201130737 六、發明說明： 【發明所屬之技術領域】 本發明係有關含有氟化開孔碳奈米角之氟儲存裝置， 及氟氣體之取出方法。 【先前技術】 氟氣體於能源產業上濃縮鈾時，自古以來被持續大胃 利用於合成U F 6用。 又，氟氣體對合成防水防油劑、鋰電池活物質、製g 半導體用乾蝕液、製造半導體用氟聚合物、高分子材料 添加劑、醫藥中間物等工業上有用之機能性材料係不可$ 缺，其使用量也逐年增加。 又，將氟氣體發展作爲次世代之半導體、製造液晶用 乾蝕液、清洗用氣體、CVD用氣體用深受期待。 但氟氣體具有極高之反應性、腐蝕性，故儲存及處理 上需極高之技術性，因此其利用上明顯受限。 即，將氟氣體儲存於金屬製料筒時，爲了確保安全性 ，除了需將壓力限制於2 Μ P a以下外，還需預先以氮等稀 釋再塡充。又’由料筒取出氟氣體時需備有數次特殊之閥 裝置、減壓裝置、安全裝置’就此等觀點氟氣體之利用 上係欠缺經濟性、生產性。另外既使爲塡入料筒前經周密 精製所得之高純度氟氣體，也會因構成料筒及閥裝置之材 料的腐餓生成物（例如各種金屬氟化物）而被污染，特別 是供給半導體製造用途時含有，需另設置精製裝置等之對 -5- 201130737 策等問題。 又，藉由電解含有氟化氫之熔融鹽所發生的氟氣體可 直接利用，但該方法除了需實施具有保安用之充分空地與 徹底遮蔽之電解槽室的周密之安全對策外，爲了確保大型 整流器、精製裝置、除害裝置需於各處所配備具有高超技 術之運轉要員、保安要員。又，通電後無法馬上取出高純 度之氟氣體，需實施長時間之預備電解。因長時間持續電 解時會發生突然陽極效果，而有時常被迫中斷電解之問題 ，故其利用上極欠缺經濟性、生產性。 又，已知以金屬氟化物作爲氟儲存材料用，藉由金屬 氟化物之熱分解而取出氟氣體之方法。例如可藉由，使 K3NiF6成爲氟化 K3NiF7後，使用時將其熱分解返回 K3NiF6而發生氟氣體。但該方式會有，K3NiF7每單位質 量之氟儲存量理論上爲較小之7.0質量％之問題。 近年來開發出新材料之碳奈米管（CNT)及碳奈米角 (CNH )，各種領域爲了利用而活躍檢討其作爲氟之儲存 材料用。 例如專利文獻1曾提案，CNT經氟化後，使所得之氟 化碳奈米管（F-CNT )加溫再取出氟氣體之方法。藉由該 方法可提升每單位質量之氟儲存量，但氟化之反應溫度爲 200°C時，F-CNT每單位質量之氟儲存量將止於52.9質量 %。取出氟氣體僅以加溫進行時，會減少氟氣體取出法之 自由度，又該方法中會有，發生相當量之不純物cf4、 C2F6等氟代烴氣體之問題，另外伴隨氟的儲存、放出循環 -6 - 201130737 含有F-CNF之物理性崩解之問題。 又，專利文獻2曾記載’以氟化碳奈米角（F_CNH) 作爲氟儲存材料用。專利文獻2曾揭示’可藉由F-CNH 加熱或減壓以取出高純度之氟氣體。 已知爲了增加CNT及CNH之吸附面積而實施開孔處 理（專利文獻3 )。又，既使專利文獻2也曾揭示，CNH 於高溫、氧雰圍下藉由實施開孔處理會有控制開孔碳奈米 角（h-CNH )之氟儲存量的可能性。 先前技術文獻 專利文獻 專利文獻1 :特開2005-273〇70號公報 專利文獻2 :國際公開第2007/077823號報告 專利文獻3 :特開2002-3 2603 2號公報 【發明內容】 發明之槪要 發明所欲解決之課題 有鑑於上述現狀，本發明之目的爲，提供含有具有較 大之氟儲存量，且可安全有效率取出高純度之氟氣體的_ 儲存構件之氟儲存裝置。 解決課題之方法 本發明係有關含有氟化開孔碳奈米角（F-h-CNH )作 爲氟儲存材料之氟儲存裝置。 201130737 作爲氟儲存材料用之F-h-CNH於氟化前之開孔碳奈米 角（h-CNH)較佳爲，bet比表面積爲1000至1500 m2/g 之物’及/或細孔容積（中孔容積與微孔容積之和）爲0.8 至1.4 cm3/g之物，及/或微孔容積爲ο」至〇 5 cm3/g之物 ’及/或拉曼分光測定所得之D頻帶之強度（ID )與G頻 帶之強度（Ig )之比（iD/iG )爲1 .8至2.6之物。 又’ F-h-CNH較佳爲，以過氧化氫處理CNH所得之 h-CNH再氟化所得之F_h-CNH。 本發明又有關，將含有氟化開孔碳奈米角之氟儲存材 料加熱’或置於減壓雰圍下，取出氟氣體之方法。 特佳爲’將含有h-CNH於0至400°C下氟化所得之F-h-CNH的氟儲存材料，於5 50°C下加熱以取出氟氣體。 又特佳爲，將含有開孔碳奈米角於0至40(TC下氟化 所得之氟化開孔碳奈米角的氟儲存材料，放置於1 P a之 5 0 kPa以下之減壓雰圍下以取出氟氣體》 本發明之方法所使用之氟化前的h-CNH較佳爲，具有 前述特性之物，又以過氧化氫處理CNH所得之h-CNH爲 佳。 發明之效果 本發明可提供，氟儲存材料每單位質量之氟儲存量較 多，耐重覆之氟儲存’又可以安全且有效率之方法取出高 純度之氟氣體的氟儲存裝置。 201130737 實施發明之形態 本發明之氟儲存裝置爲，含有氟化開孔碳奈米角（F-h-CNH)作爲氟儲存材料。 下面將說明氟化前之h-CNH，接著說明F-h-CNH。 CNH爲，僅由以雷射脫離法合成之角長10至2 0nm、 角端徑2至3nm之碳原子構成，形成具有角爲50至 1 OOnm之大理花般形狀之二次粒子的奈米碳材料。 CNH之開孔處理爲，切斷部分構成CNH之壁部及先 端部的該碳-碳鍵形成細孔之處理，已知如專利文獻3、特 開2006-72 1 7號公報等所記載之處理。具體例如下述之處 理方法。 (1 )以過氧化氫處理CNH之方法（專利文獻3 ) 例如將CNH投入備有儲存過氧化氫水之回流冷卻器 之玻璃容器中，於處理溫度25至100°C、處理時間1至 180分鐘之範圍內攪拌的同時加熱處理，其後過濾、乾燥 再粉碎。此時可使用硝酸、次亞氯酸、過二硫酸等之酸化 性物質取代過氧化氣水，又’爲了改善與CNH之親和性 ，可預先將CNH分散於乙醇等有機溶劑中’其後以過氧 化氫水等處理。 (2)氧雰圍下酸化處理之方法（專利文獻3) 以分批方式’例如於氧分壓1至1 〇1 kP a之範圍、溫 度250至700 °C之範圍內，既使會因一度處理之CNH量而 201130737 異，但以處理時間1至120分鐘加熱。一度處理之CNH 量較多時，就處理之效率性、均勻性觀點更佳爲採用流通 方式之酸化處理。 由此所得之h-CNH可藉由開孔處理條件成爲具有各種 物理性、化學性、構造性之特性之物。本發明之特佳之h -CNH爲，具有下述特性之物。 (A) BET 比表面積：1000 至 1500 m2/g BET比表面積爲影響氟之吸附量、氟之放出量、氟之 放出速度、放出氟氣體之純度、氟吸附及放出之循環特性 等之特性。 BET比表面積爲1000至1500 m2/g之範圍時，可以較 低之溫度快速吸脫附較多之氟。更佳之BET比表面積爲 1300 至 1500 m2/g，特佳爲 1400 至 1500 m2/g。 BET比表面積之測定方法如後述。 (B )細孔容積（Vtotal ) : 0.8 至 1 _4 cm3/g 細孔容積爲影響氟之吸附量、氟之放出量、氟之放出 速度、放出氣體之純度、氟吸附及放出之循環特性等之特 性。 細孔容積爲0.8至1.4 cm3/g之範圍時，可無損放出 氟氣體之純度、氟吸附及放出之循環特性下增加氟之吸附 量。更佳之細孔容積爲0.8至1.2 cm3/g。 細孔容積之測定方法如後述^ -10 - 201130737 (C)微孔容積（Vmicro) ·· 0.3 至 0.5 cm3/g 微孔容積爲影響氟之吸附量、氟之放出量、氟之放出 速度、放出氣體之純度、氟吸附及放出之循環特性等之特 性。 微孔容積爲0.3至0.5 cm3/g之範圍時，可無損放出 氟氣體之純度、氟吸附及放出之循環特性下增加氟之吸附 量。更佳之微孔容積爲0.3至0.4 cm3/g。 微孔容積之測定方法如後述。 (D )拉曼分光測定所得之D頻帶之強度（ID )與G頻帶 之強度（IG)之比（ID/IG) : 1.8至2.6 ID/IG爲影響氟之吸附量、氟之放出量、氟之放出速度 、放出氣體之純度、氟吸附及放出之循環特性等之特性。201130737 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fluorine storage device containing a fluorinated open-celled carbon nanohorn, and a method for taking out a fluorine gas. [Prior Art] When fluorine gas is enriched in uranium in the energy industry, it has been used for synthesizing U F 6 since ancient times. Further, the fluorine gas is not compatible with synthetic water- and oil-repellent agents, lithium battery active materials, dry etching liquids for semiconductors, fluoropolymers for semiconductor production, polymer material additives, and pharmaceutical intermediates. In short, its usage has also increased year by year. In addition, the development of fluorine gas as a semiconductor for the next generation, the production of a dry etching liquid for liquid crystal, a cleaning gas, and a gas for CVD are expected. However, fluorine gas is extremely reactive and corrosive, so it requires a high degree of technical storage and handling, so its utilization is obviously limited. In other words, when storing the fluorine gas in the metal cylinder, in order to ensure safety, in addition to limiting the pressure to 2 Μ P a or less, it is necessary to preliminarily dilute it with nitrogen or the like. Further, when a fluorine gas is taken out from a cylinder, a special valve device, a pressure reducing device, and a safety device are required. From the viewpoints, the utilization of fluorine gas is lacking in economy and productivity. In addition, even if the high-purity fluorine gas obtained by thorough purification before being poured into the cylinder is contaminated by the hunger-forming products (for example, various metal fluorides) constituting the material of the cylinder and the valve device, in particular, the semiconductor is supplied. In the case of manufacturing use, it is necessary to provide a refining device, etc., to the problem of -5 - 201130737. Further, the fluorine gas generated by electrolyzing the molten salt containing hydrogen fluoride can be directly used. However, in addition to the need to implement a thorough safety measure for the electrolytic cell chamber having sufficient space for security and thorough shielding, in order to secure a large rectifier, The refining device and the decontamination device are required to be equipped with highly skilled technical personnel and security personnel in various places. Further, after the energization, it is impossible to immediately take out the high-purity fluorine gas, and it is necessary to carry out the preliminary electrolysis for a long time. Since the sudden anode effect occurs due to long-term continuous electrolysis, and sometimes the problem of electrolysis is often interrupted, the use of the upper pole is lacking in economy and productivity. Further, a method in which a metal fluoride is used as a fluorine storage material and a fluorine gas is taken out by thermal decomposition of a metal fluoride is known. For example, after K3NiF6 is made into fluorinated K3NiF7, it is thermally decomposed back to K3NiF6 to generate fluorine gas during use. However, this method has a problem that the fluorine storage amount per unit mass of K3NiF7 is theoretically 7.0% by mass. In recent