TWI522314B - Large-scale production apparatus for preparing graphene and graphene oxide and the method thereof - Google Patents
Large-scale production apparatus for preparing graphene and graphene oxide and the method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 176
- 229910021389 graphene Inorganic materials 0.000 title claims description 105
- 238000000034 method Methods 0.000 title claims description 38
- 238000011031 large-scale manufacturing process Methods 0.000 title 1
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- 230000003647 oxidation Effects 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Description
本發明係關於一種石墨烯及石墨烯氧化物之製程設備及方法，特別是一種規模化量產石墨烯及石墨烯氧化物之製程設備及方法。The invention relates to a process equipment and a method for graphene and graphene oxide, in particular to a process equipment and method for mass production of graphene and graphene oxide.
石墨烯(graphene)是一種單原子層的石墨，每個碳原子之間以sp2混成與相鄰的三個原子形成鍵結，並延伸成蜂窩狀的二維結構。已知，石墨烯的載子遷移率(carrier mobility)可達200,000 cm2/V‧s，同時也具有良好的導熱及高穿透率等性質，因此目前已被廣泛應用於半導體、觸控面板或太陽能電池等領域中。Graphene is a monoatomic layer of graphite, each of which is sp 2 mixed with adjacent three atoms to form a bond and extends into a honeycomb two-dimensional structure. It is known that graphene has a carrier mobility of up to 200,000 cm 2 /V‧s, and also has good thermal conductivity and high transmittance. Therefore, it has been widely used in semiconductors and touch panels. Or in the field of solar cells.
用以製造石墨烯的習知技術包含機械剝離法(mechanical exfoliation)、磊晶成長法(epitaxial growth)、化學氣相沈積法(chemical vapor deposition,CVD)及化學剝離法(chemical exfoliation)等方法。其中，機械剝離法及磊晶成長法，雖然可以生成品質較佳之石墨烯，但這兩種方法均無法大面積合成石墨烯。化學氣相沈積法的製備過程中，則必須使用近千度的高溫及昂貴的金屬基板，且須費時數小時才能完成。化學剝離法主要係先將石墨氧化，最後再經過高溫還原的步驟使石墨烯恢復其原本的晶格形狀使其具有導電性。然而，氧化的過程會造成石墨烯的晶格受到破壞，且並非所有的氧化石墨烯均能有效地被還原。上述這些方法的不足之處，都限制了石墨烯之生產及後續的應用。Conventional techniques for producing graphene include mechanical exfoliation, epitaxial growth, chemical vapor deposition (CVD), and chemical exfoliation. Among them, the mechanical exfoliation method and the epitaxial growth method can produce graphene of better quality, but neither method can synthesize graphene over a large area. In the preparation of chemical vapor deposition, it is necessary to use nearly 1000 degrees of high temperature and expensive metal substrates, and it takes several hours to complete. The chemical stripping method mainly oxidizes the graphite first, and finally the step of high temperature reduction causes the graphene to return to its original lattice shape to make it electrically conductive. However, the oxidation process causes the crystal lattice of graphene to be destroyed, and not all of the graphene oxide can be effectively reduced. The shortcomings of these methods limit the production and subsequent application of graphene.
因此，如何提供一種方法能於常溫下生產，兼具低成本、流程簡便及快速生產高品質的石墨烯，已成為重要課題之一。美國專利US 7,790,285提供一種用以製造奈米級石墨烯小片(nano-scaled grapheme platelet)之方法，其方法包含將碳纖維或是石墨纖維以一種嵌入(intercalation)形式穿插在層間的空隙，再將被嵌入的纖維進行剝離，變成石墨烯片(graphene sheets或graphene flakes)；接著將石墨烯片進一步分離，即獲得奈米級石墨烯小片。Therefore, how to provide a method for production at room temperature, low cost, simple process and rapid production of high quality graphene has become one of the important topics. U.S. Patent 7,790,285 provides a method for making a nano-scaled grapheme platelet comprising interweaving a carbon fiber or a graphite fiber in an intercalation between layers and then being The embedded fibers are peeled off to become graphene sheets or graphene flakes; then the graphene sheets are further separated to obtain nano-scale graphene sheets.
另，美國專利US 7,892,514則係提供一種層狀物質如石墨(graphite)或氧化石墨(graphite oxide)的剝離方法，以生成具有平均厚度為0.34至1.02 nm的奈米級小片(platelet)。該方法包含在一特定蒸氣壓下，在一高於鹵素溶點或是昇華點的溫度下，對層狀物粉末進行嵌入(intercalation)；接著以第二個高於鹵素的沸點之溫度，讓嵌入的鹵素原子撐開化合物層間，使化合物剝離(exfoliation)成小片(platelet)；或是將受到嵌入的化合物溶於一液體基質中，以超音波將化合物剝離成小片物質。其中鹵素可為如Cl2，Br2，I2，ICl，IBr，BrCl，IF5，BrF3，ClF3，或其混合物，請參其說明書第4欄第10-18行。Further, U.S. Patent No. 7,892,514 provides a method of stripping a layered material such as graphite or graphite oxide to produce a nanoplatelet having an average thickness of from 0.34 to 1.02 nm. The method comprises intercalating a layer of powder at a temperature above a halogen melting point or sublimation point at a specific vapor pressure; and then allowing a second temperature above the boiling point of the halogen The embedded halogen atoms extend between the layers of the compound to exfoliate the compound into platelets; or the embedded compound is dissolved in a liquid matrix to ultrasonically strip the compound into small pieces. Wherein the halogen may be, for example, Cl 2 , Br 2 , I 2 , ICl, IBr, BrCl, IF 5 , BrF 3 , ClF 3 , or a mixture thereof, please refer to column 4, lines 10-18 of the specification.
