201236039 六、發明說明： 【發明所屬之技術領域】 本發明關於活性碳粉末與其製造方法。本發明亦關於 使用該活性碳粉末於電極活性物質的雙電層電容器。 【先前技術】 活性碳係廣泛使用於各種工業領域，以空氣淨化、放 射性物質吸附、碘捕捉、甲烷吸留、氫吸留、淨水製造、 溶劑回收、脫色、水處理、防毒面具的用途等爲目的而利 用。又，近年來，亦使用作爲電容器（雙電層電容器、鋰 離子電容器）的電極活性物質，迫切要求其高機能化。 雙電層電容器係利用電極與電解液之間的界面所形成 的雙電層之能量儲存裝置。作爲此雙電層電容器所用的電 極活性物質之活性碳，較佳爲比表面積大者，因爲與電解 液之間的界面變廣，靜電容量變大。因此，於雙電層電容 器的電極活性物質中，利用比表面積大的活性碳。活性碳 一般大致區分爲由纖維狀的活性碳粒子所成之活性碳纖維 與由非纖維狀（粒狀）的活性碳粒子所成之活性碳粉末。 非專利文獻1中記載關於雙電層電容器用的活性碳， 爲了形成在低溫與室溫下相同的雙電層容量，需要2nm以 上的細孔（P. 80)。又，於非專利文獻1的ρ· 79之表7中 ，記載比表面積爲〜25 00m2/g，平均細孔徑爲20〜40 A (2 〜4nm)，累計細孔容積爲0.5〜1.5c c/g的酚系活性碳纖維 。惟，此非專利文獻1中所記載的酚系活性碳纖維，係將 -5- 201236039 特殊的酚樹脂纖維（酚醛（no voloid)纖維）碳化活化而得之活 性碳纖維（P. 73-75)。於此非專利文獻1中，作爲酚系以 外的活性碳纖維，亦記載以縲縈（纖維素）纖維爲原料的縲 縈系與以聚丙烯腈纖維爲原料的丙烯酸系活性碳纖維，於 縲縈系的活性碳纖維中，比表面積係小到1 000〜1 5 00m2/g ，平均細孔徑亦小到14A(1.4nm)。又，即使於丙烯酸系的 活性碳纖維中，比表面積也小到700〜1 200m2/g，平均細 孔徑亦小到l〇A(1.0nm)，更且累計細孔容積爲〜l.lcc/g 〇 專利文獻1中記載作爲雙電層電容器用的活性碳粉末 ，磷原子含量爲1 000〜20000ppm，BET比表面積爲1600 〜22 00m2/g，平均細孔徑在1.7〜2.1nm的範圍，細孔直徑 在1.4〜2·0ηιη之間的細孔容積爲〇.25cm3/g以上之磷化合 物複合活性碳粉末。惟，記載細孔容積的上限較佳爲0.5 cm3/g以下（[00 3 2])。又，此專利文獻1中記載作爲上述活 性碳粉末之製造方法，在130〜170°C將活性碳原料與磷酸 混煉後進行成型，使其經過在100〜23 0°C加熱的第1加熱 步驟與在400〜600°C加熱的第2加熱步驟後，於惰性氣體 環境下以800°C以上煅燒而將活性碳與磷化合物複合化之 方法。作爲活性碳原料之例，可舉出硬木、軟木及彼等的 層、玉米的穗、咖啡豆、米的稻殼、果實之種子、果實的 殼等植物或糖蜜或木質素等的殘骸或煤、焦油、瀝青、柏 油、石油殘留物。 另一方面，專利文獻2中記載作爲活性碳粉末之製造 -6- 201236039 方法，將醋酸纖維素（醯化纖維素）碳化而生成碳化物，將 所得之碳化物活化之方法，但關於所得之活性碳粉末，沒 有記載其比表面積、平均細孔直徑及細孔容積。惟，專利 文獻2的實施例所得之活性碳粉末，係碘吸附量爲1144 mg/g左右，推測比表面積不太高。 先前技術文獻 專利文獻 專利文獻1 :特開2008-21966號公報 專利文獻2 :特開2008-20 1 664號公報 非專利文獻 非專利文獻1:西野敦、直井勝彥，「電化學電容器 的開發與應用」，CMC技術叢書173，CMC出版，2004 年6月26日發行，P. 73-80 【發明內容】 發明所欲解決的問題 非專利文獻1中記載的酚系活性碳纖維，係比表面積 、平均細孔徑及細孔容積皆大，判斷係適用作爲雙電層電 容器用的電極活性物質之材料的一個。然而，非專利文獻 1中記載的酚系活性碳纖維，係使用特殊酚樹脂纖維的酚 醛纖維作爲原料，通用性低，在生產成本有問題。又，與 非纖維狀的活性碳粒子比較下，纖維狀的活性碳粒子由於 在成形爲電極時，容易在粒子間形成間隙，故與活性碳粉 末比較下’活性碳纖維係塡充密度容易變低。另一方面， 201236039 關於專利文獻1中記載的活性碳粉末，比表面積 孔直徑及細孔容積的各特性係劣於上述非專利文 載的酚系活性碳纖維。 因此，本發明之目的在於提供比表面積、平 徑及細孔容積的各特性係與以往的酚系活性碳纖 比其優異，可有利地使用作爲雙電層電容器的電 質之活性碳粉末及其製造方法。本發明之目的亦 電容量大的雙電層電容器。 解決問題的手段 本發明者發現藉由使用一種方法，其包含： 維素加熱以使其碳化之碳化步驟，將碳化步驟所 物，以比在碳化步驟中使醋酸纖維素碳化時的 5 0 °C以上的溫度進行加熱，使殘留在碳化物的醋 發而去除之醋酸去除步驟，以及將經醋酸去除步 酸的碳化物活化處理之活化步驟，可得到B E T比 1 600〜3000m2/g的範圍，平均細孔直徑在2.0〜 範圍，而且細孔的全容積在1·〇〜3.0cm3/g的範 碳粉末。而且，該活性碳粉末在作爲雙電層電容 活性物質使用時，確認顯示高的靜電容量，而完 〇 因此，本發明係在於活性碳粉末，其B E T比 1600〜3000m2/g的範圍，平均細孔直徑在2.0〜 fe圍’而且細孔的全容積在1.0〜3.0cm3/g的範圍 、平均細 獻1中記 均細孔直 維同等或 極活性物 在於提供 將醋酸纖 得之碳化 溫度還高 酸成分揮 驟去除醋 表面積在 4 . Onm 的 圍之活性 器的電極 成本發明 表面積在 4.0nm 的 -8 - 201236039 上述本發明的活性碳粉末之較佳態樣係如以下。 (1) BET比表面積在2100〜3 000m2/g的範圍，尤其在2600 〜3000m2/g的範圍。 (2) 平均細孔直徑在2.2〜2.8nm的範圍》 (3) 細孔的全容積在1.1〜2.5cm3/g的範圍。 (4) 平均縱橫比爲5以下，更佳爲3以下，特佳爲2以下。 (5) 平均粒徑在1〜30μηι的範圍。 (6) 雙電層電容器用。 本發明亦在於雙電層電容器，其係由正極、負極與電 解液所組成的雙電層電容器，其中正極及負極中的至少一 者含有上述本發明的活性碳粉末。 本發明亦更在於上述本發明的活性碳粉末之製造方法 ，其包含：將醋酸纖維素加熱以使其碳化之碳化步驟，將 碳化步驟所得之碳化物，以比在碳化步驟中使醋酸纖維素 碳化時的溫度還高50°C以上的溫度進行加熱，使殘留在碳 化物的醋酸成分揮發而去除之醋酸去除步驟，而且將經醋 酸去除步驟去除醋酸的碳化物活化處理之活化步驟。 上述本發明的活性碳粉末之製造方法的較佳態樣係如 以下。 (1) 於碳化步驟中，在磷化合物的存在下加熱醋酸纖維素而 使其碳化。 (2) 醋酸纖維素係含有磷化合物的醋酸纖維素。 (3) 醋酸纖維素含有以磷量計爲0.1〜5.0質量％的範圍之磷 化合物。 201236039 (4) 醋酸纖維素係實質上不含有磷化合物的醋酸纖維素與含 有磷化合物的醋酸纖維素之混合物。 (5) 將醋酸纖維素與磷化合物的混合物加熱，而使醋酸纖維 素碳化。 (6) 於碳化步驟中，在惰性氣體環境下以250〜350t的溫 度加熱醋酸纖維素而使其碳化。 (7) 於醋酸去除步驟中，在惰性氣體環境下以3 80〜700 °C 的溫度加熱碳化物。 (8) 於活化步驟中，在選自由二氧化碳氣體、水蒸氣、氧氣 、氯化氫氣體、氨氣及空氣所成之群組中的氣體環境下， 以8 00〜1 100°c的溫度加熱碳化物。 [發明的效果] 本發明的活性碳粉末係在與雙電層電容器的電解液之 接觸下顯示高的靜電容量。又，本發明的活性碳粉末係非 纖維狀，與活性碳纖維比較下，由於粒子形狀或粒子大小 均勻，故可提高塡充密度。因此，使用本發明的活性碳粉 末當作電極活性物質的雙電層電容器，係顯示高的電容量 。又，迫切希望雙電層電容器用的電極活性物質係低成本 化，亦從此點來看，可以醋酸纖維素當作原料而製造的本 發明的活性碳粉末係比活性碳纖維有利。本發明的活性碳 粉末，由於具有大的BET比表面積，故亦可有利地使用作 爲氣相吸附用、氣體儲藏用、淨水用或脫色用的活性碳粉 末0 -10- 201236039 又，藉由利用本發明的製造方法，通常於原料中 廢棄的醋酸纖維素，具有可工業上有利地製造高性能 性碳粉末之優點。 【實施方式】 [實施發明的形態] 本發明的活性碳粉末係由微小的活性碳粒子所構 活性碳粒子係非纖維狀，平均縱橫比（活性碳粒子的 與短徑之比：長徑/短徑）一般爲5以下，較佳爲3以 特佳爲2以下。 本發明的活性碳粉末係BET比表面積在1 600〜 m2/g的範圍，較佳爲在2 100〜3000m2/g的範圍，更 2300〜3000m2/g的範圍，特佳在2600〜3000m2/g的 。於雙電層電容器的電極活性物質使用活性碳粉末時 於在活性碳粉末與電解液之間的界面形成雙電層，活 粉末的BET比表面積愈大則靜電容量愈高。因此，有 活性碳粉末係以大的比表面積與電解液接觸。因此， 所述，活性碳粉末的平均細孔直徑與細孔容積係重要 本發明的活性碳粉末係平均細孔直徑在2 · 0〜4 的範圍，較佳在2.0〜3.5nm的範圍，更佳在2.0〜2 的範圍，特佳在2.2〜2.8nm的範圍。平均細孔直徑 爲在活性碳粉末與雙電層電容器的電解液之接觸下， 生的電解液滲入活性碳粉末的細孔中之容易度的指標 ，平均細孔直徑愈大，則電解液愈容易滲入活性碳粉 使用 的活 成。 長徑 下， 3000 佳在 範圍 ，由 性碳 利上 如下 〇 .0 nm .8 n m 係成 而發 。即 末的 -11 - 201236039 細孔中。惟，平均細孔直徑若過度地變大，則由於活性碳 粉末中可形成的細孔之數變少，活性碳粉末的BET比表面 積容易變小。 本發明的活性碳粉末係細孔的全容積在1 .0〜3.0 cm3/g的範圍，較佳在1 . 1〜2.5cm3/g的範圍。細孔全容積 亦成爲在活性碳粉末與雙電層電容器的電解液之接觸下， 而發生的電解液滲入活性碳粉末的細孔中之容易度的指標 活性碳粉末。即，細孔全容積愈大，則電解液滲入活性碳 粉末的細孔中之量愈多。惟，細孔全容積若過度地變大， 則活性碳粉末的強度變弱。 本發明的活性碳粉末係碘吸附量較佳在1 600〜23 00 mg/g的範圍，更佳在2000〜23 00mg/g的範圍。相對於此 以mg/g的單位所表示的碘吸附量之値，以m2/g的單位所 表示的BET比表面積之比（BET比表面積/碘吸附量）較佳 在1.1〜2.0的範圍，更佳在1.1〜1.5的範圍。 本發明的活性碳粉末係平均粒徑較佳在1〜30μηι的範 圍，更佳在3〜20μηι的範圍。 本發明的活性碳粉末亦可含有磷化合物。惟，活性碳 粉未所含有的磷化合物之量，以磷量計較佳爲5.0質量％ 以下，更佳在0.3〜1質量％的範圍，特佳在0.3〜0.7質量 %的範圍。 本發明的活性碳粉末例如藉由一種方法來製造，其包 含：將醋酸纖維素加熱以使其碳化之碳化步驟；將碳化步 驟所得之碳化物，以比在碳化步驟中使醋酸纖維素碳化時 -12- 201236039 的溫度還高5 0 °C以上的溫度進行加熱’使殘留在碳化物的 醋酸成分揮發而去除之醋酸去除步驟；而且’將經醋酸去 除步驟去除醋酸的碳化物活化處理之活化步驟。 於上述的活性碳粉末之製造方法中，作爲起始原料所 用的醋酸纖維素，係醋酸的取代度較佳在2〜3的範圍。 醋酸纖維素較佳爲以三乙醯纖維素爲主成分的纖維素。醋 酸纖維素的形態係沒有限制，可爲鱗片狀、粉末狀及塊狀 中的任一形態。 醋酸纖維素亦可含有可塑劑。作爲可塑劑之例，可舉 出磷酸酯、羧酸與醇的酯及聚酯。作爲磷酸酯之例，可舉 出磷酸三苯酯、磷酸三甲苯酚酯、磷酸甲苯酚基二苯酯、 磷酸辛基二苯酯、磷酸二苯基聯苯酯、磷酸三辛酯、磷酸 三丁酯。作爲羧酸之例，可舉出苯二甲酸、檸檬酸、油酸 、蓖麻醇酸及癸二酸。作爲醇之例，可舉出脂肪族醇（較 佳爲碳原子數1〜6的脂肪族醇）、甘醇酸、二醇（較佳爲碳 原子數2〜3的二醇）、甘油、二甘油、季戊四醇及二季戊 四醇。作爲酯之例，可舉出苯二甲酸與脂肪族醇之酯（例 如苯二甲二甲酸酯、苯二甲酸二乙酯、苯二甲酸二丁酯.、 苯二甲酸二辛酯、苯二甲酸二乙基己酯）及檸檬酸與脂肪 族醇之酯（例如，檸檬酸乙醯基三乙酯、棒檬酸乙酿基三 丁酯）。作爲聚酯之例，可舉出芳香族二殘酸與二醇的聚 酯。 醋酸纖維素係利用作爲照相軟片的支持體或液晶顯示 裝置用的偏光板之保護薄膜的材料。於本發明的活性碳粉 -13- 201236039 末之製造方法的實施時，可將自照 晶顯示裝置用偏光板的生產步驟所 醋酸纖維素當作原料使用。又，於 製造方法的實施時，亦可將自照相 偏光板之使用過品所回收之醋酸纖 於碳化步驟中，較佳爲在磷化 纖維素而使其碳化。磷化合物較佳 始原料的醋酸纖維素中。即，起始 物‘的醋酸纖維素、實質上不含有磷 含有磷化合物的醋酸纖維素之混合 化合物之混合物。 含有磷化合物的醋酸纖維素 0.1〜5.0質量％的範圍之磷化合物 量％的範圍，特佳爲含有0.1〜1.0 物較佳爲磷酸酯。磷酸酯之例係如 分子分散在醋酸纖維素中。 所謂實質上不含有磷化合物的 含量低於0.1質量％，尤其低於0 . 含有磷化合物的醋酸纖維素混合之 維素，係如上述。實質上不含有磷 含有磷化合物的醋酸纖維素之混合 30: 70〜70: 30的範圍。 作爲與醋酸纖維素混合的磷化 、磷酸鹽及磷酸酯。