years, carbon nanotubes (CNTs) and carbon nanohorns (CNH) have been developed for new materials, and various fields have been actively reviewed for use as storage materials for fluorine. For example, Patent Document 1 proposes a method in which a fluorinated carbon nanotube (F-CNT) is heated and then a fluorine gas is taken out after the CNT is fluorinated. By this method, the fluorine storage amount per unit mass can be increased, but when the reaction temperature of the fluorination is 200 ° C, the fluorine storage amount per unit mass of the F-CNT will be stopped at 52.9 mass%. When the fluorine gas is taken out only by heating, the degree of freedom of the fluorine gas extraction method is reduced, and in this method, a considerable amount of impurities such as fluorocarbon gas such as cf4 and C2F6 are generated, and the storage and release of fluorine are accompanied. Cycle -6 - 201130737 contains the problem of physical disintegration of F-CNF. Further, Patent Document 2 describes that a carbon fluoride nanohorn (F_CNH) is used as a fluorine storage material. Patent Document 2 discloses that 'high-purity fluorine gas can be taken out by heating or depressurizing by F-CNH. It is known that the opening treatment is performed in order to increase the adsorption area of CNT and CNH (Patent Document 3). Further, even in Patent Document 2, it has been revealed that CNH can control the fluorine storage amount of the open-cell carbon nano angle (h-CNH) by performing the opening treatment under high temperature and oxygen atmosphere. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2007-077823. Patent Document 3: JP-A-2002-3 2603 No. 2 [Invention] In order to solve the above problems, it is an object of the present invention to provide a fluorine storage device comprising a storage member having a large fluorine storage amount and capable of safely and efficiently extracting a high-purity fluorine gas. Means for Solving the Problems The present invention relates to a fluorine storage device comprising a fluorinated open-celled carbon nanohorn (F-h-CNH) as a fluorine storage material. 201130737 Fh-CNH used as a fluorine storage material is preferably an open-cell carbon nanohorn (h-CNH) before fluorination, and a bet specific surface area of 1000 to 1500 m2/g and/or pore volume ( The sum of the mesopore volume and the micropore volume is 0.8 to 1.4 cm3/g, and/or the micropore volume is ο" to 〇5 cm3/g' and/or the D-band obtained by Raman spectrometry The ratio of the intensity (ID) to the intensity (Ig) of the G band (iD/iG) is from 1.8 to 2.6. Further, F-h-CNH is preferably an F_h-CNH obtained by re-fluorinating h-CNH obtained by treating CONH with hydrogen peroxide. Further, the present invention relates to a method of heating a fluorine storage material containing a fluorinated open-celled carbon nanohorn or placing it under a reduced pressure atmosphere to take out a fluorine gas. Particularly preferred is a fluorine storage material containing F-h-CNH obtained by fluorinating h-CNH at 0 to 400 ° C, and heating at 550 ° C to take out fluorine gas. Further preferably, the fluorine storage material containing the open-celled carbon nanohorn at 0 to 40 (fluorinated open-celled carbon nanohorn obtained by fluorination at TC is placed at a pressure of less than 50 kPa below 1 Pa The fluorine gas before the fluorination is used in the atmosphere. The h-CNH before fluorination used in the method of the present invention is preferably a substance having the above characteristics, and h-CNH obtained by treating CNH with hydrogen peroxide is preferred. The invention can provide a fluorine storage device in which a fluorine storage material per unit mass of a fluorine storage material is large, and a heavy-duty fluorine storage can be taken out, and a high-purity fluorine gas can be taken out in a safe and efficient manner. 201130737 Embodiment of the invention The fluorine storage device comprises a fluorinated open-celled carbon nanohorn (Fh-CNH) as a fluorine storage material. The following describes the h-CNH before fluorination, followed by Fh-CNH. The CNH is only separated by laser. The method comprises a carbon atom having an angular length of 10 to 20 nm and an angular end diameter of 2 to 3 nm, and a nano carbon material having a secondary particle having a shape of a marble of 50 to 100 nm is formed. The opening treatment of the CNH is The cut portion constitutes the carbon-carbon bond forming portion of the wall portion and the tip end portion of the CNH For example, the treatment described in JP-A-2006-72177, etc. is known, for example, the following treatment methods. (1) A method of treating CNH with hydrogen peroxide (Patent Document 3) The COH is put into a glass vessel equipped with a reflux cooler for storing hydrogen peroxide water, and heated at a treatment temperature of 25 to 100 ° C for a treatment time of 1 to 180 minutes, followed by filtration, drying and pulverization. In this case, the acidified material such as nitric acid, hypochlorous acid or peroxodisulfuric acid can be used to replace the peroxidic gas, and in order to improve the affinity with CNH, CNH can be dispersed in an organic solvent such as ethanol in advance. Treatment with hydrogen peroxide water, etc. (2) Method for acidizing treatment in an oxygen atmosphere (Patent Document 3) In a batch manner, for example, in the range of oxygen partial pressure of 1 to 1 〇1 kP a, temperature of 250 to 700 ° C In the range, even if the amount of CNN processed at one time is different from 201130737, it is heated by the treatment time of 1 to 120 minutes. When the amount of CNN processed at one time is large, the efficiency and uniformity of treatment are better. Acidification treatment The h-CNH can be made into various physical, chemical, and structural properties by the opening treatment conditions. The particularly preferable h-CNH of the present invention has the following properties: (A) BET specific surface area : 1000 to 1500 m2 / g BET specific surface area is a characteristic that affects the amount of fluorine adsorbed, the amount of fluorine released, the rate of release of fluorine, the purity of fluorine gas released, and the cycle characteristics of fluorine adsorption and release. The BET specific surface area is 1000 to In the range of 1500 m2/g, more fluorine can be quickly absorbed and removed at a lower temperature. More preferably, the BET specific surface area is from 1300 to 1500 m2/g, particularly preferably from 1400 to 1500 m2/g. The method for measuring the BET specific surface area will be described later. (B) pore volume (Vtotal): 0.8 to 