此外，申請人另於中華民國專利申請案第100115655號中闡明一種製備石墨烯之方法，其係以化學剝離法製造石墨烯，以電化學電解液中的離子作為嵌入物(insert)並輔以電壓將離子進行嵌入，之後再利用不同電壓將石墨烯剝離。In addition, the applicant further discloses a method for preparing graphene by using a chemical peeling method, using ions in an electrochemical electrolyte as an insert and supplemented by a method of preparing graphene in the Republic of China Patent Application No. 100115655. The voltage embeds the ions and then strips the graphene with different voltages.
上述先前技術所揭示之製造石墨烯之內容僅在於經由其所揭示之方法製備少量石墨烯。然而，因應目前半導體、觸控面板及太陽能電池等領域科技發展之廣大需求，流程簡便、大量、且連續規模化石墨烯製備之設計已日趨重要。本發明即針對如何規模化製備之課題，提供一種快速生產高品質石墨烯之製造設備之設計及方法。同樣的電解方法也可以用於生產石墨烯氧化物。The content of the manufacture of graphene disclosed in the above prior art is only to prepare a small amount of graphene by the method disclosed therein. However, in view of the current demand for technological development in the fields of semiconductors, touch panels and solar cells, the design of simple, large-scale, and continuous scale-scale graphene preparation has become increasingly important. The present invention provides a design and method for rapidly producing high quality graphene manufacturing equipment for the purpose of large-scale preparation. The same electrolysis method can also be used to produce graphene oxide.
有鑑於上述課題，本發明之一目的為提供一種低成本、流程簡便及快速生產高品質之石墨烯及石墨烯氧化物之製造設備。In view of the above problems, it is an object of the present invention to provide a manufacturing apparatus for graphene and graphene oxide which is low in cost, simple in process, and fast in producing high quality.
本發明之另一目的為提供一種規模化量產石墨烯及石墨烯氧化物之方法，基於此項技術所已知的電化學剝離法製作石墨烯及石墨烯氧化物。Another object of the present invention is to provide a method for mass production of graphene and graphene oxide, which is based on an electrochemical stripping method known in the art to produce graphene and graphene oxide.
依據本發明之一種石墨烯及石墨烯氧化物之製造設備，其包含設置：第一電極，其包含一包含石墨初始材料之電極座、第二電極、一電解槽、一電源供應器、及一過濾與分離產物之模組。在本發明之一實施態樣中，第一電極係為一包含石墨初始材料之電極座，而第二電極係亦為一包含石墨初始材料之電極座或一金屬。所謂石墨初始材料亦包含石墨與金屬之混合物。A manufacturing apparatus of graphene and graphene oxide according to the present invention, comprising: a first electrode comprising an electrode holder comprising a graphite starting material, a second electrode, an electrolytic cell, a power supply, and a A module for filtering and separating products. In one embodiment of the invention, the first electrode is an electrode holder comprising a graphite starting material, and the second electrode system is also an electrode holder or a metal comprising a graphite starting material. The so-called graphite starting material also contains a mixture of graphite and metal.
為了達到電化學剝離石墨烯之目的，本發明之製造設備設置一第一電極及一第二電極於一電解液中，第一電極為一包含石墨初始材料之電極座；於第一偏壓下，進行石墨材料之嵌入步驟；於第二偏壓下，進行石墨材料之剝離步驟；以及最終取出電解液中之固體產物。For the purpose of electrochemically stripping graphene, the manufacturing apparatus of the present invention is provided with a first electrode and a second electrode in an electrolyte, the first electrode being an electrode holder comprising a graphite starting material; And performing a step of embedding the graphite material; performing a stripping step of the graphite material under the second bias; and finally removing the solid product in the electrolyte.
在本發明中，石墨初始材料包含具石墨層狀結構之天然石墨、人工石墨、以石墨粉體製作之複合材料、或其組合，特定言之，石墨初始材料係包含天然石墨、高順向性石墨(highly-oriented pyrolytic graphite,HOPG)、瀝青石墨(pitch-based graphite,resin-based graphite)、碳纖維(PAN-and pitch-based carbon fibers)、石炭、或其他含層狀或鱗片狀石墨之碳材料。可以是塊材、碎片、粉體以及不規則形貌之石墨層結晶材料，亦可以是上述形貌之石墨材以黏著體(具導電特性)所結合之塊體。In the present invention, the graphite starting material comprises natural graphite having a graphite layer structure, artificial graphite, a composite material made of graphite powder, or a combination thereof. In particular, the graphite starting material contains natural graphite and high directivity. Highly-oriented pyrolytic graphite (HOPG), pitch-based graphite (resin-based graphite), carbon fiber (PAN-and pitch-based carbon fibers), charcoal, or other carbon containing layered or scaly graphite material. It may be a graphite layer crystal material of a block, a chip, a powder, and an irregular shape, or may be a block in which the above-mentioned topography of the graphite material is bonded by an adhesive body (having a conductive property).
