皺褶石墨烯。較佳地，內部空間210a之溫度係小於石墨烯溶液之溶劑的凝固點。在一些應用例中，內部空間210a之溫度可小於(T f-10)℃，以有助於後續皺褶結構之形成。在一些實施例中，圖2A所繪示之圓管反應槽210的尺寸沒有特別之限制，其僅須確保於進行後續之噴灑製程時，反應槽210之內部空間210a的氣體溫度可為設定之溫度。在一些實施例中，反應槽210之內部可選擇性地設有其他有助於冷卻氣體的構件(例如：供以通入冷卻媒介203之管路或結構)，惟可理解的，基於後述皺褶石墨烯的形成機制，此些構件不會影響皺褶石墨烯的形成，且不影響皺褶石墨烯的收集。 Please refer to Figure 2A. When carrying out the aforementioned cooling process, the reaction element 200a can be placed in the tank body 200, wherein the tank body 200 can be used to accommodate the cooling medium 203 (such as liquid nitrogen, dry ice, a mixed medium of acetone and dry ice, other suitable cooling medium, or Any mix of the above media). Understandably, if a gas phase medium (such as low-temperature gas) is used to carry out the cooling process, the reaction element 200a is preferably placed in a device that can form a low-temperature airtight environment, but if the temperature of the inner space 210a can be kept stable, the reaction element 200a 200a can also be placed in an open low temperature environment. In some embodiments, the tank body 200 can be made of heat insulating material to maintain the temperature of the cooling medium 203 . In order to effectively cool the temperature of the inner space 210 a of the reaction tank 210 , the reaction tank 210 is preferably made of a heat-conducting material. After the cooling process, the temperature of the inner space 210a is not higher than the freezing point (T f ) of the solvent of the graphene solution. If the temperature of the inner space 210a is higher than the freezing point of the solvent, the graphene solution sprayed through the spraying unit 220 will not be able to form three-dimensional wrinkled graphene during the subsequent spraying process. Preferably, the temperature of the inner space 210a is lower than the freezing point of the solvent of the graphene solution. In some application examples, the temperature of the inner space 210a may be lower than (T f -10)° C., so as to facilitate the formation of subsequent wrinkle structures. In some embodiments, the size of the circular tube reaction tank 210 shown in FIG. 2A is not particularly limited, it only needs to ensure that the gas temperature in the inner space 210a of the reaction tank 210 can be set during the subsequent spraying process. temperature. In some embodiments, the interior of the reaction tank 210 may optionally be provided with other components that help to cool the gas (for example: pipelines or structures for passing through the cooling medium 203), but it is understandable that based on the following wrinkles The formation mechanism of wrinkled graphene, these components will not affect the formation of wrinkled graphene, and will not affect the collection of wrinkled graphene.

在一些實施例中，反應槽210之底部211a可設有載材201。載材201可用以承接所形成之皺褶石墨烯，而有助於皺褶石墨烯之收集。在一些具體例中，載材201可包含但不限於矽晶圓、金屬載材、陶瓷載材、高分子載材、天然物殼層、其他適當之載材，或上述材料之任意組合。在一些實施例中，反應槽210中可選擇性地含有冷卻媒介，故載材201可藉由此冷卻媒介，而更容易地維持於低溫狀態，進而有助於皺褶石墨烯的生成。可理解的，載材201之頂表面係高於冷卻媒介之液面。In some embodiments, the bottom 211 a of the reaction tank 210 may be provided with a carrier 201 . The carrier 201 can be used to support the formed wrinkled graphene, and facilitate the collection of the wrinkled graphene. In some specific examples, the carrier 201 may include but not limited to silicon wafer, metal carrier, ceramic carrier, polymer carrier, natural shell, other appropriate carrier, or any combination of the above materials. In some embodiments, the reaction tank 210 may optionally contain a cooling medium, so the substrate 201 can be more easily maintained at a low temperature by the cooling medium, thereby facilitating the formation of the wrinkled graphene. Understandably, the top surface of the carrier 201 is higher than the liquid level of the cooling medium.