1 _4 cm3/g The pore volume is the influence of the amount of fluorine adsorbed, the amount of fluorine released, the release rate of fluorine, the purity of the evolved gas, the cycle characteristics of fluorine adsorption and release, etc. Characteristics. When the pore volume is in the range of 0.8 to 1.4 cm3/g, the purity of fluorine gas, the adsorption characteristics of fluorine adsorption and release, and the adsorption amount of fluorine can be increased without loss. A more preferred pore volume is from 0.8 to 1.2 cm3/g. The method for measuring the pore volume is as follows. ^ -10 - 201130737 (C) Micropore volume (Vmicro) ·· 0.3 to 0.5 cm3/g The pore volume affects the amount of fluorine adsorbed, the amount of fluorine released, the rate at which fluorine is released, The characteristics of the purity of the gas, the fluorine adsorption and the circulation characteristics of the emission are released. When the micropore volume is in the range of 0.3 to 0.5 cm3/g, the purity of fluorine gas, the adsorption characteristics of fluorine adsorption and release, and the adsorption amount of fluorine can be increased without loss of release. More preferably, the micropore volume is from 0.3 to 0.4 cm3/g. The method for measuring the micropore volume will be described later. (D) Ratio of the intensity (ID) of the D-band obtained by Raman spectrometry to the intensity (IG) of the G-band (ID/IG): 1.8 to 2.6 ID/IG is the amount of adsorption affecting fluorine, the amount of fluorine released, The characteristics of the release rate of fluorine, the purity of the evolved gas, and the cyclic characteristics of fluorine adsorption and release.
Id/1(3爲1.8至2.6之範圍時，可無損放出氟氣體之純 度、氟吸附及放出之循環特性下增加氟之吸附量。更佳之 Id/Ig 爲 2.1 至 2.6。 拉曼分光測定法如後述。 h-CNH之氟化可以，例如財團法人產業創造硏究所紀 要 Vol_25 Νο·3(通卷 99 號）2005 年 9 月，p 06 至 ρ η ;物理化學雜誌（Journal of Physical Chemistry) Β，1〇8 (28), 96 1 4-96 1 8 (2004);或第32回碳材料學會予稿集， 2005年12月7日發行，p 132至133所揭示之已知方法 實施。即，將h-CNH封入由鎳或含鎳之合金、黑鉛等對 -11 - 201130737 氟具有耐蝕性之材料所製造之反應器中，例如導入氟氣體 可氟化。 較佳之氟化反應壓力可由0.002至1.0 MPa，更佳由 0.005至0.5 MPa之範圍內，考量生產性、經濟性、安全 性後選定，但過低時會減緩氟化速度，太高時需大型反應 裝置。所使用之氟化用氣體之純度以較高者爲佳，又氟濃 度可爲1.0質量％以上，或以99質量％以下之氮、氬、氨 稀釋。較佳之氟濃度爲1質量％以上，更佳爲1 〇質量％以 上，特佳爲99質量％以上。 又，可含有四氟乙烷、六氟乙烷等氟化烴類，或氟化 氫、三氟化氮、五氟化碘等無機氟化物等或氧、水蒸氣等 〇 氟化反應可於具有充分容積之反應器中分批進行，或 適當取代氟氣體的同時進行之半分批式，又，可以流通式 進行。又，一度大量進行h-CNH之氟化時，爲了使反應 均勻化較佳爲反應器設有適當之攪拌機構。所使用的攪拌 機構可爲，利用各種攪拌翼進行攪拌、機械式回轉或震動 反應器之方法、藉由氣體流通使h-CNH之粉體層流動之 方法等，但過度攪拌恐破壞h-CNH之構造需注意。 氟化反應溫度可由-100 °C至500 °C之範圍內考量生產 性、經濟性、安定性後選定’更佳爲室溫（25°C )至350 °C，特佳爲室溫至1 5 0 °C。反應溫度太低時會減緩氟化之 速度，又，含有氟儲存量不足之問題，另外太高時會使h-CNH之分解反應提高，又’難放出儲存之氟需注意。反應 -12- 201130737 時間依存於反應方式、反應條件’無特別限定下較佳設定 於10秒至1〇〇小時之範圍內。太短時難充分進行氟化， 傾向降低h - C Ν Η之利用效率，又太長時除了助長分解反 應外，需耗較長時間會降低工業上之生產效率。 又，開孔碳奈米角（h-CNH )比較未經開孔處理之碳 奈米角（s-CNH )可以較短時間氟化（氟吸藏）（參考圖 1 ) ° 氟儲存量（氟化量）可藉由氟氣壓、反應溫度、反應 時間、添加氣體等，使氟原子與碳原子之組成比F/C爲 0.1至1.5之範圍（以F-h-CNH每單位質量換算時氟含量 相當於13.7至70.4質量％ )，更佳爲〇·5至1.5(氟含量 相當於44.2至70.4質量％ )，特佳爲1.0至1.5(氟含量 相當於61 .2至70.4質量％ )之方式選定。例如提高氟氣 壓與反應溫度，拉長反應時間可增加氟儲存量（氟化量） 〇 未經開孔處理之氟化碳奈米角（F-s-CNH )之氟原子 與碳原子之組成比F/C相對較低爲0.1至〇·6之範圍（以 F-h-CNH每單位質量換算時氟含量相當於13.7至48.7質 量％ )。 由此所得之F-h-CNH爲，構成碳奈米角之碳原子與氟 原子形成共鍵乃至半離子性鍵，常溫常壓下具安定性，含 放出極微量之氟氣體爲安定之物。 本發明之氟儲存裝置爲，含有該F-h-CNH作爲氟儲存 材料之裝置。 -13- 201130737 本發明之氟儲存裝置可儲存較多量之氟氣體，又可安 全且有效率取出高純度之氟氣體，因此對需要氟氣體之各 種產業具有較高利用可能性。即可期係被利用於使用氟氣 體之半導體用途之各種步驟及醫藥中間物等之精密合成反 應。 具體之裝置如，氟儲存彈、氟儲存筒等之可移動之儲 存容器等，但非限定於此等。又，鎳、銅、黃銅、蒙乃爾 合金、不銹鋼等之金屬製反應器可作爲儲存容器。 本發明將F-h-CNH塡入裝置之方法可爲，於裝置外將 氟化之F-h-CNH塡入儲存容器之方法；於裝置內氟化之方 法；另外製作氟儲存裝置與氟放出裝置僅更換儲存器之方 法。又’將F-h-CNH塡入儲存容器之內部時，爲了防止容 器內F-h-CNH之粉塵飛散，及確保充分之塡充量與放出速 度，可採用預先將F-h-CNH造粒或使用輥壓製機等成型爲 錠劑之方法，或附載於金屬或至少表面由金屬氟化物構成 之粒子、纖維、薄片、多孔質體之方法，或添加氟樹脂成 型爲薄膜狀、濾器狀之方法等。又，爲了提高由F-h-CNH 放出氟之效率與速度可於儲存容器之內部設置預先收納F-h-CNH之多數的盤、筒。上述所列舉之方法以h-CNH實 施後，再氟化也可得到相同之效果。製造後之CNH之容 積密度非常低爲〇.〇1 g/cm3左右，因此一般係使用乙醇等 實施濕式造粒處理後，以瑪瑙製乳鉢粉碎，使容積密度爲 0.1 g/cm3以上再供給其後之步驟。以過氧化氫處理開孔之 h-CNH之開孔處理爲濕式處理，因此必然係與進行上述造 -14- 201130737 粒處理後相同之形態供給。該類h-CNH既使儲 乎可於不改變容積下增加質量，因此每1 g之h-1 g之氟時，容積密度大約爲0.2 g/cm3。 裝置內氟化之方法中，易以1種裝置重覆進 之儲存（氟化）與放出（取出）。 又，本發明係有關由F-h-CNH取出高純度之 方法。 由F-h-CNH取出高純度之氟氣體之方法如 CNH加熱之方法、將F-h-CNH放置於減壓雰圍 、組合此等之方法等。 (1 )將F-h-CNH加熱之方法 藉由加熱切斷構成F_h-CNH之碳原子與氟原 (脫氟化反應），放出氟氣體（F2 )。施加之熱 溫度）可爲，常壓（大氣壓）下保持100°C以上 由保持於比h-CNH之氟化溫度更高之溫度下， 取出氟氣體。 加熱溫度會因氟化溫度而異，但較佳爲1 00 ，更佳爲100至45 0°C。加熱溫度太高時，會因 增加氟代烴不純物之發生量，又會改變F-h-CNH 爲重覆使用之障礙。又，若加熱溫度過低時，則 速度過於遲緩，於作爲裝置時則會欠缺經濟性。 本發明之特徵之一爲，取出之氟氣體中含有 不純物氟代烴氣體。特開20 05 -2 73 〇7〇號公報所 存氟也幾 CNH儲存 行氟氣體 氟氣體之 ，將 F - h - 下之方法 子之鍵結 量（加熱 ，又，藉 可更有效 至 5 5 0 °C 熱分解而 之構造成 氟之釋出 極少量之 提案之F- -15- 201130737 s-CNH中，藉由加溫取出之氣體中多半由分解物CF4、 C2F6等之氟代烴氣體所佔有，但本發明加熱取出之氟氣體 中之氟氣體（F2 )濃度爲99質量％以上（雰圍氣體除外） ，較佳爲99.5質量％以上，更佳爲99.9質量％以上’特佳 爲99.99質量％以上之高純度之氟氣體。 (2) 將F-h-CNH放置於減壓雰圍下之方法 本發明也可藉由將氟化碳奈米角放置於減壓雰圍下取 出高純度之氟氣體（脫氟化反應）。 減壓程度接近真空狀時可更有效率取出氟氣體。具體 上可考量必要之氟量及氣體壓力、氟氣體放出速度等後選 擇。前述脫氟化中反應容器內之減壓度一般較佳爲100 kPa以下，更佳爲1 pa至50 kPa。 該減壓方法無需加熱，因此不僅可提高安全性及能源 效率，也可減少不純物氟代烴氣體發生。 (3) 減壓雰圍下加熱之方法 藉由減壓雰圍下將F-h-CNH加熱，可更有效率且可抑 制不純物氟化烴氣體發生下取出氟氣體。 具體上可考量減壓程度、必要之氟氣體壓力、氟氣體 放出速度等後選擇，例如減壓雰圍爲1 Pa至50 kPa時， 可由加熱溫度100至550 °C之範圍內適當選擇。 本發明可取出之氟氣體量（放出比率）爲，氟儲存量 (氟化量）之99質量。/。以上。 -16- 201130737 本發明作爲氟儲存材料用之開孔處理後之F-h-CN Η與 先前未開孔處理之F-s-CNH的最大不同點爲，F-s-CNH之 氟化溫度較高時氟氣體之放出比率較大，但F-h-CNH之氟 化溫度較低之物的氟氣體之放出比率較大（參考圖2)。 如上述可以較低溫度氟化後以較高比率取出氟氣體， 因此可提高熱效率削減能源成本，又，可減少賦予 F-h-CNH之損害，故可期待長期間持續儲存-取出循環。 【實施方式】 實施例 下面將舉實施例等具體說明本發明，但本發明非限定 於該實施例。 本發明所採用之各種物性之測定方法如下述。 (1 ) BET比表面積（m2/g) 裝置：Quantachrome 製之 Autosorb-1 MP 測定方法：將試料導入2 0 m g程度測定單元中，4 8 2 K： 下真空加熱處理後’ 7 7 K下以純度9 9.9 9 9 9 5 %以上之純氮 氣體作爲試驗氣體’以容量法測定，再以Β ΕΤ法解析測定 數據。 測定條件：482Κ下真空加熱處理後，測定77Κ下之 氣吸附等溫線。 (2 )細孔容積（c m3 / g ) -17- 201130737 裝置· Quantachrome 公司製之 Autosorb-l MP 測定方法：將試料導入20 mg程度測定單元中，48 2K 下真空加熱處理後，77Κ下以純度99.99995%以上之純氮 氣體作爲試驗氣體，以容量法測定。 測定條件：482Κ下真空加熱處理後，測定77Κ下之 氮吸附等溫線。 (3) 微孔容積（cm3/g) 裝置：Quantachrome 製之 Autosorb-l MP 測定方法：將試料導入20 mg程度測定單元中，482K 下真空加熱處理後，77K下以純度99·99995%以上之純氮 氣體作爲試驗氣體，以容量法測定，再以DR法算出。 測定條件：4 8 2 Κ下真空加熱處理後，測定7 7 Κ下之 氮吸附等溫線。 (4) 藉由拉曼分光測定之D頻帶與G頻帶之強度比（ Id/Ig ) 裝置：普卡歐公司製之RFS100 測定方法：傅里叶變換方式Raman分光法。將試料載 置於玻璃載片上，以目視確認試料位置的同時照射雷射光 進行測定。 測定條件：使用激勵波長7 8 5 nm之半導體雷射光， 以電子冷卻方式之InGaA.s檢驗器測定. 201130737 (5 )尺寸計測（CNH之長、徑、細孔徑等） 裝置：日本電子（股）製之】EM-201〇 測定方法：以微量樣品管取少量試料後，加入乙醯藉 由照射超音波使其分散。將數滴分散液滴在銅製之TEM 用微柵極上，其後充分乾燥。將載置試料之柵極裝置於 TEM本體後，拍攝高分解像，估算數據畫像上之長度、徑 、細孔徑。 測定條件：加速電壓200 kV。利用藉由液體氮冷卻之 防污裝置，以2Kx2K畫素之CCD相機拍攝至40萬倍之高 分解能TEM像。 (6 ) CNH之質量變化 裝置：里佳庫（股）製之耐氟雰圍方式差示熱天秤 TG-DTA 8 120 測定方法：將約1 .5 m g之試料塡入蒙乃爾製試料容 器中，利用差動型差示熱天秤以一定溫度、一定時間測定 起因於儲存氟氣體之質量增加率。氟儲存測定後於純氮氣 體雰圍中將試料溫度降溫至室溫。其次於氮氣流中乃至減 壓下利用差動型差示熱天秤以一定時間測定起因於儲存氟 之試料CNH ( F_CNH )放出氟氣體之質量減少率。以高純 度氟氣體（關東化學工業（股）製純度99.5% )流量〇.2 ml/min、TG-DTA裝置保護用之隔絕氣體流量1〇〇 ml/min 之條件測定。質量變化測定敏感度± 1 . 5 1 μ8以內。 -19- 201130737 (7) 放出氣體中之氟氣體（F2)濃度 將放出氣體導入具有氟化鋇單結晶製之窗的氣體單元 (直徑1 5mm、長80mm、內容積1 _8ml )中，以紫外可視 分光光度計（UV 1600型，島津製作所（股）製）同時解 析歸屬於波長283 nm之氟氣體之吸收光譜與先前準備之 檢量線，使發生之氟氣體量定量》 (8) 放出氣體之定量分析 直接將發生氣體導入傅叶里變換式紅外分光光度計（ IG-10 〇〇型，大塚電子公司製）中，定性定量分析氟氣體 以外之成份。