在本發明中，為了達到量產效率，電極之兩極可以都是石墨初始材料或包含石墨初始材料之電極座，且以陣列式或平行排列等叢集串接方式來設置。In the present invention, in order to achieve mass production efficiency, the two poles of the electrode may be graphite starting materials or electrode holders containing graphite starting materials, and are arranged in a series connection manner such as array or parallel arrangement.
在本發明中，第一電極並不侷限於只有一個，可以同時***多個並聯之第一電極。In the present invention, the first electrode is not limited to only one, and a plurality of parallel first electrodes can be simultaneously inserted.
在本發明中，第二電極並不侷限於只有一個，可以同時***多個並聯之第二電極。In the present invention, the second electrode is not limited to only one, and a plurality of parallel second electrodes can be simultaneously inserted.
在本發明之一實施態樣中，金屬係為耐酸鹼之貴重金屬，例如為鉑(Pt)、銀(Ag)、金(Au)、銥(Ir)、鋨(Os)、鈀(Pd)、銠(Rh)、或釕(Ru)等。其亦可包括但不限於一不易被化學蝕刻之導電材料，例如銅(Cu)、不銹鋼(stainless steel)、玻璃碳(glassy carbon)、導電高分子(conducting polymer)等。In one embodiment of the present invention, the metal is an acid-base precious metal such as platinum (Pt), silver (Ag), gold (Au), iridium (Ir), osmium (Os), palladium (Pd). ), 铑 (Rh), or 钌 (Ru), etc. It may also include, but is not limited to, a conductive material that is not easily chemically etched, such as copper (Cu), stainless steel, glassy carbon, conducting polymer, and the like.
在本發明之一實施態樣中，所述設備之電解槽為一可以填充電解液之容器，其材質可以是玻璃、壓克力、PP、PS、PVC等高分子聚合材料、不銹鋼或其他金屬材料所製成之容器。In an embodiment of the present invention, the electrolysis cell of the device is a container capable of filling an electrolyte, and the material thereof may be a polymer material such as glass, acrylic, PP, PS, PVC, stainless steel or other metal. a container made of materials.
在本發明之一實施態樣中，電解液包含溴化氫、鹽酸、或硫酸。In one embodiment of the invention, the electrolyte comprises hydrogen bromide, hydrochloric acid, or sulfuric acid.
在本發明之一實施態樣中，電解液係添加氫氧化鉀。In one embodiment of the invention, the electrolyte is added with potassium hydroxide.
在本發明之一實施態樣中，電解液更包含一氧化劑，該氧化劑係包含重鉻酸鉀、過錳酸、或過錳酸鉀。In one embodiment of the invention, the electrolyte further comprises an oxidizing agent comprising potassium dichromate, permanganic acid, or potassium permanganate.
在本發明之一實施態樣中，為了提升電解石墨烯及石墨烯氧化物之效率或產物品質，電解過程可以視需要輔以加溫、超音波震盪、微波或是具高能量之光源照射、於電解液中以轉子(rotor)製造渦旋(stirring)等方式來輔助剝離出石墨烯及石墨烯氧化物。In an embodiment of the present invention, in order to improve the efficiency or product quality of the electroplated graphene and graphene oxide, the electrolysis process may be supplemented by heating, ultrasonic vibration, microwave or high-energy light source, as needed. In the electrolyte solution, a rotor or the like is manufactured by a rotor to assist in stripping off graphene and graphene oxide.
在本發明中，為了達到連續化製程之目的，所剝離之產物可以進料至一過濾與分離產物之模組，此模組之第一構件為一微孔隙之篩網，其尺寸係在18至1,250網孔(mesh)之間，較佳係在35至500網孔(mesh)之間，用以過濾未剝離之粗粒徑石墨顆粒，以及透過篩選得到適當尺寸之產物；此模組之第二構件為一孔隙尺寸自200至1,200 nm，較佳係300至800 nm之過濾膜，其目的可以收集通過上述篩網之石墨烯片層產物。此外，第二構件上所收集之石墨烯產物可以接續以大量去離子水來去除殘留之電解液，或以其他可以溶解、取代殘餘離子(如K+或SO2 -)之離子溶液(如HCl等)。 In the present invention, in order to achieve the purpose of the continuous process, the stripped product can be fed to a module for filtering and separating the product. The first member of the module is a microporous screen having a size of 18 Between 1,250 meshes, preferably between 35 and 500 meshes, for filtering unpeeled coarse-grained graphite particles, and by screening to obtain products of appropriate size; The second member is a filter membrane having a pore size from 200 to 1,200 nm, preferably from 300 to 800 nm, for the purpose of collecting the graphene sheet product through the screen. In addition, the graphene product collected on the second member can be followed by a large amount of deionized water to remove the residual electrolyte, or other ionic solution (such as HCl) that can dissolve and replace residual ions (such as K + or SO 2 - ). Wait).