請參照圖2B，其係繪示依照本發明之一些實施例之製備三維皺褶石墨烯的設備之剖視示意圖。圖2B所繪示之設備大致上與圖2A所繪示之設備相同，兩者之差異在於：反應元件200b之反應槽210可由部件211與213結合組成；噴灑單元220經由管路220a與噴出孔221將石墨烯溶液噴灑至內部空間210a中；以及反應元件200b具有減壓單元230。Please refer to FIG. 2B , which is a schematic cross-sectional view of an apparatus for preparing three-dimensional wrinkled graphene according to some embodiments of the present invention. The equipment shown in Figure 2B is substantially the same as the equipment shown in Figure 2A, the difference between the two is: the reaction tank 210 of the reaction element 200b can be formed by combining parts 211 and 213; the spraying unit 220 passes through the pipeline 220a and the spray hole 221 sprays the graphene solution into the inner space 210 a; and the reaction element 200 b has a decompression unit 230 .

為了有助於收集所形成之三維皺褶石墨烯，反應槽210可由部件211與213結合組成，其中部件211與213可藉由螺固、緊配合、其他適當之方式來結合，或上述結合方式之任意組合。部件211與213之結合沒有特別之限制，惟須確保反應槽210係氣密的且可穩定維持內部空間210a係低溫的。換言之，於進行冷卻製程後，冷卻媒介203或其他物質(如外界氣體)不會經由部件211與213之結合位置滲入反應槽210之內部空間210a中。相同前述圖2A之反應槽210，部件211與213可利用導熱材料製成，以有效冷卻反應槽210內之氣體。In order to facilitate the collection of the formed three-dimensional wrinkled graphene, the reaction tank 210 can be composed of components 211 and 213, wherein the components 211 and 213 can be combined by screwing, tight fitting, or other appropriate methods, or the above-mentioned combination any combination of The combination of the components 211 and 213 is not particularly limited, but it must be ensured that the reaction tank 210 is airtight and the inner space 210a can be stably maintained at a low temperature. In other words, after the cooling process is performed, the cooling medium 203 or other substances (such as external air) will not infiltrate into the inner space 210a of the reaction tank 210 through the joint position of the components 211 and 213 . Similar to the aforementioned reaction tank 210 in FIG. 2A , the components 211 and 213 can be made of heat-conducting materials to effectively cool the gas in the reaction tank 210 .

當反應槽210係由部件211與213組成時，於進行前述之冷卻製程前，載材201可先放置於部件211之底部211a，再結合部件211與213。因此，後續僅須分離部件211與213即可便利地取出載材201。When the reaction tank 210 is composed of parts 211 and 213 , before performing the aforementioned cooling process, the carrier 201 can be placed on the bottom 211 a of the part 211 first, and then the parts 211 and 213 are combined. Therefore, the carrier 201 can be conveniently taken out only by separating the parts 211 and 213 later.

管路220a係穿過開孔213b，並延伸至內部空間210a中，故噴灑單元220可利用管路220a泵送石墨烯溶液，且進一步利用噴出孔221將石墨烯液滴噴灑至內部空間210a中。為了避免氣體經由反應槽210與管路220a之結合位置滲入反應槽210中，管路220a與部件213可為一體成形的，或者係藉由其他可達到氣密效果之方式來結合。The pipeline 220a passes through the opening 213b and extends into the inner space 210a, so the spraying unit 220 can use the pipeline 220a to pump the graphene solution, and further use the spray hole 221 to spray the graphene droplets into the inner space 210a . In order to prevent the gas from infiltrating into the reaction tank 210 through the junction of the reaction tank 210 and the pipeline 220a, the pipeline 220a and the component 213 can be integrally formed, or combined in other ways that can achieve an airtight effect.