又，數mg之實驗中，藉由差示熱天秤-光 離子化質量分析同時測定系統（Thermo Mass Photo型， 里佳庫公司製），定量質量變化的同時定量氟氣體及不純 物氣體。 參考例1 (藉由氧開孔處理製造h-CNH ) 碳奈米角（s-CNH )爲，僅由以雷射脫離法合成之角 長10至20 nm、角端徑2至3 nm之碳原子構成，形成具 有角爲50至100 nm之大理花般形狀之二次粒子的奈米碳 材料，又使用純度90質量％以上之物（日本電氣（股）製 )。 該原料s-CNH之細孔容積0.80 cm3/g，BET比表面積 爲455 m2/g，微孔容積0.18 cm3/g，拉曼分光測定所得之 D頻帶與G頻帶之強度比（ID/IG)爲1.88。 -20- 201130737 使用純度99.9 %以上之純氧，以62 6K以上、10分鐘 以上之條件對該s-CNH進行開孔處理，製造h-CNH。 所得之h-CNH之細孔容積爲1.32 cm3/g，BET比表面 積爲1041 m2/g，微孔容積爲0.36 cm3/g，拉曼分光測定 所得之D頻帶與G頻帶之強度比（ID/IG )爲2.41。 參考例2 (製造F-h-CNH-200) 將參考例1製造之h-CNH約50 mg載置於鎳製之皿 上，封入蒙乃爾製反應容器（內容積360 cm3)中，首先 經由液體氮凝汽閥以接連之油回轉式真空啷筒將反應器內 部減壓至0.5 kPa後，加熱至20CTC。將反應器內溫安定 保持於200°C下以流速20 ml/min使氟氣體（純度99_5質 量％以上，關東電化工業（股）製）流通1 80分鐘進行氟 化（爲了保護TG-DTA測定裝置以100 ml/min使氮氣體流 通作爲隔絕氣體）。其間以TG-DTA測定裝置監控起因於 氟化之h-CNH之質量增加。結束反應後放冷至35°C以下 再以流速1 00 ml/min以下使高純度氬氣體流通。充分取代 殘存於反應器內部之氟氣體後，於氬雰圍之乾燥箱內解放 反應器，得質量約100 mg之F-h-CNH-200。 相對於氟化反應時間之質量增加之曲線如圖1所示。 所得之F-h-CNH-200藉由反應前後之質量變化求取之 F / C如表1所示。 參考例3 (製造F-h-CNH-100) -21 - 201130737 參考例2中除了氟化反應溫度爲1 〇〇°C外其他相同， 得質量約 78 mg 之 F-h-CNH-100。 相對於氟化反應時間之質量增加之曲線如圖1所示。 所得之F-h-CNH-100藉由反應前後之質量變化求取的 F/C如表1所示。 參考例4 (製造F-h-CNH-RT) 參考例2中除了氟化反應溫度爲室溫（約25 °C)外其 他相同，得質量約73 mg之F-h-CNH-RT。 相對於氟化反應時間之質量增加之曲線如圖1所示。 所得之F-h-CNH-RT藉由反應前後之質量變化求取的 F/C如表1所示。 參考例5 (製造F-s-CNH-200) 參考例2 (氟化反應溫度：200 °C )中，除了氟化 CNH使用未開孔處理之S-CNH外其他相同，得質量約90 mg 之 F-s-CNH-200。 相對於氟化反應時間之質量增加之曲線如圖1所示。 所得之F-s-CNH-200藉由反應前後之質量變化求取的 F/C如表1所示。 參考例6 (製造F-s-CNH-100 ) 參考例3 (氟化反應溫度：100 °c )中’除了氟化 CNH使用未開孔處理之S-CNH外其他相同，得質量約6 1 -22- 201130737 mg 之 F-s-CNH-1 00。 相對於氟化反應時間之質量增加之曲線如圖1所示。 所得之F-S-CNH-100藉由反應前後之質量變化求取的 F/C如表1所示。 參考例7 (製造F-s-CNH-RT) 參考例4 (氟化反應溫度：室溫）中，除了氟化CN Η 使用未開孔處理之s-CNH外其他相同，得質量約60 mg之 F-s-CNH-RT。 相對於氟化反應時間之質量增加之曲線如圖1所示。 所得之F-S-CNH-RT藉由反應前後之質量變化求取的 F / C如表1所示。 表1 氟化處理溫度 oc) F/C s-CNH — — h-CNH — — F-h-CNH-200 200 0.53 F-h-CNH-lOO 100 0.35 F-h-CNH-RT 室溫 0.29 F-s-CNH-200 200 0.5 F—s—CNH—100 100 0.14 F-s-CNH-RT 室溫 0.13When Id/1 (3 is in the range of 1.8 to 2.6, the purity of fluorine gas can be released without loss, and the adsorption capacity of fluorine can be increased under the cycle characteristics of fluorine adsorption and release. The better Id/Ig is 2.1 to 2.6. Raman spectrometry As will be described later, the fluorination of h-CNH can be, for example, a record of the establishment of a research institute for the industry. Vol_25 Νο·3 (Tongfu 99) September 2005, p 06 to ρ η; Journal of Physical Chemistry Β,1〇8 (28), 96 1 4-96 1 8 (2004); or the 32nd Carbon Materials Institute, the publication of the December 7, 2005 issue, p 132 to 133. That is, h-CNH is encapsulated in a reactor made of a material having corrosion resistance of nickel, a nickel-containing alloy, black lead, or the like, for example, a fluorine gas is introduced, and a fluorine gas is introduced to fluorinate. It can be selected from the range of 0.002 to 1.0 MPa, more preferably from 0.005 to 0.5 MPa, considering productivity, economy, and safety, but when it is too low, the fluorination rate is slowed down, and when it is too high, a large reaction device is required. The purity of the fluorination gas is preferably higher, and the fluorine concentration may be 1.0% by mass. The above is diluted with 99% by mass or less of nitrogen, argon or ammonia. Preferably, the fluorine concentration is 1% by mass or more, more preferably 1% by mass or more, particularly preferably 99% by mass or more. Further, it may contain tetrafluoroethane. Fluorinated hydrocarbons such as alkane and hexafluoroethane, or inorganic fluorides such as hydrogen fluoride, nitrogen trifluoride, and iodine pentafluoride, or fluorination of oxygen, water vapor, etc., can be batched in a reactor having a sufficient volume. The semi-batch type, which is carried out at the same time as the fluorine gas is appropriately replaced, can be carried out in a flow-through manner. Further, when the fluorination of h-CNH is performed in a large amount, in order to homogenize the reaction, it is preferred to equip the reactor with appropriate stirring. The stirring mechanism used may be a method of stirring by a variety of stirring blades, a mechanical rotation or a vibration reactor, a method of flowing a powder layer of h-CNH by gas circulation, etc., but excessive stirring may cause damage. The structure of -CNH should be noted. The fluorination reaction temperature can be selected from -100 °C to 500 °C, and the productivity, economy and stability are selected, preferably from room temperature (25 ° C) to 350 ° C. Particularly preferred is room temperature to 150 ° C. The reaction temperature is too It will slow down the rate of fluorination, and it will contain insufficient fluorine storage. If it is too high, the decomposition reaction of h-CNH will increase, and it will be difficult to release the stored fluorine. Reaction -12- 201130737 Time depends on The reaction mode and the reaction conditions are preferably set within a range of from 10 seconds to 1 hour without particular limitation. When it is too short, it is difficult to sufficiently perform fluorination, and it tends to lower the utilization efficiency of h - C Ν ,, and is too long except In addition to facilitating the decomposition reaction, it takes a long time to reduce the industrial production efficiency. Moreover, the open-cell carbon nano-angle (h-CNH) can be fluorinated in a shorter period of time than the carbon nano-angle (s-CNH) without opening treatment (fluorine occlusion) (refer to Figure 1) ° Fluorine storage ( The amount of fluorine can be adjusted by the fluorine gas pressure, the reaction temperature, the reaction time, the addition gas, etc., so that the fluorine atom and the carbon atom composition ratio F/C is in the range of 0.1 to 1.5 (the fluorine content per unit mass of Fh-CNH per unit mass) Equivalent to 13.7 to 70.4% by mass), more preferably 〇·5 to 1.5 (fluorine content equivalent to 44.2 to 70.4% by mass), particularly preferably 1.0 to 1.5 (fluorine content equivalent to 61.2 to 70.4% by mass) Selected. For example, increasing the fluorine gas pressure and the reaction temperature, and elongating the reaction time can increase the fluorine storage amount (fluorination amount). The composition ratio of the fluorine atom to the carbon atom of the carbon fluoride nano-angle (Fs-CNH) which is not subjected to the opening treatment. /C is relatively low in the range of 0.1 to 〇6 (the fluorine content is equivalent to 13.7 to 48.7 mass% in terms of Fh-CNH per unit mass). The F-h-CNH thus obtained is such that the carbon atom constituting the carbon nanohorn forms a co-bond or a semi-ionic bond with the fluorine atom, and has stability at normal temperature and pressure, and