磷酸包含正磷 相軟片的生產步驟或液 產生的不良品所回收之 本發明的活性碳粉末之 軟片或液晶顯示裝置用 維素當作原料使用。 合物的存在下加熱醋酸 爲在加熱前預先加在起 原料較佳爲含有磷化合 化合物的醋酸纖維素與 物，或醋酸纖維素與磷 ，較佳爲以磷量計含有 ，更佳爲含0.1〜3.0質 質量％的範圍。磷化合 前述，磷化合物較佳爲 醋酸纖維素，就是指磷 01質量％。與實質上不 含有磷化合物的醋酸纖 化合物的醋酸纖維素與 比，以質量比計較佳在 合物之例，可舉出磷酸 酸及縮合磷酸。作爲磷 -14 - 201236039 酸鹽之例，可舉出銨鹽、鹼金屬鹽及鹼土 酯之例係如前述。磷化合物較佳爲磷酸酯 磷化合物的混合物，較佳爲以磷量計含有 的範圍的磷化合物，更佳爲含有0.1〜3.0 特佳爲含有0.1〜1.0質量％的範圍。醋酸 有磷化合物的醋酸纖維素，也可爲實質上 的醋酸纖維素。 於碳化步驟中，較佳爲在惰性氣體: 3 50°C的溫度加熱醋酸纖維素而使其碳化 之例，可舉出氮氣及氬氣、氮氣、氙氣、 體。加熱時間可爲至少使醋酸纖維素成爲 常爲5〜180分鐘的範圍，例如爲5〜30 分鐘的範圍。於碳化步驟中，醋酸纖維素 接著在固化後進行碳化。醋酸纖維素藉由 料的醋酸纖維素含有磷化合物時，可使磷 散於碳化物中。所得之碳化物係藉由在下 步驟中揮發去除碳化物中所殘留的醋酸， 者，於此碳化步驟中，通常的醋酸的一部 被去除。 於醋酸去除步驟中，較佳爲藉由在惰 熱碳化物，使醋酸成分揮發而去除。加熱 〜7 00°C的範圍，較佳爲5 00〜650°C的範 體之例，可舉出氮氣及氬氣、氦氣、氙氣 氣體。加熱時間一般爲1 〇分鐘〜1 〇小時 類金屬鹽。磷酸 。醋酸纖維素與 0.1〜5.0質量％ 質量％的範圍， 纖維素係可爲含 不含有磷化合物 養境下以25 0〜 。作爲惰性氣體 氣氣等的稀有氣 碳化物爲止，通 分鐘或30〜120 通常暫時熔融， 暫時熔融，於原 化合物均勻地分 一個的醋酸去除 而形成細孔。再 分亦藉由揮發而 性氣體環境下加 溫度一般爲3 8 0 圍。作爲惰性氣 、氖氣等的稀有 的範圍，較佳爲 -15- 201236039 30分鐘〜5小時的範圍。於醋酸去除步驟中，在醋酸成分 自碳化物揮發時，所生成的通路係作爲細孔而多數地形成 在碳化物內。於醋酸去除步驟中，在碳化物內形成多數的 細孔者，係可藉由測定碳化物的碘吸附量來確認。醋酸去 除步驟前的碳化物係蛛吸附量通常爲l〇〇mg/g以下，但醋 酸去除步驟後的碳化物係碘吸附量通常爲300〜800mg/g 的範圍，尤其400〜800mg/g的範圍之大幅變大。於上述 的惰性氣體中若混合二氧化碳氣體、水蒸氣、氧、空氣等 的氧化性氣體，則會促進細孔的形成。氧化性氣體的使用 量，係相對於惰性氣體與氧化性氣體之合計量而言，較佳 成爲20質量％以下之量，特佳成爲5〜15質量％的範圍之 量。又，可於碳化步驟在惰性氣體中混合該氧化性氣體， 連續且在同一環境下進行醋酸去除步驟。醋酸去除步驟後 之碳化物中所殘留的醋酸之量，係相對於碳化物的全體量 而言，醋酸含量較佳成爲20質量％以下之量，特佳成爲 10質量％以下之量。 碳化步驟及醋酸去除步驟中所產生之含有醋酸的揮發 氣體，係可被燃燒，也可進行液化而回收。所回收之含有 醋酸的液體係可利用作爲農業用途製品、工業用醋酸及燃 料等的原料。又，藉由將所回收的液體加到原料的醋酸纖 維素中，而促進醋酸去除步驟中的碳化物之細孔形成，提 高活性碳的特性。 於活化步驟中，活化處理較佳爲藉由在活化氣體的存 在下加熱碳化物而進行。作爲活化氣體之例，可舉出二氧 -16- 201236039 化碳氣體、水蒸氣、氧氣、氯化氫氣體、氨氣及空氣。作 爲活化氣體，較佳爲二氧化碳氣體及水蒸氣，特佳爲水蒸 氣。加熱溫度一般爲800〜1100 °C的範圍，較佳爲900〜 1 1 00°C的範圍。加熱時間一般爲1 0分鐘〜1 〇小時的範圍 ，較佳爲30分鐘〜5小時的範圍。藉由活化處理，在醋酸 去除步驟中碳化物內所形成的細孔係發達，細孔的直徑或 容積變大。可理解分散於碳化物內的磷化合物係具有促進 活化處理所致的細孔之發達的效果。 於活化氣體中使用二氧化碳氣體時，在活化步驟所排 出者係含有一氧化碳氣體與二氧化碳氣體的混合氣體。此 排出的混合氣體係可回收而利用活化氣體。利用混合氣體 當作活化氣體時，更佳爲預先將該混合氣體中所含的一氧 化碳氣體轉換成二氧化碳氣體，以增加混合氣體中的二氧 化碳氣體量。作爲將混合氣體中的一氧化碳氣體轉換成二 氧化碳氣體之方法，可舉出在氧的存在下使混合氣體與氧 化觸媒接觸之方法，在水蒸氣存在下使混合氣體與轉化觸 媒接觸之方法，在氧的存在下將混合氣體燃燒之方法。 爲了實施碳化步驟、醋酸去除步驟及活化步驟，可使 用眾所周知的加熱爐。加熱爐可爲分批式或連續式。作爲 分批式加熱爐之例，可舉出碳窯式碳化爐、攪拌式碳化爐 、吊運車式碳化爐及流動層式碳化爐。於連續式加熱爐中 ，爐內的被加熱物之搬送方式係沒有特別的限制。作爲被 加熱物的搬送方式之例，可舉出輥式、帶式輸送機式、流 動層式、旋轉窯式及螺旋輸送機式。生產效率上較佳爲使 -17- 201236039 用連續式加熱爐。 碳化步驟、醋酸去除步驟及活化步驟的各步驟，係可 各自使用不同的加熱爐依順序進行，也可使用一個加熱爐 連續地進行。又，也可使用一個加熱爐連續地進行碳化步 驟與醋酸去除步驟，活化步驟使用另一個加熱爐進行，也 可使用一個加熱爐連續地進行醋酸去除步驟與活化步驟， 碳化步驟使用另一個加熱爐進行。 碳化步驟與醋酸去除步驟的加熱處理係在不攪拌下的 靜置狀態下進行，有得到細孔發達的碳化物之傾向。因此 ，碳化步驟與醋酸去除步驟較佳係使用爐內的被加熱物之 搬送方式爲輥式或帶式輸送機式的連續式加熱爐來進行。 於連續式加熱爐中，較佳爲使用被加熱物的搬送方式爲輥 式的輥道窯，因爲爐內的溫度之控制容易。 於輥道窯中，將爐內分爲經調整至250〜3 50°C的溫度 之第一加熱區域、與比第一加熱區域還高50°C以上且經調 整至380〜700 °C的溫度之第二加熱區域，較佳爲藉由將收 納原料的醋酸纖維素之耐熱容器自第一區域輸送到第二區 域，而進行碳化步驟與醋酸去除步驟。爲了得到均質的碳 化物，可重疊二個以上的耐熱容器。 活化步驟係爲了提高生產效率，較佳爲使用旋轉窯進 行。 活化處理後的碳化物（活性碳）宜視需要地進行粉碎處 理及分級處理，而調整粒子大小。於粉碎處理中，例如可 使用球磨機、圓盤磨機、珠磨機及噴射磨機等的粉碎裝置 -18- 201236039 。粉碎裝置較佳爲使用球磨機（尤其行星式球磨機）、圓盤 磨機（尤其石磨式圓盤磨機）。此等磨機的粉碎介質，爲了 防止金屬對活性碳的混入，較佳爲氧化鋁製、陶瓷製或氧 化錯製的任一者。於分級處理中，例如可使用不鏽鋼製的 篩或旋風型分級機。 其次，說明使用本發明的活性碳粉末於電極活性物質 的雙電層電容器。 圖1係依照本發明的雙電層電容器之一例的截面圖。 圖1所示的雙電層電容器係一般稱爲硬幣型的雙電層 電容器。圖1中，雙電層電容器包含：正極容器1，裝載 於正極容器1的底部表面之上，壓黏正極集電體2與正極 活性物質薄片3而形成之正極薄片4，裝載於正極薄片4 上的隔板5，裝載於隔板5上，壓黏負極活性物質薄片6 與負極集電體7而形之負極薄片8,覆蓋於負極薄片8上 之負極容器9，密封正極容器1與負極容器9之墊圈10, 而且封入在內部的電解液（未圖示）。 正極活性物質薄片3及負極活性物質薄片6 —般皆由 電極活性物質、黏結劑與導電材之混合物所構成。於本發 明中，在正極活性物質薄片3及負極活性物質薄片6中的 至少一者（較佳爲兩者）之電極活性物質中使用本發明的活 性碳粉末。作爲黏結劑之例，可舉出聚四氟乙烯及聚偏二 氟乙烯。作爲導電材之例，可舉出乙炔黑及碳黑。 作爲電解液，一般使用含有電解質的有機溶劑溶液。 作爲電解質之例，可舉出四烷基銨六氟磷酸酯、四烷基辚 -19- 201236039 六氟磷酸酯、四烷基鱗四氟硼酸酯及四烷基銨四氟硼酸酯 。此等電解質係可單獨使用一種，也可倂用二種以上。作 爲有機溶劑之例，可舉出碳酸伸丙酯或碳酸伸乙酯等的碳 酸伸烷酯、γ-丁內酯、二甲基甲醯胺、二甲亞颯、乙腈、 四氫呋喃、二甲氧基乙烷及甲酸甲酯。此等有機溶劑係可 單獨使用一種，也可倂用二種以上。電解液的電解質之濃 度一般在0.5〜2.0莫耳/升的範圍。 於正極容器1、正極集電體2、負極集電體7及負極 容器9的材料中，一般使用金屬。作爲金屬之例，可舉出 鋁及不鏽鋼。於隔板5中，一般使用多孔質薄片。作爲多 孔質薄片之例，可舉出玻璃棉薄片及不織布薄片。於墊圈 10的材料中，使用樹脂。作爲樹脂之例，可舉出聚丙烯、 聚乙烯、聚丁烯及聚醯胺。 本發明的雙電層電容器係不限定於硬幣型雙電層電容 器。本發明的雙電層電容器亦可爲捲繞型雙電層電容器。 所謂的捲繞型雙電層電容器，就是在長條狀的正極活性物 質薄片與長條狀的負極活性物質薄片之間，以隔著隔板的 狀態捲繞而製作的電極捲筒，將電解液收納在容器中而密 封之構成的雙電層電容器。 實施例 [實施例1] <活性碳粉末之製造> 將含有磷酸三苯酯的醋酸纖維素（磷量：0·1〜5質量 -20- 201236039 %)粉碎成鱗片狀，置入耐熱容器中。於該容器上蓋上具備 溫度計、氮氣導入口與氣體排氣口之蓋子。其次，一邊對 耐熱容器的氮氣導入口供應氮氣，一邊加熱以使耐熱容器 的內部溫度成爲3 00 °C。於耐熱容器內的醋酸纖維素鱗片 溶解成爲液體後，進行碳化而生成碳化物（碳化步驟）。 生成碳化物後，使耐熱容器的內部溫度升溫至600°C 爲止，於該溫度保持1小時，以去除殘留在碳化物的醋酸 (醋酸去除步驟）。加熱後，放置冷卻到室溫爲止後，打開 蓋子，取出碳化物。測定醋酸去除步驟後的碳化物之碘吸 附量，結果爲580mg/g。醋酸去除步驟後的碳化物中之醋 酸含量爲6.0質量％。 將醋酸去除步驟所得的碳化物投入具備氮氣導入口、 二氧化碳氣體導入口與氣體排氣口的旋轉窯爐中。使旋轉 窯爐以lrpm的旋轉速度旋轉，一邊對二氧化碳氣體導入 口以1 6L/分鐘的流量供應二氧化碳氣體，一邊將爐內溫度 升溫至105 (TC爲止。於該溫度保持3小時，以將碳化物活 化（活化步驟）。然後，放置冷卻，於爐內溫度成爲800°C 的時間點，停止二氧化碳氣體的供給，對氮氣導入口供應 氮氣，於爐內溫度成爲l〇〇°C的時間點，自爐內取出經活 化處理的碳化物（活性碳）。藉由使用氧化鉻製的容器與瓶 之行星式球磨機來粉碎處理所得之活性碳後，進行分級處 理而得到活性碳粉末。所得之活性碳粉末的磷含量爲0.56 質量％。而且，活性碳粉末的平均粒徑爲3 . 8 μιη。 -21 - 201236039 <活性碳粉末之評價> 藉由以下的方法來測定所得之活性碳粉末的BET比表 面積、平均細孔直徑、細孔全容積、碘.吸附量及與雙電層 電容器用電解液之接觸下的靜電容量。表1中顯示其結果 (BET比表面積、平均細孔直徑及細孔全容積之測定方法） 由使用氮氣的BET法所測定之吸附等溫線來算出。 (碘吸附量之測定方法） 依照J1S K- 1 474(活性碳試驗方法）中所規定的方法進 行測定。 (靜電容量之測定方法） 如下述，製造硬幣型雙電層電容器，測定靜電容量。 (1)硬幣型雙電層電容器之製造 秤量活性碳粉末l〇mg、乙炔黑4mg與聚四氟乙烯 (PTFE)2mg，將此等置入乳鉢中進行混煉。將所得之混煉 物成型爲直徑16mm的圓形薄片狀，將其當作活性物質薄 片°其次，將此活性物質薄片壓黏於網眼狀的鋁製集電體 上’以製作電極薄片。電極薄片係製作二個，一個爲正極 薄片’另一個爲負極薄片。接著，在減壓下加熱乾燥正極 薄片與負極薄片。 -22- 201236039 將經加熱乾燥的正極薄片與負極薄片置入氬氣環境的 手套箱內，於該手套箱內，製造如圖1所示的硬幣型雙電 層電容器。即，以使正極容器的底部表面與電極薄片的鋁 製集電體接觸的方式，在正極容器中層合正極薄片，接著 於正極薄片上，層合玻璃棉製隔板。接著，直接在玻璃棉 製隔板上滴下電解液（含有1.5莫耳/升的三乙基甲基銨六 氟磷酸酯之碳酸伸丙酯溶液），使電解液充分滲入上述隔 板後，以隔板表面與負極薄片的活性物質薄片接觸的方式 ，在隔板上層合負極薄片。最後，自負極薄片之上覆蓋負 極容器，用墊圈來密封。 (2)靜電容量之測定 以1mA(每電極面積的電流密度：0.5mA/cm2)的恆定 電流，將硬幣型雙電層電容器充電直到電壓成爲3.0V爲 止。其次，以1mA的恆定電流將已充電硬幣型雙電層電 容器放電直到電壓成爲0V爲止，繪製硬幣型雙電層電容 器的放電電壓與放電時間之關係，作成放電曲線，自放電 曲線的梯度，依照常用方法算出活性碳粉末的靜電容量。 [實施例2] 除了關於實施例1的活性碳粉末之製造，使醋酸去除 步驟的加熱溫度成爲400°C以外，與實施例1同樣地處理 ，以製造活性碳粉末。再者，醋酸去除步驟後的碳化物係 碘吸附量爲386mg/g，醋酸含量爲6.0質量％。所得之活 -23- 201236039 性碳粉末係磷含量爲0.58質量％，平均粒徑爲3.7 μιη。與 實施例1同樣地測定所得之活性碳粉末的BET比表面積、 平均細孔直徑、細孔全容積、碘吸附量及靜電容量。表1 中顯不其結果。 [比較例1 ] 對於市售的雙電層電容器用活性碳粉末，與實施例1 同樣地測定靜電容量。表1中顯示其結果與活性碳粉末的 比表面積、細孔全容積及碘吸附量。