如圖2B所示。減壓單元230可經由管路230a與管路220a連通內部空間210a。減壓單元230可用以降低反應槽210之內部壓力，以有助於後續噴灑製程之進行。在一些具體例中，反應槽210之內部壓力可略小於1 atm。當反應槽210之內部壓力略小於1 atm時，略為低壓之環境有助於使石墨烯溶液由噴出孔221噴出，且利用噴灑單元220之噴出壓力噴出的石墨烯液滴可具有朝向底部211a移動之驅動力，故其不易與其他石墨烯液滴再結合。由於石墨烯溶液之噴入，反應槽210之內部壓力將回復至常壓，故減壓單元230可再次降低內部壓力。須注意的是，為使反應槽210之內部空間210a為低溫環境，反應槽210之內部不可為真空狀態。於圖2B中，雖然減壓單元230係透過管路230a與管路220a連通內部空間210a，但本發明不以此為限，在一些實施例中，減壓單元230亦可藉由管路230a直接連通內部空間210a，其中管路230a係設置於部件213之頂部213a。在此些實施例中，管路230a與反應槽210之結合須確保反應槽210係氣密的。在一些實施例中，減壓單元230亦可用以置換反應槽210內之氣體，以有助於皺褶石墨烯之生成。舉例而言，減壓單元230可將反應槽210內之氣體置換為滿足前述壓力範圍之氮氣、其他適當之氣體，或上述氣體之任意混合。As shown in Figure 2B. The decompression unit 230 can communicate with the inner space 210a through the pipeline 230a and the pipeline 220a. The decompression unit 230 can be used to reduce the internal pressure of the reaction tank 210 to facilitate the subsequent spraying process. In some embodiments, the internal pressure of the reaction tank 210 may be slightly less than 1 atm. When the internal pressure of the reaction tank 210 is slightly less than 1 atm, the slightly low-pressure environment helps the graphene solution to be ejected from the ejection hole 221, and the graphene droplets ejected by the ejection pressure of the spray unit 220 can move toward the bottom 211a The driving force, so it is not easy to recombine with other graphene droplets. Due to the injection of the graphene solution, the internal pressure of the reaction tank 210 will return to normal pressure, so the decompression unit 230 can reduce the internal pressure again. It should be noted that, in order to make the inner space 210a of the reaction tank 210 a low-temperature environment, the inside of the reaction tank 210 cannot be in a vacuum state. In FIG. 2B, although the decompression unit 230 communicates with the internal space 210a through the pipeline 230a and the pipeline 220a, the present invention is not limited thereto. It directly communicates with the inner space 210a, wherein the pipeline 230a is arranged on the top 213a of the component 213 . In these embodiments, the combination of the pipeline 230a and the reaction tank 210 must ensure that the reaction tank 210 is airtight. In some embodiments, the decompression unit 230 can also be used to replace the gas in the reaction tank 210 to facilitate the formation of the wrinkled graphene. For example, the decompression unit 230 can replace the gas in the reaction tank 210 with nitrogen meeting the aforementioned pressure range, other appropriate gases, or any mixture of the aforementioned gases.

請同時參照圖1與圖2B。在一些實施例中，於進行前述之冷卻製程(即操作120)前，方法100可選擇性地對反應元件200b進行減壓製程，以使反應槽210內之氣體壓力係略小於1 atm。在一些實施例中，冷卻製程與減壓製程亦可同時進行。在其他實施例中，冷卻製程與前述之氣體置換製程亦可同時進行。Please refer to FIG. 1 and FIG. 2B at the same time. In some embodiments, before performing the aforementioned cooling process (ie, operation 120 ), the method 100 may optionally perform a decompression process on the reaction element 200b so that the gas pressure in the reaction tank 210 is slightly less than 1 atm. In some embodiments, the cooling process and the decompression process can also be performed simultaneously. In other embodiments, the cooling process and the aforementioned gas replacement process can also be performed simultaneously.