contains a trace amount of fluorine gas as a stable substance. The fluorine storage device of the present invention is a device containing the F-h-CNH as a fluorine storage material. -13- 201130737 The fluorine storage device of the present invention can store a large amount of fluorine gas, and can safely and efficiently extract high-purity fluorine gas, thereby having a high utilization possibility for various industries requiring fluorine gas. It can be used for precise synthesis reactions such as various steps of semiconductor use using fluorine gas and pharmaceutical intermediates. The specific device is, for example, a movable storage container such as a fluorine storage cartridge or a fluorine storage cartridge, but is not limited thereto. Further, a metal reactor such as nickel, copper, brass, monel or stainless steel can be used as a storage container. The method for injecting the Fh-CNH into the device of the present invention may be a method of immersing the fluorinated Fh-CNH into the storage container outside the device; a method of fluorinating in the device; and separately preparing the fluorine storage device and the fluorine releasing device to be replaced only The method of the storage. In addition, when Fh-CNH is poured into the inside of the storage container, in order to prevent the dust of the Fh-CNH in the container from scattering, and to ensure sufficient charge and discharge speed, it is possible to granulate Fh-CNH in advance or use a roll press. A method of molding into a tablet, or a method of attaching a metal, or a particle, a fiber, a sheet, or a porous body having at least a surface of a metal fluoride, or a method of forming a fluororesin into a film or a filter. Further, in order to increase the efficiency and speed of fluorine emission from the F-h-CNH, a disk or a cylinder in which a large number of F-h-CNHs are accommodated in advance may be provided inside the storage container. The above-exemplified methods are carried out by h-CNH, and the same effect can be obtained by refluorination. Since the bulk density of the manufactured CNN is very low at about g1 g/cm3, it is generally pulverized by an agate mash and then a bulk density of 0.1 g/cm3 or more. The next step. The opening treatment of h-CNH treated with hydrogen peroxide is wet treatment, and therefore it is inevitably supplied in the same form as that after the above-mentioned treatment of -14-201130737. This type of h-CNH allows the mass to be added without changing the volume, so that the bulk density per gram of h-1 g of fluorine is about 0.2 g/cm3. In the method of fluorination in the apparatus, storage (fluorination) and discharge (removal) are easily repeated in one apparatus. Further, the present invention relates to a method of taking out high purity from F-h-CNH. A method of taking out a high-purity fluorine gas from F-h-CNH, such as a method of heating by CNH, a method of placing F-h-CNH in a reduced pressure atmosphere, and a combination thereof. (1) Method of heating F-h-CNH A carbon atom constituting F_h-CNH and a fluorocarbon (defluorination reaction) are cut by heating to release a fluorine gas (F2). The applied heat temperature may be maintained at 100 ° C or more under normal pressure (atmospheric pressure). The fluorine gas is taken out at a temperature higher than the fluorination temperature of h-CNH. The heating temperature varies depending on the fluorination temperature, but is preferably 100%, more preferably 100 to 45 °C. When the heating temperature is too high, the amount of fluorohydrocarbon impurities will increase, which will change the obstacle of repeated use of F-h-CNH. Further, if the heating temperature is too low, the speed is too slow, and when it is used as a device, it is not economical. One of the features of the present invention is that the fluorine gas taken out contains an impurity fluorohydrocarbon gas. Special opening 20 05 -2 73 〇7〇 bulletin stored in the fluorine also a few CNH storage of fluorine gas fluorine gas, the F- h - under the method of the amount of bonding (heating, again, can be more effective to 5 5 F ° -15- 201130737 In the s-CNH, which is thermally decomposed and thermally decomposed, most of the gases taken out by heating are decomposed by CF4, C2F6, etc. However, the concentration of the fluorine gas (F2) in the fluorine gas heated and extracted in the present invention is 99% by mass or more (excluding the atmosphere), preferably 99.5% by mass or more, more preferably 99.9% by mass or more, and particularly preferably 99.99. High-purity fluorine gas of a mass % or more. (2) Method of placing Fh-CNH in a reduced-pressure atmosphere The present invention can also take out a high-purity fluorine gas by placing a carbon fluoride nanohorn under a reduced pressure atmosphere. (Defluorination reaction) When the degree of decompression is close to the vacuum, the fluorine gas can be taken out more efficiently. Specifically, the necessary amount of fluorine, gas pressure, fluorine gas release rate, etc. can be selected, and the above-mentioned defluorination reaction vessel is used. The degree of pressure reduction is generally preferably 100 kPa or less, more preferably 1 pa to 50 kPa. This decompression method does not require heating, so it can not only improve safety and energy efficiency, but also reduce the occurrence of impurities in fluorinated hydrocarbon gas. (3) Heating under reduced pressure atmosphere by depressurizing atmosphere Fh-CNH heating can be more efficient and can suppress the removal of fluorine gas under the impurity-fluorinated hydrocarbon gas. Specifically, the degree of decompression, the necessary fluorine gas pressure, the fluorine gas release rate, etc. can be selected, for example, the decompression atmosphere is When it is 1 Pa to 50 kPa, it can be appropriately selected from the range of the heating temperature of 100 to 550 ° C. The amount of fluorine gas (release ratio) which can be taken out in the present invention is 99 mass of the fluorine storage amount (fluorination amount). -16- 201130737 The maximum difference between the Fh-CN Η after the open-hole treatment of the fluorine storage material of the present invention and the previously unopened Fs-CNH is that the fluorine gas of the Fs-CNH has a higher fluorination temperature. The emission ratio is large, but the fluorine gas having a lower fluorination temperature of Fh-CNH has a larger release ratio (refer to Fig. 2). As described above, the fluorine gas can be taken out at a higher ratio after fluorination at a lower temperature, so Improve thermal efficiency reduction In addition, the cost