201236039 VI. Description of the Invention: [Technical Field to Which the Invention Is Alonged] The present invention relates to an activated carbon powder and a method for producing the same. The present invention also relates to an electric double layer capacitor using the activated carbon powder in an electrode active material. [Prior Art] Activated carbon is widely used in various industrial fields, such as air purification, radioactive substance adsorption, iodine capture, methane storage, hydrogen storage, water purification, solvent recovery, decolorization, water treatment, and use of gas masks. Used for the purpose. In addition, in recent years, an electrode active material as a capacitor (electric double layer capacitor or lithium ion capacitor) has been used, and high performance has been demanded. An electric double layer capacitor is an energy storage device for an electric double layer formed by an interface between an electrode and an electrolyte. The activated carbon of the electrode active material used for the electric double layer capacitor is preferably a large specific surface area, because the interface with the electrolytic solution is broadened, and the electrostatic capacity is increased. Therefore, in the electrode active material of the electric double layer capacitor, activated carbon having a large specific surface area is used. The activated carbon is generally roughly classified into an activated carbon fiber composed of fibrous activated carbon particles and an activated carbon powder composed of non-fibrous (granular) activated carbon particles. Non-Patent Document 1 describes activated carbon for an electric double layer capacitor. In order to form the same electric double layer capacity at a low temperature and a room temperature, pores of 2 nm or more (P. 80) are required. Further, in Table 7 of ρ·79 of Non-Patent Document 1, the specific surface area is 0.25 m 2 /g, the average pore diameter is 20 to 40 A (2 to 4 nm), and the cumulative pore volume is 0.5 to 1.5 cc / G phenolic activated carbon fiber. The phenolic activated carbon fiber described in Non-Patent Document 1 is an activated carbon fiber (P. 73-75) obtained by carbonizing and activating a special phenol resin fiber (no voloid fiber) of -5-201236039. In the non-patent document 1, as the activated carbon fiber other than the phenol type, an oxime system using yttrium (cellulose) fiber as a raw material and an acrylic activated carbon fiber using a polyacrylonitrile fiber as a raw material are also described. In the activated carbon fiber, the specific surface area is as small as 1 000 to 1 500 m 2 /g, and the average pore diameter is as small as 14 A (1.4 nm). Further, even in the acrylic activated carbon fiber, the specific surface area is as small as 700 to 1 200 m 2 /g, the average pore diameter is as small as l 〇 A (1.0 nm), and the cumulative pore volume is 〜l.lcc/g. Patent Document 1 describes an activated carbon powder for an electric double layer capacitor having a phosphorus atom content of 1,000 to 20,000 ppm, a BET specific surface area of 1,600 to 2,200 m 2 /g, and an average pore diameter of 1.7 to 2.1 nm. A phosphorus compound composite activated carbon powder having a pore volume of between 1.4 and 2·0 ηηη and having a pore volume of 〇.25 cm 3 /g or more. However, the upper limit of the pore volume is preferably 0.5 cm 3 /g or less ([00 3 2]). Further, in Patent Document 1, the method for producing the activated carbon powder is obtained by kneading an activated carbon raw material and phosphoric acid at 130 to 170 ° C, and then molding it to pass the first heating at 100 to 23 ° C. After the heating step and the second heating step of heating at 400 to 600 ° C, the activated carbon is combined with the phosphorus compound by calcination at 800 ° C or higher in an inert gas atmosphere. Examples of the activated carbon raw material include hardwood, softwood, and the like, corn ear, coffee bean, rice husk, fruit seed, fruit shell, and the like, or residues such as molasses or lignin, or coal. , tar, asphalt, asphalt, petroleum residues. On the other hand, Patent Document 2 describes a method for producing carbonized cellulose (deuterated cellulose) to form a carbide as a method for producing activated carbon powder, and a method for activating the obtained carbide. The activated carbon powder has no specific surface area, average pore diameter, and pore volume. However, the activated carbon powder obtained in the examples of Patent Document 2 has an iodine adsorption amount of about 1144 mg/g, and the specific surface area is not so high. CITATION LIST Patent Literature PATENT DOCUMENT 1: JP-A-2008-201966 PATENT DOCUMENT 2 Non-Patent Document Non-Patent Document 1: Nishino, Naoki Katsuhiko, "Development of Electrochemical Capacitors And the application, CMC Technical Series 173, CMC Publishing, issued June 26, 2004, P. 73-80. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The phenolic activated carbon fiber described in Non-Patent Document 1 is a specific surface area. The average pore diameter and the pore volume are large, and it is judged that it is suitable as one of the materials of the electrode active material for the electric double layer capacitor. However, the phenolic activated carbon fiber described in Non-Patent Document 1 is a phenolic fiber using a special phenol resin fiber as a raw material, and has low versatility and has a problem in production cost. Further, in comparison with the non-fibrous activated carbon particles, the fibrous activated carbon particles tend to form a gap between the particles when they are formed into an electrode, so that the activated carbon fiber enthalpy is easily changed in comparison with the activated carbon powder. low. On the other hand, in the activated carbon powder described in Patent Document 1, the characteristics of the specific surface pore diameter and the pore volume are inferior to those of the above-mentioned non-patented phenol-based activated carbon fiber. Therefore, an object of the present invention is to provide each of the characteristics of the specific surface area, the flat diameter, and the pore volume, which is superior to the conventional phenol-based activated carbon fiber, and it is advantageous to use an electric activated carbon powder as an electric double layer capacitor and Its manufacturing method. The object of the present invention is also an electric double layer capacitor having a large capacitance. Means for Solving the Problems The present inventors have found that by using a method comprising: a carbonization step in which a vitamin is heated to carbonize, the carbonization step is carried out at a temperature of 50 ° when the cellulose acetate is carbonized in the carbonization step. The BET ratio of 1 600 to 3000 m 2 /g can be obtained by heating at a temperature higher than C, an acetic acid removal step of removing the vinegar remaining in the carbide, and an activation step of activating the carbide removal reaction with acetic acid. The average pore diameter is in the range of 2.0 to 1, and the total volume of the pores is in the range of 1 〇 to 3.0 cm 3 /g of the fan carbon powder. Further, when the activated carbon powder is used as an electric double layer capacitor active material, it is confirmed that the electrostatic capacitance is high, and the present invention is based on the activated carbon powder having a BET ratio of 1600 to 3000 m 2 /g. The average pore diameter is in the range of 2.0 to fe and the total volume of the pores is in the range of 1.0 to 3.0 cm 3 /g, and the average fineness is 1 or the average pore size is equal or the polar active substance is provided to provide carbonization of the cellulose acetate. The temperature is also high acid component volatilization to remove the surface area of the vinegar at 4. Onm. The electrode cost of the active device is -8 - 201236039. The preferred embodiment of the activated carbon powder of the present invention is as follows. (1) The BET specific surface area is in the range of 2100 to 3 000 m 2 /g, particularly in the range of 2600 to 3000 m 2 /g. (2) The average pore diameter is in the range of 2.2 to 2.8 nm. (3) The total volume of the pores is in the range of 1.1 to 2.5 cm 3 /g. (4) The average aspect ratio is 5 or less, more preferably 3 or less, and particularly preferably 2 or less. (5) The average particle diameter is in the range of 1 to 30 μm. (6) For electric double layer capacitors. The present invention also resides in an electric double layer capacitor which is an electric double layer capacitor composed of a positive electrode, a negative electrode and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode contains the above-described activated carbon powder of the present invention. The present invention is also a method for producing the activated carbon powder of the present invention, which comprises: a carbonization step of heating cellulose acetate to carbonize, and a carbide obtained by the carbonization step to make cellulose acetate in a carbonization step. The temperature at which the carbonization at the time of carbonization is further increased by a temperature of 50 ° C or more, the acetic acid removal step of volatilization of the acetic acid component remaining in the carbide is removed, and the activation step of the carbide activation treatment of the acetic acid removal step is removed. The preferred embodiment of the method for producing the activated carbon powder of the present invention is as follows. (1) In the carbonization step, cellulose acetate is heated and carbonized in the presence of a phosphorus compound. (2) Cellulose acetate is a cellulose acetate containing a phosphorus compound. (3) Cellulose acetate contains a phosphorus compound in a range of 0.1 to 5.0% by mass based on the amount of phosphorus. 201236039 (4) Cellulose acetate is a mixture of cellulose acetate which does not substantially contain a phosphorus compound and cellulose acetate containing a phosphorus compound. (5) A mixture of cellulose acetate and a phosphorus compound is heated to carbonize cellulose acetate. (6) In the carbonization step, cellulose acetate is heated and heated at a temperature of 250 to 350 t in an inert gas atmosphere. (7) In the acetic acid removal step, the carbide is heated at a temperature of 3 80 to 700 ° C under an inert gas atmosphere. (8) in the activation step, heating the carbide at a temperature of 800 to 1 100 ° C in a gas atmosphere selected from the group consisting of carbon dioxide gas, water vapor, oxygen gas, hydrogen chloride gas, ammonia gas, and air. . [Effects of the Invention] The activated carbon powder of the present invention exhibits a high electrostatic capacitance in contact with an electrolyte of an electric double layer capacitor. Further, the activated carbon powder of the present invention is non-fibrous, and the enthalpy density can be improved because the particle shape or the particle size is uniform as compared with the activated carbon fiber. Therefore, an electric double layer capacitor using the activated carbon powder of the present invention as an electrode active material exhibits a high capacitance. Further, it is highly desirable that the electrode active material for an electric double layer capacitor is reduced in cost, and from this point of view, the activated carbon powder of the present invention which can be produced by using cellulose acetate as a raw material is more advantageous than the activated carbon fiber. Since the activated carbon powder of the present invention has a large BET specific surface area, it can be advantageously used as an activated carbon powder for gas phase adsorption, gas storage, water purification or decolorization. 