請同時參照圖1與圖2A。於進行前述之冷卻製程後，進行噴灑製程，即可製得本發明之三維皺褶石墨烯，如操作130與操作140所示。噴灑製程係利用噴灑單元220將石墨烯溶液噴灑至內部空間210a中。當石墨烯溶液經由噴出孔221噴出時，由於內部空間210a之氣體溫度係不大於石墨烯溶液之溶劑的凝固點，故所噴出之石墨烯液滴中的溶劑液體將凝固，而使得石墨烯可形成皺褶結構，進而製得本發明之立體的皺褶石墨烯。當石墨烯液滴由噴出孔221噴出時，根據內部空間210a之溫度，石墨烯液滴之液體可於氣相環境中逐漸或迅速地凝固，而形成石墨烯冰晶(含有皺褶石墨烯與固化之溶劑)。藉由噴出孔221之噴出壓力與重力，尚未完全凝固之石墨烯液滴與已完全凝固之石墨烯冰晶可飄落並附著於反應槽210之內壁與/或載材201上。較佳地，石墨烯液滴於附著於反應槽210之內壁與/或載材201前，已完全凝固形成石墨烯冰晶。在一些具體例中，噴出孔221與底部211a之內壁或載材201的距離可為大於1公釐。更佳地，於石墨烯液滴噴出後，每一個石墨烯液滴與石墨烯冰晶均不會與另一未完全凝固之石墨烯液滴結合，以使所形成之皺褶石墨烯可具有更均一之粒徑尺寸。於進行噴灑製程後，為了避免立體之皺褶結構因液態溶劑之存在而再度被拉平(即回復為平整結構)，石墨烯冰晶中已凝固之溶劑係藉由昇華方式來移除。於移除凝固態之溶劑後，由於本發明所製得之皺褶石墨烯的皺褶結構可自立存在，故其不易再改變。因此，於反應槽210回復至室溫後，可利用刮除之方式、取出載材之方式，或者其他適當之方式來收集皺褶石墨烯。由於皺褶石墨烯係藉由低溫氣體來冷卻形成，故為更有效製得皺褶石墨烯，內部空間210a中之氣體較佳係不含有水份。Please refer to FIG. 1 and FIG. 2A at the same time. After performing the aforementioned cooling process, the spraying process is performed to obtain the three-dimensional wrinkled graphene of the present invention, as shown in operation 130 and operation 140 . The spraying process uses the spraying unit 220 to spray the graphene solution into the inner space 210a. When the graphene solution is ejected through the ejection hole 221, since the temperature of the gas in the inner space 210a is not greater than the freezing point of the solvent of the graphene solution, the solvent liquid in the ejected graphene droplets will solidify, so that graphene can be formed Wrinkle structure, and then make the three-dimensional wrinkled graphene of the present invention. When the graphene droplet is ejected from the ejection hole 221, according to the temperature of the inner space 210a, the liquid of the graphene droplet can solidify gradually or rapidly in the gas phase environment to form graphene ice crystals (containing wrinkled graphene and solidified graphene). solvent). With the ejection pressure and gravity of the ejection hole 221 , the graphene droplets that have not been completely solidified and the graphene ice crystals that have been completely solidified can fall and adhere to the inner wall of the reaction tank 210 and/or the carrier 201 . Preferably, the graphene droplets have completely solidified to form graphene ice crystals before attaching to the inner wall of the reaction tank 210 and/or the carrier 201 . In some specific examples, the distance between the spray hole 221 and the inner wall of the bottom 211 a or the carrier 201 may be greater than 1 mm. More preferably, after the graphene droplets are ejected, each graphene droplet and graphene ice crystal will not combine with another incompletely solidified graphene droplet, so that the formed wrinkled graphene can have more Uniform particle size. After the spraying process, in order to prevent the three-dimensional wrinkled structure from being flattened again (that is, returning to a flat structure) due to the presence of liquid solvents, the solidified solvent in the graphene ice crystals is removed by sublimation. After removing the solidified solvent, since the wrinkled structure of the wrinkled graphene prepared by the present invention can stand on its own, it is difficult to change again. Therefore, after the reaction tank 210 returns to room temperature, the wrinkled graphene can be collected by scraping, removing the carrier, or other appropriate methods. Since the wrinkled graphene is formed by cooling the low-temperature gas, in order to produce the wrinkled graphene more efficiently, the gas in the inner space 210 a preferably does not contain water.