can be reduced, and the damage to the Fh-CNH can be reduced. Therefore, the present invention can be expected to be described in detail by way of examples and the like, but the present invention is not limited to the embodiment. The measurement methods of various physical properties used in the present invention are as follows: (1) BET specific surface area (m2/g) Device: Autosorb-1 MP manufactured by Quantachrome Method: The sample is introduced into a measuring unit of 20 mg, 4 8 2 K: After vacuum heating treatment, a pure nitrogen gas having a purity of 9 9.9 9 9 9 5 % or more was used as a test gas at 7 7 K, and was measured by a volumetric method, and the measurement data was analyzed by the enthalpy method. Measurement conditions: After vacuum heating treatment at 482 Torr, the gas adsorption isotherm at 77 Torr was measured. (2) Pore volume (c m3 / g ) -17- 201130737 Apparatus · Autosorb-l MP manufactured by Quantachrome Inc. Determination method: The sample was introduced into a measuring unit of 20 mg, and vacuum-heated at 48 2 K, 77 Κ A pure nitrogen gas having a purity of 99.99995% or more was used as a test gas and measured by a volumetric method. Measurement conditions: After vacuum heating treatment at 482 Torr, the nitrogen adsorption isotherm at 77 Torr was measured. (3) Micropore volume (cm3/g) Device: Autosorb-l MP manufactured by Quantachrome. Method: The sample is introduced into a measuring unit of 20 mg. After vacuum heating at 482 K, the purity is 99.99995% at 77K. The pure nitrogen gas was used as a test gas and measured by a volumetric method, and then calculated by the DR method. Measurement conditions: After 4 8 2 under vacuum heating, the nitrogen adsorption isotherm at 7 7 Torr was measured. (4) Intensity ratio of D band to G band measured by Raman spectrometry (Id/Ig) Device: RFS100 manufactured by Pukaco Co., Ltd. Measurement method: Fourier transform method Raman spectrometry. The sample was placed on a glass slide, and the position of the sample was visually confirmed while irradiating the laser light for measurement. Measurement conditions: using semiconductor laser light with an excitation wavelength of 785 nm, measured by an InGaA.s tester with electronic cooling. 201130737 (5) Dimensional measurement (CNH length, diameter, pore size, etc.) Device: Japan Electronics Co., Ltd. Manufacture method: EM-201 〇 measurement method: After taking a small amount of sample with a small sample tube, add acetonitrile to disperse it by irradiating ultrasonic waves. A few drops were dispersed on a microgrid for TEM made of copper, and then dried sufficiently. After the gate device on which the sample is placed is placed on the TEM body, a high-resolution image is taken, and the length, diameter, and pore diameter of the data image are estimated. Measurement conditions: Acceleration voltage 200 kV. Using an anti-fouling device cooled by liquid nitrogen, a CCD camera with a 2Kx2K pixel was used to capture a 400,000-fold high resolution TEM image. (6) CNH quality change device: Fluorine-resistant atmosphere type differential heat balance TG-DTA 8 120 made by Lijiaku (stock). Method: About 1.5 mg of the sample was poured into a Monel sample container, and utilized. The differential type differential heat balance measures the mass increase rate of the stored fluorine gas at a certain temperature and for a certain period of time. After the fluorine storage was measured, the temperature of the sample was lowered to room temperature in a pure nitrogen atmosphere. Next, the mass reduction rate of the fluorine gas emitted from the sample CNH (F_CNH) which is stored in fluorine is measured by a differential type differential heat balance in a nitrogen stream or even under a reduced pressure. It was measured under the conditions of high purity fluorine gas (purity of 99.5% by Kanto Chemical Industry Co., Ltd.) flow rate of 22 ml/min, and isolation gas flow rate of 1 〇〇 ml/min for protection of TG-DTA apparatus. The mass change measurement sensitivity is within ± 1 5 1 μ8. -19- 201130737 (7) The concentration of fluorine gas (F2) in the evolved gas is introduced into the gas unit (diameter 15 mm, length 80 mm, internal volume 1 _8 ml) with a window made of cesium fluoride single crystal, in the form of UV A visible spectrophotometer (UV 1600, manufactured by Shimadzu Corporation) simultaneously analyzes the absorption spectrum of a fluorine gas belonging to a wavelength of 283 nm and a previously prepared calibration curve to quantify the amount of fluorine gas generated. (8) Release gas The quantitative analysis directly introduces a gas into a Fourier transform infrared spectrophotometer (IG-10 〇〇 type, manufactured by Otsuka Electronics Co., Ltd.) to qualitatively and quantitatively analyze components other than fluorine gas. Further, in the experiment of several mg, the differential gas mass-photoionization mass spectrometry simultaneous measurement system (Thermo Mass Photo type, manufactured by Lijiku Co., Ltd.) was used to quantify the fluorine gas and the impurity gas while quantifying the mass change. Reference Example 1 (manufacturing of h-CNH by oxygen opening treatment) The carbon nano angle (s-CNH) is an angular length of 10 to 20 nm and an angular end diameter of 2 to 3 nm synthesized only by laser detachment. A carbon nanoparticle is formed, and a nanocarbon material having a secondary particle having a shape of a marble of 50 to 100 nm is formed, and a substance having a purity of 90% by mass or more (manufactured by Nippon Electric Co., Ltd.) is used. The raw material s-CNH has a pore volume of 0.80 cm3/g, a BET specific surface area of 455 m2/g, a micropore volume of 0.18 cm3/g, and an intensity ratio of the D-band to the G-band obtained by Raman spectrometry (ID/IG). It is 1.88. -20- 201130737 The s-CNH was subjected to a perforation treatment using pure oxygen having a purity of 99.9% or more and a condition of 62 6 K or more and 10 minutes or more to produce h-CNH. The obtained h-CNH has a pore volume of 1.32 cm 3 /g, a BET specific surface area of 1041 m 2 /g, a pore volume of 0.36 cm 3 /g, and an intensity ratio of the D band to the G band obtained by Raman spectrometry (ID/ IG) is 2.41. Reference Example 2 (Production of Fh-CNH-200) About 50 mg of h-CNH manufactured in Reference Example 1 was placed on a nickel dish and sealed in a Monel reaction vessel (volume 360 cm3), first via liquid nitrogen. The steam trap is decompressed to 0.5 kPa inside the reactor with a continuous oil rotary vacuum cylinder and heated to 20 CTC. The internal temperature of the reactor was kept at 200 ° C. The flow rate of 20 ml/min