在本發明中，偏壓係以一電源供應器來提供，其可以是直流電或交流電供應。在本發明之一實施態樣中，第一偏壓係介於+0.5伏特至+10伏特，較佳介於+2.5伏特至+5伏特。在本發明之一實施態樣中，第二偏壓係介於+5伏特至+220伏特，較佳介於+10伏特至+100伏特。 In the present invention, the bias voltage is provided by a power supply, which may be a direct current or an alternating current supply. In one embodiment of the invention, the first bias voltage is between +0.5 volts and +10 volts, preferably between +2.5 volts and +5 volts. In one embodiment of the invention, the second bias voltage is between +5 volts to +220 volts, preferably between +10 volts and +100 volts.
綜上所述製造設備，本發明提供一種量產化石墨烯及石墨烯氧化物的製造方法，其係以電化學剝離的方式進行，亦即於室溫下透過電壓的改變即可完成嵌入及剝離石墨材料的步驟，無須另外施加高溫進行還原，故能簡化製程，且於短時間內即可大量製成層數少、側向尺寸大及高度石墨化之石墨烯。利於工業上大規模生產並應用於各領域中。 In summary, the present invention provides a method for producing mass-produced graphene and graphene oxide by electrochemical stripping, that is, embedding can be completed by changing the transmission voltage at room temperature. The step of stripping the graphite material eliminates the need for additional high temperature for reduction, so that the process can be simplified, and graphene having a small number of layers, a large lateral dimension, and a high degree of graphitization can be produced in a short time. Conducive to industrial mass production and application in various fields.
該量產化石墨烯及石墨烯氧化物的製造方法係包含：設置第一電極及第二電極於一電解液中，該第一電極為一包含石墨初始材料之電極座，該第二電極為包含石墨初始材料之電極座或一金屬(所謂石墨初始材料亦包含石墨與金屬之混合物)；於第一偏壓下，進行該石墨初始材料之嵌入步驟；於第二偏壓下，進行該石墨初始材料之剝離步驟；及將剝離之產物進料至一過濾與分離產物之模組，該模組包含第一構件，其係一微孔隙之篩網，以及第二構件，其係一過濾膜；於過濾膜上收集石墨烯產物及石墨烯氧化物。The method for producing the mass-produced graphene and the graphene oxide comprises: disposing a first electrode and a second electrode in an electrolyte; the first electrode is an electrode holder comprising a graphite starting material, and the second electrode is An electrode holder comprising a graphite starting material or a metal (the so-called graphite starting material also comprises a mixture of graphite and metal); performing the embedding step of the graphite starting material under a first bias; and performing the graphite under a second bias a stripping step of the starting material; and feeding the stripped product to a module for filtering and separating the product, the module comprising a first member, which is a microporous screen, and a second member, which is a filter membrane The graphene product and the graphene oxide are collected on the filter membrane.
上述之製備方法係如下所述：設置一第一電極及一第二電極以分別作為陽極及陰極，並透過電極線纏繞浸於一電解液中。首先，利用第一偏壓來進行石墨材料之嵌入步驟，目的是讓電解液中之陰離子如硫酸根、硝酸根離子等透過電壓差而嵌插到相鄰的兩層石墨層之間及或其晶粒邊界(grain boundary)上，其中第一偏壓係介於+0.5伏特至+10伏特，較佳介於+2.5伏特至+5伏特，作用時間約1至30分鐘，較佳為1至5分鐘。The preparation method described above is as follows: a first electrode and a second electrode are provided as an anode and a cathode, respectively, and are immersed in an electrolyte through the electrode wire. First, the first bias is used to perform the step of embedding the graphite material, so that the anions such as sulfate, nitrate ions, etc. in the electrolyte are intercalated between adjacent two layers of graphite layers and On the grain boundary, wherein the first bias voltage is between +0.5 volts and +10 volts, preferably between +2.5 volts and +5 volts, and the action time is about 1 to 30 minutes, preferably 1 to 5 minute.