在一些實施例中，石墨烯溶液包含氧化石墨烯，且石墨烯溶液之濃度可例如為不小於0.05 mg/mL。其中，氧化石墨烯係採用所屬技術領域常用之原料與反應(如哈默法(Hummers’ method))來製作，故在此不另贅述。當石墨烯溶液之濃度為此範圍時，經由噴出孔221噴出之石墨烯液滴於凝固時可具有較佳之收縮效果。石墨烯溶液之溶劑可選用氧化石墨烯於其中具有良好分散性之溶劑。在一些具體例中，石墨烯溶液之溶劑可例如為水、二甲基甲醯胺(DMF)、N-甲基吡咯烷酮(NMP)、四氫呋喃(THF)、乙二醇(EG)、其他適當之溶劑，或上述溶劑之任意混合。較佳地，石墨烯溶液之濃度可為5 mg/mL至10 mg/mL。In some embodiments, the graphene solution includes graphene oxide, and the concentration of the graphene solution may be not less than 0.05 mg/mL, for example. Wherein, graphene oxide is produced by using commonly used raw materials and reactions in the technical field (such as the Hummers' method), so details will not be described here. When the concentration of the graphene solution is within this range, the graphene droplets ejected through the ejection hole 221 can have a better shrinkage effect when solidified. The solvent of the graphene solution may be a solvent in which graphene oxide has good dispersibility. In some specific examples, the solvent of the graphene solution can be, for example, water, dimethylformamide (DMF), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), ethylene glycol (EG), other suitable solvent, or any mixture of the above solvents. Preferably, the concentration of the graphene solution may be 5 mg/mL to 10 mg/mL.

在一些實施例中，請參照圖2B，當石墨烯液滴由噴出孔221噴出，且反應槽210內之壓力係小於1 atm時，低壓低溫之環境有助於使石墨烯液滴中之液體更迅速地凝固，而有助於皺褶石墨烯之形成。In some embodiments, please refer to FIG. 2B, when the graphene droplets are ejected from the ejection hole 221, and the pressure in the reaction tank 210 is less than 1 atm, the environment of low pressure and low temperature helps to make the liquid in the graphene droplets Solidifies more rapidly, which contributes to the formation of wrinkled graphene.

在一些應用例中，本發明所製得之皺褶石墨烯具有立體的皺褶結構，而具有較佳之熱傳導性質，且其耐壓性可不小於400 kg/cm 2。其中，石墨烯之立體皺褶結構可自立(free-standing)存在，而不須依靠外力或額外之設備來維持。再者，將所製得之三維皺褶石墨烯(1 mg)均勻分散於3 mL之乙醇中，於經過9小時後，三維之皺褶石墨烯仍具有極佳之分散性，且於經過23小時後，其仍具有良好之分散性。另外，本案之三維皺褶石墨烯具有均一之粒徑分布。舉例而言，本發明之三維皺褶石墨烯的粒徑可為250 nm至數百微米(如300 μm)。 In some application examples, the wrinkled graphene produced by the present invention has a three-dimensional wrinkled structure, has better heat conduction properties, and its pressure resistance can be no less than 400 kg/cm 2 . Among them, the three-dimensional wrinkled structure of graphene can exist independently (free-standing), without relying on external force or additional equipment to maintain. Furthermore, the prepared three-dimensional wrinkled graphene (1 mg) was uniformly dispersed in 3 mL of ethanol. After 9 hours, the three-dimensional wrinkled graphene still had excellent dispersion, and after 23 After hours, it still has good dispersibility. In addition, the three-dimensional wrinkled graphene of this case has a uniform particle size distribution. For example, the particle size of the three-dimensional wrinkled graphene of the present invention can be from 250 nm to hundreds of microns (eg, 300 μm).

以下利用實施例以說明本發明之應用，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。The following examples are used to illustrate the application of the present invention, but they are not intended to limit the present invention. Anyone skilled in this art can make various changes and modifications without departing from the spirit and scope of the present invention.