was used to fluorinate the fluorine gas (purity of 99_5 mass% or more, manufactured by Kanto Electrochemical Co., Ltd.) for 180 minutes (to protect TG-DTA). The apparatus circulated the nitrogen gas at 100 ml/min as an insulating gas). During this time, the mass increase due to fluorinated h-CNH was monitored by a TG-DTA measuring device. After the completion of the reaction, the mixture was allowed to cool to 35 ° C or lower, and then a high-purity argon gas was passed at a flow rate of 100 m/min or less. After sufficiently replacing the fluorine gas remaining in the inside of the reactor, the reactor was liberated in a dry box in an argon atmosphere to obtain F-h-CNH-200 having a mass of about 100 mg. The curve of the mass increase relative to the fluorination reaction time is shown in Fig. 1. The obtained F-h-CNH-200 was determined by the mass change before and after the reaction, and F / C is shown in Table 1. Reference Example 3 (Production of F-h-CNH-100) -21 - 201130737 In Reference Example 2, except that the fluorination reaction temperature was 1 〇〇 ° C, a yield of about 78 mg of F-h-CNH-100 was obtained. The curve of the mass increase relative to the fluorination reaction time is shown in Fig. 1. The F/C obtained by the mass change of the obtained F-h-CNH-100 by the reaction before and after the reaction is shown in Table 1. Reference Example 4 (Production of F-h-CNH-RT) Reference Example 2 was obtained in the same manner except that the fluorination reaction temperature was room temperature (about 25 ° C), and a mass of about 73 mg of F-h-CNH-RT was obtained. The curve of the mass increase relative to the fluorination reaction time is shown in Fig. 1. The F/C obtained by the F-h-CNH-RT obtained by the mass change before and after the reaction is shown in Table 1. Reference Example 5 (manufacturing Fs-CNH-200) In Reference Example 2 (fluorination reaction temperature: 200 ° C), except that the fluorinated CNH was the same as the unopened S-CNH, an Fs of about 90 mg was obtained. CNH-200. The curve of the mass increase relative to the fluorination reaction time is shown in Fig. 1. The F/C obtained by the mass change of the obtained F-s-CNH-200 by the reaction before and after the reaction is shown in Table 1. Reference Example 6 (manufacturing Fs-CNH-100) In Reference Example 3 (fluorination reaction temperature: 100 °c), except that the fluorinated CNH was the same as the unopened S-CNH, the mass was about 6 1 -22- 201130737 mg of Fs-CNH-1 00. The curve of the mass increase relative to the fluorination reaction time is shown in Fig. 1. The F/C obtained by the mass change of the obtained F-S-CNH-100 by the reaction before and after the reaction is shown in Table 1. Reference Example 7 (manufacturing Fs-CNH-RT) In Reference Example 4 (fluorination reaction temperature: room temperature), except that the fluorinated CN Η was the same as the s-CNH which was not treated with an open pore, a Fs having a mass of about 60 mg was obtained. CNH-RT. The curve of the mass increase relative to the fluorination reaction time is shown in Fig. 1. The F/C obtained by the F-S-CNH-RT obtained by the mass change before and after the reaction is shown in Table 1. Table 1 Fluorination treatment temperature oc) F/C s-CNH — — h-CNH — — Fh-CNH-200 200 0.53 Fh-CNH-lOO 100 0.35 Fh-CNH-RT Room temperature 0.29 Fs-CNH-200 200 0.5 F-s-CNH-100 100 0.14 Fs-CNH-RT Room temperature 0.13
$表1及圖1得知，氟吸存量強勢依存於吸存溫度。 s-CNH於l〇〇°C以下之低溫的吸存量非常小（F/C<0.2 )。 h-CNH既使於loot#下也可吸存F/c = 0.3至0.4。h-CNH -23- 201130737 於200°C之吸存量非常大，CNH每單位質量可吸存100% 以上。s-CNH既使於200°C，也傾向得到與理論化學量論 (F/C = 0.5 )同程度以上之吸存量，故暗示氟吸存過程中 將C N Η開孔，角內空間可利用於吸存。 實施例1 將參考例2至7各自製造之氟化碳奈米角（F-h-CNH 及F-s-CNH) 63 mg封入，預先於420°C下封入氟氣體24 小時經不動體化處理之內容積約3 00 ml之蒙乃爾製反應 器之內部後，經由液體氮凝汽閥以接連之油回轉式真空啷 筒將反應器內部減壓至0.5 kPa，再放置12小時》 其後以流速300 ml/min流通氦氣體的同時以5°/min 之升溫速度將反應器由室溫（約25 °C )加熱至400 °C後， 40 0°C下再放置300分鐘放出氟氣體（雰圍壓力爲大氣壓 )°$Table 1 and Figure 1 show that the amount of fluorine absorption depends on the storage temperature. The absorption of s-CNH at a low temperature below l ° ° C is very small (F/C < 0.2 ). h-CNH can also store F/c = 0.3 to 0.4 even under loot#. h-CNH -23- 201130737 The absorption capacity at 200 °C is very large, and CNH can absorb more than 100% per unit mass. s-CNH tends to obtain the same amount of absorption as the theoretical stoichiometry (F/C = 0.5) at 200 °C, suggesting that CN Η is opened during the fluoridation process, and the intraangular space is available. Suction. Example 1 63 mg of carbon fluoride nanohorns (Fh-CNH and Fs-CNH) manufactured in Reference Examples 2 to 7 were sealed, and the inner volume of the fluorine gas was sealed in 420 ° C for 24 hours. After the inside of the reactor of about 300 ml Monel, the inside of the reactor was depressurized to 0.5 kPa by a liquid nitrogen steam trap with a continuous oil rotary vacuum cylinder, and then placed for 12 hours, followed by a flow rate of 300 ml. /min flows the gas at a temperature of 5 ° / min while heating the reactor from room temperature (about 25 ° C) to 400 ° C, then placed at 40 ° C for 300 minutes to release fluorine gas (atmospheric pressure is Atmospheric pressure)°
相對於加熱時間（ 300分鐘）之F-h-CNH或F-s-CNH 之質量減少的經時變化如圖2所示。 由圖2得知下述事項。 (1 )吸存溫度至1 00°C之試料，無關非開孔、開孔及 放出條件，幾乎可放出90至100 %之吸存量。 (2) 2 00 °C吸存試料之放出率爲60至80%，可若干 提升s-CNH之放出水準。又反映出h_CNH之吸存量比s-CNH多，可期待提升400分鐘以上之長時間放出時h-CNH 之放出率。 -24- 201130737 (3 )放出率到達1 〇 0 %所放出之氣體會含有少量 COF2、C02、HF。 放出之氟爲高純度氟（純度99 ν〇ι%以上）。 又，藉由透過型電子顯微鏡確認’反應前之h-CNH、 F-h-CNH及氟氣體放出後之h-CNH中任何形狀均無變化， 爲耐重覆儲存氟之物。 實施例2 將參考例2至7各自製造之氟化碳奈米角（F-h-CNH-200、F-h-CNH-100、F-h-CNH-RT、F-s-CNH-200、F-S-CNH-100 及 F-s-CNH-RT) 63 mg 封入，預先於 420°C 下封 入氟氣體24小時經不動體化處理的內容積約300 ml之蒙 乃爾製反應器之內部後，經由液體氮凝汽閥以接連之油回 轉式真空唧筒將反應器內部減壓至1 〇 p a，再放置1 2小時 〇 其後以5°C /min之升溫速度將反應器由室溫（25°C ) 加熱至400°C後，400t下再放置300分鐘放出氟氣體（雰 圍壓力爲1〇 PO 。 相對於加熱時間（ 300分鐘）之F-h-CNH及F-s-CNH 之質量減少的經時變化如圖3所示，藉由反應前後之質量 變化求取之F/C如表2所示。