接著，再利用第二偏壓來進行石墨材料之剝離步驟，其中第二偏壓係大於第一偏壓，且介於+5伏特至+220伏特，較佳介於+10伏特至+100伏特，作用時間無限制。需說明的是，本發明之石墨烯及石墨烯氧化物製造方法更可包含：於一第三偏壓下，進行石墨材料之剝離步驟。也就是除了於第二偏壓作用一段時間，來進行剝離步驟之外，還可以利用與第二偏壓不同的第三偏壓，來進行剝離步驟。例如，第三偏壓之極性可與第二偏壓之極性相反，或是極性相同，但大小有差異，其中，第二偏壓和第三偏壓可分別為直流電或交流電。若第三偏壓之極性與第二偏壓之極性相反，則正向電壓可用以促進剝離並氧化石墨烯，之後之負向電壓則可將被氧化的石墨烯還原。在本發明一實施態樣中，第二偏壓係使用+10伏特而第三偏壓係使用-10伏特，操作時間並分別為2秒及5秒，並交替持續一段時間。Then, the second bias voltage is used to perform the stripping step of the graphite material, wherein the second bias voltage is greater than the first bias voltage and is between +5 volts and +220 volts, preferably between +10 volts and +100 volts. There is no limit to the duration of action. It should be noted that the method for producing graphene and graphene oxide of the present invention may further comprise: performing a stripping step of the graphite material under a third bias. That is, in addition to the second biasing for a period of time to perform the stripping step, the stripping step may be performed using a third bias different from the second bias. For example, the polarity of the third bias may be opposite to the polarity of the second bias, or the polarity may be the same, but the size may be different, wherein the second bias and the third bias may be direct current or alternating current, respectively. If the polarity of the third bias is opposite to the polarity of the second bias, the forward voltage can be used to promote stripping and oxidation of graphene, and then the negative voltage can reduce the oxidized graphene. In one embodiment of the invention, the second biasing system uses +10 volts and the third biasing system uses -10 volts, the operating time is 2 seconds and 5 seconds, respectively, and alternates for a period of time.
另外，本發明之嵌入步驟及剝離步驟更可依據所使用的電解液成份及酸鹼度之不同，而使用不同的第一偏壓及第二偏壓條件進行變換，以達最佳的品質及產量。In addition, the embedding step and the stripping step of the present invention can be converted using different first bias voltages and second bias conditions depending on the electrolyte composition and pH used to achieve the best quality and yield.
經過剝離步驟後，所剝離之產物可以經進料端至一過濾與分離產物之模組，此模組之第一構件為一微孔隙之篩網(35 mesh)，用以過濾未剝離之粗粒徑石墨顆粒，以及透過篩選得到適當尺寸之產物；此模組之第二構件為一400 nm孔隙之過濾膜，其目的可以收集通過篩網之石墨烯片層產物。此外，第二構件上所收集之石墨烯產物及石墨烯氧化物可以接續以大量去離子水來去除殘留之電解液，或以其他可以溶解、取代殘餘離子(如K+或SO2 -)之離子溶液(如HCl等)來去除殘留之電解液。而本模組主要以一抽氣裝置S12來加速抽濾之步驟。本實施例以真空過濾法來進行過濾與分離。After the stripping step, the stripped product can pass through the feed end to a module for filtering and separating the product. The first member of the module is a microporous screen (35 mesh) for filtering unpeeled coarse The graphite particles of the particle size and the product of appropriate size are obtained by screening; the second component of the module is a 400 nm pore filter membrane, the purpose of which is to collect the graphene sheet product through the screen. In addition, the graphene product and the graphene oxide collected on the second member may be followed by a large amount of deionized water to remove the residual electrolyte, or other dissolved or substituted residual ions (such as K + or SO 2 - ). An ionic solution (such as HCl) is used to remove the residual electrolyte. The module mainly uses an air extracting device S12 to accelerate the step of suction filtration. This example was subjected to filtration and separation by vacuum filtration.
在本文中，除非特別限定，單數形「一」及「該」亦包括其複數形。本文中任何及所有實施例及例示性用語(如「例如」)目之僅為了更加突顯本發明，並非針對本發明之範圍構成限制，本案說明書中之用語不應被視為暗示任何未請求之組件可構成實施本發明時之必要組件。In this document, the singular forms "a" and "the" are also used in the plural. The use of any and all examples and exemplifications (such as "such as") are intended to be illustrative of the invention and are not intended to limit the scope of the invention. The components may form an essential component in the practice of the invention.
以下將參照相關圖式，說明依本發明較佳實施例之一種石墨烯及石墨烯氧化物之製造方法，其中相同的元件將以相同的參照符號加以說明。Hereinafter, a method for producing graphene and graphene oxide according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings, wherein the same elements will be described with the same reference numerals.