製備三維皺褶石墨烯Preparation of three-dimensional wrinkled graphene

實施例1Example 1

實施例1係先將氧化石墨烯分散於水中，以獲得濃度為0.5 mg/mL之石墨烯溶液。然後，利用如圖2A所繪示之設備來製作皺褶石墨烯，其中所選用之冷卻媒介為液態氮。In Example 1, graphene oxide was first dispersed in water to obtain a graphene solution with a concentration of 0.5 mg/mL. Then, the wrinkled graphene is fabricated using the equipment shown in FIG. 2A , wherein the cooling medium selected is liquid nitrogen.

實施例1所製得之三維皺褶石墨烯的掃描式電子顯微鏡照片如圖3A與圖3B所示，其中圖3A與圖3B之比例尺規均代表500 nm。The scanning electron micrographs of the three-dimensional wrinkled graphene prepared in Example 1 are shown in FIG. 3A and FIG. 3B , wherein the scale bars in FIG. 3A and FIG. 3B both represent 500 nm.

實施例1之三維皺褶石墨烯的耐壓性係將所製得之皺褶石墨烯放置於壓錠模具中，並利用壓錠器具對皺褶石墨烯施加 400 kg/cm 2之壓力。於移除壓力後，將加壓後之皺褶石墨烯加至乙醇中。若仍具有良好分散性，代表皺褶石墨烯仍具有皺褶結構，故所製得之皺褶石墨烯具有良好之耐壓性。 The pressure resistance of the three-dimensional corrugated graphene in Example 1 is to place the obtained corrugated graphene in a pelletizing mold, and apply a pressure of 400 kg/cm 2 to the corrugated graphene using a pelletizing tool. After the pressure was removed, the pressurized wrinkled graphene was added to ethanol. If it still has good dispersion, it means that the wrinkled graphene still has a wrinkled structure, so the prepared wrinkled graphene has good pressure resistance.

實施例2至實施例4Example 2 to Example 4

實施例2至實施例4係使用與實施例1之三維皺褶石墨烯相同之製備方法，不同之處在於實施例2之石墨烯濃度為0.2 mg/mL；實施例3之石墨烯濃度為5 mg/mL；且實施例4之石墨烯濃度為10 mg/mL。實施例2至實施例4所製得之三維皺褶石墨烯的掃描式電子顯微鏡照片分別如圖4A與4B、圖5A與5B和圖6A與6B所示。Embodiment 2 to embodiment 4 use the same preparation method as the three-dimensional wrinkled graphene of embodiment 1, the difference is that the concentration of graphene in embodiment 2 is 0.2 mg/mL; the concentration of graphene in embodiment 3 is 5 mg/mL; mg/mL; and the graphene concentration of embodiment 4 is 10 mg/mL. The scanning electron micrographs of the three-dimensional wrinkled graphene prepared in Examples 2 to 4 are shown in FIGS. 4A and 4B , FIGS. 5A and 5B , and FIGS. 6A and 6B , respectively.

據此，本發明的製作方法藉由將石墨烯溶液噴灑至低溫氣相環境中，以利用低溫氣體來冷卻石墨烯液滴，以使其凝固為石墨烯冰晶，而可製得三維皺褶石墨烯。由於所製得之石墨烯具有皺褶結構，故除石墨烯原有之x-y平面熱傳導路徑，皺褶結構可進一步提升石墨烯於z軸方向的熱傳導性能。再者，皺褶結構亦可提升三維皺褶石墨烯之耐壓性。相較於一般之石墨烯材料，本發明之三維皺褶石墨烯具有較佳的分散性，且經長時間靜置後，其仍可良好地分散。另外，本發明之製作方法可有效地避免石墨烯液滴於凝固時，形成液滴結合之現象，故可製得粒徑分布均一之三維皺褶石墨烯。Accordingly, the production method of the present invention sprays the graphene solution into a low-temperature gas-phase environment, so that the graphene droplets are cooled by the low-temperature gas, so that they are solidified into graphene ice crystals, and three-dimensional wrinkled graphite can be produced alkene. Since the prepared graphene has a wrinkled structure, in addition to the original x-y plane heat conduction path of graphene, the wrinkled structure can further improve the heat conduction performance of graphene in the z-axis direction. Furthermore, the wrinkled structure can also improve the pressure resistance of the three-dimensional wrinkled graphene. Compared with general graphene materials, the three-dimensional wrinkled graphene of the present invention has better dispersibility, and it can still be well dispersed after standing for a long time. In addition, the production method of the present invention can effectively avoid the phenomenon that the graphene droplets are combined when they are solidified, so three-dimensional wrinkled graphene with uniform particle size distribution can be produced.