0 -10- 201236039 By using the production method of the present invention, cellulose acetate which is usually discarded in raw materials has an advantage that industrially advantageous high-performance carbon powder can be produced. [Embodiment] The activated carbon powder of the present invention is composed of fine activated carbon particles, and the activated carbon particles are non-fibrous, and the average aspect ratio (the ratio of the activated carbon particles to the short diameter: long diameter) The / short diameter is generally 5 or less, preferably 3 or more preferably 2 or less. The activated carbon powder of the present invention has a BET specific surface area in the range of 1 600 to m 2 /g, preferably in the range of 2 100 to 3000 m 2 /g, more preferably 2300 to 3000 m 2 /g, particularly preferably 2600 to 3000 m 2 / g. When an activated carbon powder is used as the electrode active material of the electric double layer capacitor, an electric double layer is formed at the interface between the activated carbon powder and the electrolytic solution, and the higher the BET specific surface area of the active powder, the higher the electrostatic capacity. Therefore, the activated carbon powder is in contact with the electrolytic solution with a large specific surface area. Therefore, the average pore diameter and the pore volume of the activated carbon powder are important. The average pore diameter of the activated carbon powder of the present invention is in the range of 2 · 0 to 4, preferably in the range of 2.0 to 3.5 nm. More preferably in the range of 2.0 to 2, especially in the range of 2.2 to 2.8 nm. The average pore diameter is an index of the ease with which the raw electrolyte penetrates into the pores of the activated carbon powder in contact with the electrolyte of the electric double layer capacitor, and the larger the average pore diameter, the electrolysis The more easily the liquid penetrates into the active use of the activated carbon powder. Under the long diameter, 3000 is in the range, and the carbonity is as follows: 0 nm .8 n m is formed. That is, the last -11 - 201236039 in the pores. However, if the average pore diameter is excessively large, the number of pores which can be formed in the activated carbon powder becomes small, and the BET specific surface area of the activated carbon powder tends to be small. The activated carbon powder of the present invention has a total volume of pores in the range of 1.0 to 3.0 cm 3 /g, preferably in the range of 1.1 to 2.5 cm 3 /g. The full volume of the pores is also an indicator of the ease of penetration of the electrolyte into the pores of the activated carbon powder in contact with the electrolyte of the electric double layer capacitor and the electric double layer capacitor. Activated carbon powder. That is, the larger the total volume of the pores, the more the electrolyte penetrates into the pores of the activated carbon powder. However, if the total volume of the pores becomes excessively large, the strength of the activated carbon powder becomes weak. The amount of iodine adsorbed by the activated carbon powder of the present invention is preferably in the range of 1 600 to 230,000 mg/g, more preferably in the range of 2000 to 2300 mg/g. The ratio of the BET specific surface area (BET specific surface area / iodine adsorption amount) expressed in units of m 2 /g is preferably in the range of 1.1 to 2.0, based on the amount of iodine adsorption expressed in units of mg/g. Better in the range of 1.1 to 1.5. The activated carbon powder of the present invention preferably has an average particle diameter of from 1 to 30 μm, more preferably from 3 to 20 μm. The activated carbon powder of the present invention may also contain a phosphorus compound. The amount of the phosphorus compound not contained in the activated carbon powder is preferably 5.0% by mass or less, more preferably 0.3 to 1% by mass, particularly preferably 0.3 to 0.7% by mass, based on the amount of phosphorus. The activated carbon powder of the present invention is produced, for example, by a method comprising: a carbonization step of heating cellulose acetate to carbonize; and carbonizing the carbide obtained by the carbonization step to carbonize cellulose acetate in a carbonization step The temperature of -12-201236039 is also heated at a temperature higher than 50 °C to remove the acetic acid removal step of volatilizing the acetic acid component remaining in the carbide; and 'the carbide activation treatment for removing the acetic acid by the acetic acid removal step Activation step. In the above method for producing activated carbon powder, the degree of substitution of acetic acid in cellulose acetate used as a starting material is preferably in the range of 2 to 3. Cellulose acetate is preferably cellulose having triethyl sulfonium cellulose as a main component. The form of the cellulose acetate is not limited, and may be any of a scaly form, a powder form, and a block form. Cellulose