圖1，其係為製備石墨烯及石墨烯氧化物設備之一示意圖。設置一第一電極S02及一第二電極S11以分別作為陽極及陰極，並透過電極線纏繞浸於一電解液S04中。第一電極S02係為一石墨材料或包含石墨之電極座，而第二電極S11則也可為一石墨材料、包含石墨之電極座、或為一金屬。其中，石墨材料除了包含石墨外，還可以是高順向性石墨(highly oriented pyrolytic graphite,HOPG)、瀝青石墨、或石炭等等，而金屬係為一不易被化學蝕刻之貴重金屬，例如為鉑、銀、金、銥、鋨、鈀、銠、或釕等，或其他導電材料，如銅、不鏽鋼、玻璃碳、導電高分子等。此外，在本實施例中，第一電極係為一石墨初始材料，而第二電極係亦為一石墨初始材料。其中石墨初始材料可以是塊材、碎片、粉體以及不規則形貌之石墨層結晶材料，亦可以是上述形貌之石墨材以黏著體(具導電特性)所結合之塊體。在本發明之一實施例中，為了達到量產效率，兩電極之石墨初始材料得以陣列式或平行排列等叢集串接方式來設置。Figure 1, which is a schematic diagram of one of the devices for preparing graphene and graphene oxide. A first electrode S02 and a second electrode S11 are disposed as an anode and a cathode, respectively, and are immersed in an electrolyte S04 through the electrode wires. The first electrode S02 is a graphite material or an electrode holder containing graphite, and the second electrode S11 may also be a graphite material, an electrode holder containing graphite, or a metal. Among them, in addition to graphite, the graphite material may be highly oriented pyrolytic graphite (HOPG), pitch graphite, or carbon charcoal, etc., and the metal is a precious metal that is not easily chemically etched, such as platinum. , silver, gold, rhodium, ruthenium, palladium, iridium, or osmium, or other conductive materials, such as copper, stainless steel, glassy carbon, conductive polymers. Further, in the embodiment, the first electrode is a graphite starting material, and the second electrode is also a graphite starting material. The graphite starting material may be a graphite layer crystalline material of a block, a chip, a powder and an irregular shape, or may be a block in which the graphite material of the above-mentioned morphology is bonded by an adhesive body (having a conductive property). In an embodiment of the present invention, in order to achieve mass production efficiency, the graphite initial materials of the two electrodes are arranged in a series connection manner such as array or parallel arrangement.
在本發明中，所述設備之電解槽為一可以填充電解液之容器S01，其材質可以是玻璃、壓克力、PP、PS、PVC等高分子聚合材料、不銹鋼或其他金屬材料所製成之容器。本實施例中所使用的為玻璃容器。In the present invention, the electrolysis cell of the device is a container S01 which can be filled with an electrolyte, and the material thereof can be made of high-molecular polymer materials such as glass, acrylic, PP, PS, PVC, stainless steel or other metal materials. Container. What is used in this embodiment is a glass container.
在本發明中，為了提升電解石墨烯之效率或產物品質，電解過程可以輔以加溫、超音波震盪、微波或是具高能量之光源照射、於電解液中以轉子(rotor)製造渦旋等方式來輔助剝離出石墨烯。本實施例中使用轉子S05及溫度控制器S06來輔助剝離出石墨烯。In the present invention, in order to improve the efficiency or product quality of the electroplated graphene, the electrolysis process may be supplemented by heating, ultrasonic oscillating, microwave or high-energy light source, and a vortex is formed in the electrolyte by a rotor. Etc. to assist in stripping out graphene. In the present embodiment, the rotor S05 and the temperature controller S06 are used to assist in stripping off the graphene.
本實施例以直流偏壓供應偏壓。第一偏壓係介於+0.5伏特至+10伏特，第二偏壓係介於+5伏特至+220伏特。This embodiment supplies a bias voltage with a DC bias. The first bias voltage is between +0.5 volts and +10 volts and the second bias voltage is between +5 volts and +220 volts.
在本發明中，為了達到連續化製程之目的，以抽水馬達S07將所剝離之產物由進料端S01轉移至一過濾與分離產物之模組S08，此模組之第一構件S09為一微孔隙之篩網(35 mesh)，用以過濾未剝離之粗粒徑石墨顆粒，以及透過篩選得到適當尺寸之產物；此模組之第二構件S10為一400 nm孔隙之過濾膜，其目的可以收集通過篩網之石墨烯片層產物。此外，第二構件上所收集之石墨烯產物可以接續以大量去離子水來去除殘留之電解液，或以其他可以溶解、取代殘餘離子(如K+或SO2 -)之離子溶液(如HCl等)來去除殘留之電解液。而本模組主要以一抽氣裝置S12來加速抽濾之步驟。本實施例以真空過濾法來進行過濾與分離。In the present invention, in order to achieve the purpose of the continuous process, the stripped product is transferred from the feeding end S01 to the module S08 for filtering and separating the product by the pumping motor S07, and the first component S09 of the module is a micro A mesh screen (35 mesh) for filtering unpeeled coarse-grained graphite particles and a product of appropriate size by screening; the second member S10 of the module is a 400 nm pore filter membrane, the purpose of which is The graphene sheet product passing through the screen is collected. In addition, the graphene product collected on the second member can be followed by a large amount of deionized water to remove the residual electrolyte, or other ionic solution (such as HCl) that can dissolve and replace residual ions (such as K + or SO 2 - ). Etc.) to remove residual electrolyte. The module mainly uses an air extracting device S12 to accelerate the step of suction filtration. This example was subjected to filtration and separation by vacuum filtration.