其中，由於本案係直接利用低溫氣體使石墨烯液滴凝固，故相較於直接將石墨烯溶液噴灑至冷卻媒介中，本發明不易使冷卻媒介激烈汽化 (因常溫石墨烯液滴與低溫冷卻媒介(如液態氮)的溫度差所引起)。據此，本發明已凝固之石墨烯冰晶不會受到沸騰氣體之帶動，故不易與其他未凝固之石墨烯液滴再結合，進而可具有較均一之粒徑分布。Wherein, since the present case directly utilizes low-temperature gas to solidify the graphene droplets, compared with directly spraying the graphene solution into the cooling medium, the present invention is not easy to vaporize the cooling medium (due to the normal temperature graphene droplets and the low-temperature cooling medium (such as caused by the temperature difference of liquid nitrogen). Accordingly, the solidified graphene ice crystals of the present invention are not driven by the boiling gas, so they are not easy to recombine with other unsolidified graphene droplets, and can have a more uniform particle size distribution.

雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various modifications and changes without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.

100:方法 110,120,130,140:操作 200:槽體 200a,200b:反應元件 201:載材 210a:內部空間 203:冷卻媒介 210:反應槽 211,213:部件 211a:底部 213a:頂部 213b:開孔 220:噴灑單元 220a,230a:管路 221:噴出孔 230:減壓單元 100: method 110, 120, 130, 140: operation 200: tank body 200a, 200b: Response elements 201: carrier 210a: Internal space 203: cooling medium 210: Reaction tank 211,213: Parts 211a: bottom 213a: Top 213b: opening 220: spraying unit 220a, 230a: piping 221: ejection hole 230: decompression unit

為了對本發明之實施例及其優點有更完整之理解，現請參照以下之說明並配合相應之圖式。必須強調的是，各種特徵並非依比例描繪且僅係為了圖解目的。相關圖式內容說明如下。 圖1係繪示依照本發明之一些實施例之三維皺褶石墨烯的製作方法之流程圖。 圖2A與圖2B分別係繪示依照本發明之一些實施例之製備三維皺褶石墨烯的設備之剖視示意圖。 圖3A至圖6B分別係顯示依照本發明之實施例1至實施例4之三維皺褶石墨烯的掃描式電子顯微鏡照片。 In order to have a more complete understanding of the embodiments of the present invention and their advantages, please refer to the following descriptions together with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of related drawings are explained as follows. FIG. 1 is a flowchart illustrating a method for manufacturing three-dimensional wrinkled graphene according to some embodiments of the present invention. FIG. 2A and FIG. 2B are respectively schematic cross-sectional views illustrating an apparatus for preparing three-dimensional wrinkled graphene according to some embodiments of the present invention. 3A to 6B are scanning electron micrographs showing three-dimensional wrinkled graphene according to Embodiment 1 to Embodiment 4 of the present invention, respectively.

國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無 Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none

100:方法 100: method

110,120,130,140:操作 110, 120, 130, 140: operation

Claims (9)