acetate may also contain a plasticizer. Examples of the plasticizer include phosphate esters, esters of carboxylic acids and alcohols, and polyesters. Examples of the phosphate ester include triphenyl phosphate, tricol phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, and tributyl phosphate. ester. Examples of the carboxylic acid include phthalic acid, citric acid, oleic acid, ricinoleic acid, and sebacic acid. Examples of the alcohol include an aliphatic alcohol (preferably an aliphatic alcohol having 1 to 6 carbon atoms), a glycolic acid, a diol (preferably a diol having 2 to 3 carbon atoms), and glycerin. Diglycerin, pentaerythritol and dipentaerythritol. Examples of the ester include esters of phthalic acid and an aliphatic alcohol (for example, phthalic acid ester, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, benzene). Ethyl hexyl dicarboxylate) and an ester of citric acid with an aliphatic alcohol (for example, ethyltriethyl citrate, tributyl citrate). As an example of the polyester, a polyester of an aromatic diacid and a diol can be mentioned. Cellulose acetate is a material which is used as a support for a photographic film or a protective film for a polarizing plate for a liquid crystal display device. In the practice of the production method of the activated carbon powder of the present invention -13-201236039, the cellulose acetate of the production step of the polarizing plate for the self-illuminating crystal display device can be used as a raw material. Further, in the practice of the production method, the cellulose acetate recovered from the used product of the photographic polarizing plate may be carbonized in the carbonization step, preferably in the phosphating cellulose. The phosphorus compound is preferably used in the cellulose acetate of the starting material. Namely, a mixture of the cellulose acetate of the starting material, and a mixed compound of cellulose acetate which does not substantially contain phosphorus and a phosphorus compound. The cellulose acetate containing phosphorus compound is in the range of 0.1% by mass to 5.0% by mass of the phosphorus compound, and particularly preferably 0.1% to 1.0. Examples of phosphates are molecules dispersed in cellulose acetate. The content of substantially no phosphorus compound is less than 0.1% by mass, particularly less than 0. The cellulose acetate mixed vitamin containing the phosphorus compound is as described above. Substantially free of phosphorus. Mixture of cellulose acetate containing phosphorus compounds 30: 70~70: 30 range. As a phosphating, phosphate and phosphate mixed with cellulose acetate. The phosphoric acid or the liquid crystal display device of the present invention is used as a raw material for the production of the phosphoric acid or the liquid crystal display device. The acetic acid is heated in the presence of the compound, and the cellulose acetate and the cellulose, which are preferably contained in the raw material, or the cellulose acetate and phosphorus, preferably contained in the amount of phosphorus, more preferably A range of 0.1 to 3.0 mass%. Phosphate compounding The phosphorus compound is preferably cellulose acetate, which means that phosphorus is 01% by mass. The ratio of the cellulose acetate to the cellulose acetate compound which does not substantially contain a phosphorus compound is preferably a mass ratio, and examples thereof include phosphoric acid and condensed phosphoric acid. Examples of the phosphorus-14 - 201236039 acid salt include the examples of the ammonium salt, the alkali metal salt and the alkaline earth ester as described above. The phosphorus compound is preferably a mixture of phosphoric acid phosphorus compounds, preferably a phosphorus compound in a range of phosphorus, more preferably 0.1 to 3.0, particularly preferably 0.1 to 1.0% by mass. Acetic acid Cellulose acetate having a phosphorus compound may also be substantially cellulose acetate. In the carbonization step, it is preferred to heat the cellulose acetate at a temperature of 3 to 50 ° C to carbonize it, and examples thereof include nitrogen gas, argon gas, nitrogen gas, helium gas and gas. The heating time may be such that at least the cellulose acetate is in the range of usually 5 to 180 minutes, for example, in the range of 5 to 30 minutes. In the carbonization step, the cellulose acetate is then carbonized after curing. When the cellulose acetate cellulose acetate-containing material contains a phosphorus compound, phosphorus can be dispersed in the carbide. The obtained carbide is obtained by volatilization in the next step to remove the acetic acid remaining in the carbide, and in this carbonization step, a part of the usual acetic acid is removed. In the acetic acid removal step, it is preferred to remove the acetic acid component by volatilizing the inactive thermal carbide. Examples of the heating range of ～700 ° C, preferably 500 to 650 ° C, include nitrogen gas, argon gas, helium gas, and helium gas. The heating time is usually 1 〜 minutes ~ 1 〇 hours of metal salt. Phosphoric acid. Cellulose acetate is in the range of 0.1 to 5.0% by mass in mass%, and the cellulose system may be contained in a nutrient containing no phosphorus compound at 25 0~. As a rare gas carbide such as an inert gas, it is usually melted in a minute or 30 to 120, and temporarily melted, and the original compound is uniformly divided into one acetic acid to form fine pores. In addition, the temperature is usually increased by 380 in a volatile gas atmosphere. As a rare range of inert gas, helium gas, etc., it is preferably -15-201236039 ranging from 30 minutes to 5 hours. In the acetic acid removal step, when the acetic acid component is volatilized from the carbide, the formed passage is formed in the carbide as a fine pore. In the acetic acid removal step, a large number of fine pores are formed in the carbide, which can be confirmed by measuring the amount of iodine adsorption of the carbide. The amount of carbide adsorption before the acetic acid removal step is usually less than 10 mg/g, but the amount of carbide-based iodine adsorption after the acetic acid removal step is usually in the range of 300 to 800 mg/g, especially 400 to 800 mg/g. The scope has greatly increased. When an oxidizing gas such as carbon dioxide gas, water vapor, oxygen, or air is mixed in the above inert gas, the formation of pores is promoted. The amount of the oxidizing gas to be used is preferably 20% by mass or less, and particularly preferably 5 to 15% by mass based on the total amount of the inert gas and the oxidizing gas. Further, the oxidizing gas may be mixed in an inert gas in the carbonization step, and the acetic acid removing step may be carried out continuously and under the same environment. The amount of the acetic acid remaining in the carbide after the step of removing the acetic acid is preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the total amount of the carbide. The volatilization gas containing acetic acid generated in the carbonization step and the acetic acid removal step can be burned or recovered by liquefaction. The recovered liquid system containing acetic acid can be used as a raw material for agricultural products, industrial acetic acid, and fuel. Further, by adding the recovered liquid to the cellulose acetate of the raw material, the formation of pores of the carbide in the acetic acid removing step is promoted, and the characteristics of the activated carbon are enhanced. In the activation step, the activation treatment is preferably carried out by heating the carbide in the presence of an activating gas. Examples of the activating gas include dioxo-16-201236039 carbonized gas, steam, oxygen, hydrogen chloride gas, ammonia gas, and air. As the activating gas, carbon dioxide gas and water vapor are preferred, and water vapor is particularly preferred. The heating temperature is usually in the range of 800 to 1100 ° C, preferably in the range of 900 to 1 00 ° C. The heating time is generally in the range of 10 minutes to 1 hour, preferably in the range of 30 minutes to 5 hours. By the activation treatment, the pores formed in the carbide are developed in the acetic acid removal step, and the diameter or volume of the pores becomes large. It is understood that the phosphorus compound dispersed in the carbide has an effect of promoting the development of pores due to the activation treatment. When carbon dioxide gas is used in the activating gas, the exhaust gas in the activation step contains a mixed gas of carbon monoxide gas and carbon dioxide gas. This discharged mixed gas system can be recycled to utilize the activated gas. When the mixed gas is used as the activating gas, it is more preferable to convert the carbon monoxide gas contained in the mixed gas into carbon dioxide gas in advance to increase the amount of carbon dioxide gas in the mixed gas. As a method of converting carbon monoxide gas in a mixed gas into carbon dioxide gas, a method of bringing a mixed gas into contact with an oxidation catalyst in the presence of oxygen, and a method of bringing the mixed gas into contact with a conversion catalyst in the presence of steam, A method of burning a mixed gas in the presence of oxygen. In order to carry out the carbonization step, the acetic acid removal step and the activation step, a well-known heating furnace can be used. The furnace can be batch or continuous. Examples of the batch type heating furnace include a carbon kiln type carbonization furnace, a stirring type carbonization furnace, a trolley type carbonization furnace, and a fluidized bed type carbonization furnace. In the continuous heating furnace, the manner of conveying the object to be heated in the furnace is not particularly limited. Examples of the conveying method of the object to be heated include a roll type, a belt conveyor type, a fluid layer type, a rotary kiln type, and a screw conveyor type. The production efficiency is preferably such that a continuous heating furnace is used for -17-201236039. The steps of the carbonization step, the acetic acid removal step, and the activation step may be carried out sequentially using different heating furnaces, or may be carried out continuously using one heating furnace. Further, the carbonization step and the acetic acid removal step may be continuously performed using one heating furnace, the activation step may be carried out using another heating furnace, or the acetic acid removal step and the activation step may be continuously performed using one heating furnace, and the other carbonization step may be used for the carbonization step. get on. The carbonization step and the heat treatment in the acetic acid removal step are carried out in a static state without stirring, and tend to have carbides having fine pores. Therefore, the carbonization step and the acetic acid removal step are preferably carried out using a continuous heating furnace of a roll type or a belt conveyor type using a method of conveying the object to be heated in the furnace. In the continuous heating furnace, it is preferable to use a roller type kiln in which the object to be heated is conveyed because the