圖2為包含石墨初始材料之電極座設備示意圖。若初始材料為公分(以上)尺度之塊材時，可直接連接線路形成電極；若初始材料為碎片或粉體時，則必須使用圖2所示之電極座，此構件可做為第一電極S02或第二電極S11。其中石墨初始材料S13可以是碎片、粉體及其他微細不易直接連接導電線路之石墨層結晶材料。隔離網S14為一濾網(孔徑：0.1至5 mm)、多孔性薄膜，或具孔洞之構件，其主要功能有三：一．使零散之石墨初始材料保持緊緻及彼此導通之狀態，俾與金屬電極S15形成通路，連接至電源供應器；二．使電解液S04容易進出，有效產生電化學剝離；三．使分解的石墨烯產物容易擴散至溶液中，方便電解液與未反應之石墨初始材料進行後續反應。隔離網孔洞大小之選擇與初始材料尺寸相關，以不使未反應之材料通過為原則。隔離網係為一耐酸鹼之絕緣體，由玻璃、壓克力、PE、PP等或其他高分子聚合物，或經絕緣防蝕處理之金屬材料所構成。金屬電極S15目的為石墨初始材料及外部電路之連接，並可對石墨材料S13施加一固定壓力，使其導電效果更佳。2 is a schematic view of an electrode holder device including a graphite starting material. If the initial material is a block of the centimeters (above) scale, the electrode may be directly connected to form an electrode; if the initial material is a chip or a powder, the electrode holder shown in FIG. 2 must be used, and the member can be used as the first electrode. S02 or second electrode S11. The graphite starting material S13 may be a graphite layer crystalline material which is a chip, a powder and other fine particles which are not easily connected directly to the conductive line. The isolation net S14 is a filter (pore size: 0.1 to 5 mm), a porous film, or a member having a hole, and its main functions are three: one. The scattered graphite initial material is kept in a state of being tight and mutually conductive, and the metal electrode S15 forms a path and is connected to the power supply; Make the electrolyte S04 easy to enter and exit, effectively produce electrochemical stripping; The decomposed graphene product is easily diffused into the solution to facilitate subsequent reaction of the electrolyte with the unreacted graphite starting material. The choice of the size of the isolation mesh is related to the initial material size so as not to pass unreacted material. The isolation network is an acid and alkali resistant insulator composed of glass, acrylic, PE, PP, etc. or other high molecular polymers, or metal materials treated by insulation and corrosion protection. The metal electrode S15 is intended to be a connection between the graphite starting material and an external circuit, and a fixed pressure can be applied to the graphite material S13 to make the conductive effect better.
圖3為經過本實施例所獲得之石墨烯於二甲基甲醯胺溶液(dimethylformamide,DMF)中之分散溶液。3 is a dispersion solution of graphene obtained in the present example in dimethylformamide (DMF).
圖4為經過本實施例所獲得之石墨烯固體粉末。Fig. 4 is a graphene solid powder obtained by the present embodiment.
本實施例透過掃描式電子顯微鏡(scanning electron microscope,SEM,JEOL-6330F)、原子力顯微鏡(atomic force microscope,AFM,Veeco Dimension-Icon system)，以進行觀察石墨烯薄片製成後之外觀。圖5為本實施例中石墨烯薄片固體粉末之掃瞄式電子顯微影像。顯示本實施例所獲得之石墨烯粉末為層狀堆疊且高純度之石墨烯。將石墨烯墨水於二氧化矽(SiO2)之基板上以滴鍍方式形成一薄膜，再利用原子力顯微鏡觀察石墨烯薄片之形態。如圖6所示，所獲得之石墨烯分散液中，石墨烯薄片之厚度均小於或等於3 nm，且當中約有65%的石墨烯薄片之厚度小於2 nm，可見由本實施例所製造出來的石墨烯薄片之厚度非常小。In the present embodiment, a scanning electron microscope (SEM, JEOL-6330F) or an atomic force microscope (AFM, Veeco Dimension-Icon system) was used to observe the appearance of the graphene sheet. Figure 5 is a scanning electron micrograph of the graphene flake solid powder in the present embodiment. The graphene powder obtained in the present example is shown to be a layered stacked and high-purity graphene. A graphene ink was formed on a substrate of cerium oxide (SiO 2 ) by drop plating to form a thin film, and the morphology of the graphene sheets was observed by an atomic force microscope. As shown in FIG. 6, in the obtained graphene dispersion, the thickness of the graphene sheet is less than or equal to 3 nm, and about 65% of the graphene sheets have a thickness of less than 2 nm, which can be seen from the present embodiment. The thickness of the graphene sheets is very small.