一種三維皺褶石墨烯的製作方法，包含：提供一反應元件，其中該反應元件之一反應槽包含一封閉底部與一頂部；對該反應元件進行一冷卻製程；以及進行一噴灑製程，以製得該三維皺褶石墨烯，其中該噴灑製程係由該頂部噴入一石墨烯溶液至該反應元件中，且該冷卻製程係使該反應元件內之一氣體溫度係不大於該石墨烯溶液之一溶劑之凝固點，當該氣體溫度不大於該溶劑之該凝固點時，噴入該石墨烯溶液至該反應元件中，其中該石墨烯溶液包含一石墨烯材料與該溶劑，該石墨烯材料係分散於該溶劑中，且該石墨烯溶液之濃度係不小於0.05mg/mL。 A method for manufacturing three-dimensional wrinkled graphene, comprising: providing a reaction element, wherein a reaction tank of the reaction element includes a closed bottom and a top; performing a cooling process on the reaction element; and performing a spraying process to produce The three-dimensional wrinkled graphene is obtained, wherein the spraying process is to spray a graphene solution into the reaction element from the top, and the cooling process is to make a gas temperature in the reaction element not greater than that of the graphene solution The freezing point of a solvent, when the temperature of the gas is not higher than the freezing point of the solvent, the graphene solution is sprayed into the reaction element, wherein the graphene solution includes a graphene material and the solvent, and the graphene material is dispersed In the solvent, the concentration of the graphene solution is not less than 0.05mg/mL. 如請求項1所述之三維皺褶石墨烯的製作方法，其中該冷卻製程係將該反應元件放置於一冷卻媒介中。 The manufacturing method of three-dimensional wrinkled graphene according to claim 1, wherein the cooling process is to place the reaction element in a cooling medium. 如請求項1所述之三維皺褶石墨烯的製作方法，於進行該冷卻製程前，該製作方法更包含：放置一載材於該封閉底部上。 According to the manufacturing method of three-dimensional wrinkled graphene described in Claim 1, before performing the cooling process, the manufacturing method further includes: placing a carrier on the closed bottom. 如請求項1所述之三維皺褶石墨烯的製作方法，於進行該冷卻製程前，該製作方法更包含： 對該反應元件進行一減壓製程，以使該反應槽內之一氣體壓力係小於1atm。 As the method for manufacturing three-dimensional wrinkled graphene described in claim 1, before performing the cooling process, the method further includes: A decompression process is performed on the reaction element, so that a gas pressure in the reaction tank is less than 1 atm. 如請求項1所述之三維皺褶石墨烯的製作方法，其中該石墨烯材料包含氧化石墨烯。 The manufacturing method of three-dimensional wrinkled graphene as described in Claim 1, wherein the graphene material comprises graphene oxide. 一種三維皺褶石墨烯，藉由如請求項1至5中之任一項所述之製作方法所製成，其中該三維皺褶石墨烯係球型的，且該三維皺褶石墨烯之耐壓性係不小於400kg/cm2。 A three-dimensional wrinkled graphene, made by the manufacturing method as described in any one of claims 1 to 5, wherein the three-dimensional wrinkled graphene is spherical, and the resistance of the three-dimensional wrinkled graphene Pressure property is not less than 400kg/cm 2 . 一種製備三維皺褶石墨烯的設備，包含：一槽體，配置以容納一冷卻媒介；以及一反應元件，放置於該槽體中，其中該反應元件包含；一反應槽，包含；一封閉底部；以及一頂部，相對於該封閉底部，且該頂部具有一開孔，其中該開孔係高於該冷卻媒介；以及一噴灑單元，設於該開孔，以使該反應元件係氣密的，其中該噴灑單元之一噴出孔係延伸至該反應元件中，且該噴灑單元係配置以經由該噴出孔噴入一石墨烯溶液至該反應元件中。 A device for preparing three-dimensional wrinkled graphene, comprising: a tank configured to accommodate a cooling medium; and a reaction element placed in the tank, wherein the reaction element includes; a reaction tank includes; a closed bottom and a top, opposite to the closed bottom, and the top has an opening, wherein the opening is higher than the cooling medium; and a spray unit is arranged in the opening, so that the reaction element is airtight , wherein one of the spray holes of the spray unit extends into the reaction element, and the spray unit is configured to spray a graphene solution into the reaction element through the spray hole. 如請求項7所述之製備三維皺褶石墨烯的設 備，其中該反應槽係由一導熱材料所製成。 The device for preparing three-dimensional wrinkled graphene as described in claim item 7 equipment, wherein the reaction tank is made of a heat-conducting material. 如請求項7所述之製備三維皺褶石墨烯的設備，其中該反應槽更包含：一減壓管，設於該頂部。 The equipment for preparing three-dimensional wrinkled graphene as described in claim 7, wherein the reaction tank further comprises: a decompression tube disposed on the top.
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