The change with time of mass reduction of F-h-CNH or F-s-CNH relative to the heating time (300 minutes) is shown in FIG. The following matters are known from Fig. 2. (1) Samples with a temperature of up to 100 °C, irrespective of non-opening, opening and releasing conditions, can release almost 90 to 100% of the stored amount. (2) The release rate of the sample stored at 2 00 °C is 60 to 80%, which can improve the discharge level of s-CNH. It is also reflected that h_CNH has more storage than s-CNH, and it can be expected to increase the release rate of h-CNH when it is released for a long time of 400 minutes or more. -24- 201130737 (3) The release rate reaches 1 〇 0% and the released gas will contain a small amount of COF2, CO2, HF. The fluorine released is high-purity fluorine (purity of 99 ν〇ι% or more). Further, it was confirmed by a transmission electron microscope that the h-CNH, the F-h-CNH, and the h-CNH after the release of the fluorine gas before the reaction did not change in any shape, and it was resistant to repeated storage of fluorine. Example 2 The carbon fluoride nanohorns prepared by reference examples 2 to 7 (Fh-CNH-200, Fh-CNH-100, Fh-CNH-RT, Fs-CNH-200, FS-CNH-100, and Fs) -CNH-RT) 63 mg was sealed, and the fluorine gas was sealed in 420 ° C for 24 hours. After the internal volume of the reactor was about 300 ml, the internal pressure of the reactor was passed through a liquid nitrogen trap. The oil rotary vacuum cylinder depressurizes the inside of the reactor to 1 〇pa, and then holds it for 12 hours, then heats the reactor from room temperature (25 ° C) to 400 ° C at a temperature increase rate of 5 ° C /min. At 400t, it is left for another 300 minutes to release fluorine gas (the atmospheric pressure is 1〇PO. The change with time of mass reduction of Fh-CNH and Fs-CNH relative to the heating time (300 minutes) is shown in Figure 3, by reaction The F/C of the mass change before and after is shown in Table 2.
S -25- 201130737 表2 氟化處理溫度 (X) F/C F-h-CNH-200 200 0.66 F~h-CNH-100 100 0.41 F~h-CNH-RT 室溫 0.35 F-s-CNH-200 200 0.52 F-s-CNH-100 100 0.19 F-s-CNH-RT 室溫 0.15 由表2及圖3得知，以i 〇crC以下之低溫吸存氟時， F-h-CNH之質量減少率可大幅超出s-CNH之質量減少率。 2〇〇°C吸存試料中F-h-CNH與F-s-CNH之質量減少率爲相 同程度。任何一種之放出率均無法大幅超出1 0 0 %，故暗 示會抑制吸存氟之CNH骨架之熱分解。放出氣體含有極 微量之C02、HF、COF2，爲高純度氟（99vol%以上）。 又’藉由透過型電子顯微鏡確認，反應前之h-CNH、 F-h-CNH及氟氣體放出後之h-CNH中任何無狀均無變化， 爲耐重覆氟儲存之物。 參考例8 (過氧化氫開孔處理） 碳奈米角（s-CNH )爲，使用參考例1所使用之純度 90質量％以上之物（日本電氣（股）製）（細孔容積： 0.8 0 cm3/g，BET 比表面積：45 5 m2/g，微孔容積：0.18 cm3/g，拉曼分光測定所得之D頻帶與G頻帶之強度比（ Id/Ig ) : 1.88)。 以少量乙醇濕潤該s-CNH後投入25°C之過氧化氫水 -26- 201130737 中，結束發泡後以磁力攪拌器攪拌2小時進行開孔處理’ 過濾乾燥後以瑪瑙製乳鉢粉碎，製造h-CNH。 測定所得之h-CNH之BET比表面積 '微孔容積。 BET比表面積爲1462 m2/g，微孔容積爲〇.39cm3/g。 參考例9至10 除了使用參考例8所製造之h-CNH外同參考例2至4 以 200°C、50°C 氟化各自得 F-h-CNH-200、F-h-CNH-50。 F/C 之値（質量變化），F-h-CNH-200 爲 0.58 ’ F-h-CNH-5 0 爲（K2 8。 實施例3 除了使用參考例9至10所製造之F-h-CNH外同實施 例1於大氣壓下放出氟氣體。 加熱時間（3 00分鐘）之質量減少量，F-h-CNH-200 爲1 9.2質量％，F-h-CNH-50爲34.4質量％。此等之値相 對於單位質量之h-CNH之氟吸附量，各自相當於41%、 1〇〇%° 由該結果得知，藉由使用以過氧化氫處理碳奈米角所 得之開孔碳奈米角可實現’特別是以5 0 °C般較低之溫度進 行吸脫操作時，每單位質量之h_CN H之氟儲存量雖較少 ，但不會殘存吸附之氟均可放出之更高效率的氟儲存裝置 〇 又，調查各自由F_h-CN Η放出之氣體之氟氣體濃度及 -27- 201130737 氣體組成，結果除了確認二氧化碳外，還可以雜音程度之 微量確認四氟化碳、氟化氫，但可得至少99%以上之純度 之氟氣體。 如上述藉由使用以過氧化氫處理碳奈米角所得之開孔 碳奈米角經氟化所得之氟化開孔碳奈米角，可實現更高效 率之氟儲存裝置。 又，藉由透過型電子顯微鏡確認，反應前之h-CNH、 F-h-CNH及氟氣體放出後之h-CNH中任何形狀均無變化， 爲耐重覆氟儲存之物。 【圖式簡單說明】 圖1爲，參考例2至7所測定之氟化處理之重量增加 曲線圖。 圖2爲，實施例1所測定之氟放出處理之重量減少曲 線圖。 圖3爲’實施例2所測定之氟放出處理之重量減少曲 線圖。 -28-S -25- 201130737 Table 2 Fluorination treatment temperature (X) F/C Fh-CNH-200 200 0.66 F~h-CNH-100 100 0.41 F~h-CNH-RT Room temperature 0.35 Fs-CNH-200 200 0.52 Fs-CNH-100 100 0.19 Fs-CNH-RT Room temperature 0.15 It is known from Table 2 and Figure 3 that the mass reduction rate of Fh-CNH can greatly exceed the s-CNH when the fluorine is stored at a low temperature below i 〇crC. Quality reduction rate. The mass reduction rate of F-h-CNH and F-s-CNH in the 2〇〇°C storage sample was the same. The release rate of any one of them cannot be significantly exceeded by 100%, so it is indicated that the thermal decomposition of the CNH skeleton which absorbs fluorine is suppressed. The evolved gas contains a very small amount of CO 2 , HF, and COF 2 and is a high-purity fluorine (99 vol% or more). Further, it was confirmed by transmission electron microscopy that h-CNH, F-h-CNH, and any of the h-CNH after the release of the fluorine gas before the reaction did not change, and it was a product resistant to heavy fluorine storage. Reference Example 8 (Hydrogen peroxide opening treatment) The carbon nano angle (s-CNH) was obtained by using the purity of 90% by mass or more (manufactured by Nippon Electric Co., Ltd.) used in Reference Example 1 (fine pore volume: 0.8) 0 cm3/g, BET specific surface area: 45 5 m2/g, micropore volume: 0.18 cm3/g, intensity ratio of D-band to G-band obtained by Raman spectrometry (Id/Ig): 1.88). The s-CNH was wetted with a small amount of ethanol, and then poured into hydrogen peroxide water at 26 ° C to -26-201130737. After the foaming was completed, the mixture was stirred for 2 hours with a magnetic stirrer for the opening treatment. After filtration and drying, it was pulverized with an agate mortar. h-CNH. The BET specific surface area of the obtained h-CNH was measured as 'micropore volume. The BET specific surface area was 1462 m 2 /g, and the micropore volume was 〇.39 cm 3 /g. Reference Examples 9 to 10 F-h-CNH-200, F-h-CNH-50 were obtained by fluorinating at respective temperatures of 200 ° C and 50 ° C except that h-CNH manufactured in Reference Example 8 was used. F/C (mass change), Fh-CNH-200 is 0.58 'Fh-CNH-5 0 is (K2 8. Example 3 except that Fh-CNH manufactured by Reference Examples 9 to 10 is used. Fluorine gas is evolved at atmospheric pressure. The mass reduction of heating time (300 minutes) is 15.2% by mass for Fh-CNH-200 and 34.4% by mass for Fh-CNH-50. The amount of fluorine adsorbed by -CNH is equivalent to 41% and 1% by weight. From the results, it can be understood that the use of the open-celled carbon nano angle obtained by treating the carbon nanohorn with hydrogen peroxide can be achieved. When the suction operation is performed at a temperature lower than 50 °C, the fluorine storage per unit mass of h_CN H is small, but there is no more efficient fluorine storage device that can be released from the adsorbed fluorine. Investigate the concentration of fluorine gas in the gas emitted by F_h-CN and the composition of gas from -27 to 201130737. In addition to confirming carbon dioxide, carbon tetrafluoride and hydrogen fluoride can be confirmed in a small amount of noise, but at least 99% can be obtained. Fluorine gas of purity. The above is obtained by treating carbon nanohorn with hydrogen peroxide as described above. The fluorinated open-cell carbon nanohorn obtained by fluorination of the open-cell carbon nano-angle can realize a higher efficiency fluorine storage device. Further, it is confirmed by transmission electron microscopy that h-CNH and Fh-CNH before the reaction. And any shape of h-CNH after the release of fluorine gas is unchanged, and is a material resistant to heavy fluoride storage. [Simplified Schematic] FIG. 1 is a graph showing the weight increase of the fluorination treatment measured in Reference Examples 2 to 7. Fig. 2 is a graph showing the weight reduction of the fluorine release treatment measured in Example 1. Fig. 3 is a graph showing the weight reduction of the fluorine release treatment measured in Example 2.