請參照圖7，其為石墨烯薄片以拉曼光譜儀(NT-MDT confocal Raman microscopic system)分析其鍵結之數據圖。本實施例取一經AFM觀察得知厚度為1.6 nm之石墨烯薄片，利用拉曼光譜儀以473 nm之波長下進行激發並分析石墨烯之分子鍵結結構。如圖中所示，出現位於約1580 cm-1之G峰呈現較窄且強度較高之形態，顯示由本發明之製備方法所獲得之石墨烯具有較佳石墨結晶型態(graphitization)。一般而言，單層之石墨烯之2D/G強度比值通常大於雙層石墨烯之2D/G強度比值，與圖7中所觀察位於2720 cm-1出現之2D峰，其與G峰之比值卻較習知方法中製成之單層還原態氧化石墨烯(reduced graphene oxide)比值大，因此再次證明本發明之石墨烯具有較佳的石墨化。Please refer to FIG. 7 , which is a graph of graphs of graphene sheets analyzed by a NT-MDT confocal Raman microscopic system. In this example, a graphene sheet having a thickness of 1.6 nm was observed by AFM, and the molecular bonding structure of graphene was analyzed by Raman spectroscopy at a wavelength of 473 nm. As shown in the figure, the appearance of the G peak at about 1580 cm -1 exhibiting a narrower and higher intensity shows that the graphene obtained by the production method of the present invention has a better graphite graphitization. In general, the 2D/G intensity ratio of a single layer of graphene is usually greater than the 2D/G intensity ratio of the bilayer graphene, and the 2D peak at 2720 cm -1 observed in Figure 7, the ratio to the G peak is The ratio of the reduced graphene oxide produced in the conventional method is large, and thus the graphene of the present invention is again proved to have better graphitization.
另於製備過程中，將電解直流偏壓增加或是增加電解液酸度，可以產出石墨烯氧化物，其純化過程僅需過濾及水洗即可，其生產方式步驟及原料設備皆同於上述製備石墨烯之敘述。以此方法製備之石墨烯氧化物其拉曼光譜儀特徵峰如圖8所示。In the preparation process, the electrolytic DC bias is increased or the acidity of the electrolyte is increased, and the graphene oxide can be produced. The purification process only needs to be filtered and washed, and the production steps and raw material equipment are the same as the above preparation. Description of graphene. The graphene oxide prepared by this method has a Raman spectrometer characteristic peak as shown in FIG.
以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the present invention should be included in the scope of the appended claims.
S01．．．電解槽S01. . . Electrolytic cell
S02．．．第一電極S02. . . First electrode
S03．．．電源供應器S03. . . Power Supplier
S04．．．電解液S04. . . Electrolyte
S05．．．轉子S05. . . Rotor
S06．．．溫度控制器S06. . . Temperature Controller
S07．．．抽水馬達S07. . . Pumping motor
S08．．．過濾與分離產物之模組S08. . . Module for filtering and separating products
S09．．．第一構件S09. . . First member
S10．．．第二構件S10. . . Second member
S11．．．第二電極S11. . . Second electrode
S12．．．抽氣裝置S12. . . Air suction device
S13．．．石墨材料S13. . . Graphite material
S14．．．隔離網S14. . . Isolation network
S15．．．金屬電極S15. . . Metal electrode
圖1.為本發明石墨烯之製程設備示意圖Figure 1. Schematic diagram of the process equipment for graphene of the present invention
圖2.為包含石墨初始材料之電極座設備示意圖Figure 2. Schematic diagram of an electrode holder device containing graphite starting material
圖3.為石墨烯之溶液(分散於250mL DMF溶液)Figure 3. Graphene solution (dispersed in 250mL DMF solution)
圖4.為分離過濾後石墨烯固體Figure 4. Graphene solids after separation and filtration
圖5.為石墨烯固體之掃描式電子顯微鏡影像圖Figure 5. Scanning electron microscope image of graphene solids
圖6.為石墨烯之原子力顯微圖像Figure 6. Atomic force microscopy image of graphene
圖7.為石墨烯以拉曼光譜儀分析其鍵結型態之訊號Figure 7. Signals for graphene analysis of its bond type by Raman spectroscopy
圖8.為石墨烯氧化物以拉曼光譜分析其鍵結之訊號Figure 8. Signals for the bonding of graphene oxides by Raman spectroscopy
S01．．．電解槽S01. . . Electrolytic cell
S02．．．第一電極S02. . . First electrode
S03．．．電源供應器S03. . . Power Supplier
S04．．．電解液S04. . . Electrolyte
S05．．．轉子S05. . . Rotor
S06．．．溫度控制器S06. . . Temperature Controller
S07．．．抽水馬達S07. . . Pumping motor
S08．．．過濾與分離產物之模組S08. . . Module for filtering and separating products
S09．．．第一構件S09. . . First member
S10．．．第二構件S10. . . Second member
S11．．．第二電極S11. . . Second electrode
S12．．．抽氣裝置S12. . . Air suction device
Claims (19)
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| GB2520496B (en) * | 2013-11-20 | 2020-05-27 | Univ Manchester | Production of graphene oxide |
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| CN106435632A (en) * | 2016-09-20 | 2017-02-22 | 南昌大学 | Preparation method for boron-doped graphene |
| RU2675146C2 (en) * | 2017-02-21 | 2018-12-17 | Владимир Васильевич Журавлев | Graphene, graphene films and coatings production method |
| AU2018201650B2 (en) * | 2017-03-09 | 2022-06-09 | First Graphene Ltd | Equipment and/or method(s) for use in graphene production |
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| BR112013028162B1 (en) * | 2011-12-14 | 2020-10-27 | National University Of Singapore | process to form minerals in expanded hexagonal layers and derivatives using electrochemical loading and composition of matter for that |
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