temperature inside the furnace is easily controlled. In the roller kiln, the furnace is divided into a first heating zone adjusted to a temperature of 250 to 3 50 ° C, and is 50 ° C higher than the first heating zone and adjusted to 380 to 700 ° C. The second heating zone of the temperature is preferably subjected to a carbonization step and an acetic acid removal step by transporting the heat-resistant container of cellulose acetate containing the raw material from the first region to the second region. In order to obtain a homogeneous carbide, two or more heat-resistant containers may be stacked. The activation step is preferably carried out using a rotary kiln in order to increase production efficiency. The activated carbide (activated carbon) should be subjected to pulverization treatment and classification treatment as needed to adjust the particle size. In the pulverization treatment, for example, a pulverizing apparatus -18-201236039 such as a ball mill, a disc mill, a bead mill, or a jet mill can be used. Preferably, the pulverizing means uses a ball mill (especially a planetary ball mill) and a disc mill (especially a stone mill disc mill). The pulverizing medium of these mills is preferably made of alumina, ceramic or oxidized in order to prevent the incorporation of metal into the activated carbon. In the classification treatment, for example, a stainless steel sieve or a cyclone type classifier can be used. Next, an electric double layer capacitor using the activated carbon powder of the present invention as an electrode active material will be described. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing an example of an electric double layer capacitor in accordance with the present invention. The electric double layer capacitor shown in Fig. 1 is generally referred to as a coin type electric double layer capacitor. In the electric double layer capacitor, the positive electrode container 1 is placed on the bottom surface of the positive electrode container 1, and the positive electrode sheet 4 formed by pressing the positive electrode current collector 2 and the positive electrode active material sheet 3 is placed on the positive electrode sheet 4. The upper separator 5 is placed on the separator 5, and the negative electrode sheet 8 is formed by pressure-bonding the negative electrode active material sheet 6 and the negative electrode current collector 7, covering the negative electrode container 9 on the negative electrode sheet 8, and sealing the positive electrode container 1 and the negative electrode. The gasket 10 of the container 9 is sealed with an electrolyte (not shown) inside. The positive electrode active material sheet 3 and the negative electrode active material sheet 6 are generally composed of a mixture of an electrode active material, a binder and a conductive material. In the present invention, the active carbon powder of the present invention is used for the electrode active material of at least one (preferably both) of the positive electrode active material sheet 3 and the negative electrode active material sheet 6. Examples of the binder include polytetrafluoroethylene and polyvinylidene fluoride. Examples of the conductive material include acetylene black and carbon black. As the electrolytic solution, an organic solvent solution containing an electrolyte is generally used. Examples of the electrolyte include tetraalkylammonium hexafluorophosphate, tetraalkylphosphonium-19-201236039 hexafluorophosphate, tetraalkylbarium tetrafluoroborate, and tetraalkylammonium tetrafluoroborate. These electrolytes may be used alone or in combination of two or more. Examples of the organic solvent include alkylene carbonate such as propyl carbonate or ethyl carbonate, γ-butyrolactone, dimethylformamide, dimethyl hydrazine, acetonitrile, tetrahydrofuran, and dimethoxygen. Ethyl ethane and methyl formate. These organic solvents may be used singly or in combination of two or more. The electrolyte concentration of the electrolyte is generally in the range of 0.5 to 2.0 mol/liter. Metal is generally used for the materials of the positive electrode container 1, the positive electrode current collector 2, the negative electrode current collector 7, and the negative electrode container 9. Examples of the metal include aluminum and stainless steel. In the separator 5, a porous sheet is generally used. Examples of the porous sheet include a glass wool sheet and a non-woven sheet. In the material of the gasket 10, a resin is used. Examples of the resin include polypropylene, polyethylene, polybutene, and polyamine. The electric double layer capacitor of the present invention is not limited to a coin type electric double layer capacitor. The electric double layer capacitor of the present invention may also be a wound type electric double layer capacitor. The wound electric double layer capacitor is an electrode roll which is wound between a long positive electrode active material sheet and a long strip of negative electrode active material sheet, and is wound with a separator interposed therebetween, and is electrolyzed. An electric double layer capacitor formed by sealing a liquid in a container. EXAMPLES [Example 1] <Production of activated carbon powder> Cellulose acetate (amount of phosphorus: 0·1 to 5 mass -20 - 201236039 %) containing triphenyl phosphate was pulverized into scaly shapes, and placed. Heat resistant container. A lid having a thermometer, a nitrogen gas introduction port, and a gas exhaust port is attached to the container. Next, while supplying nitrogen gas to the nitrogen gas introduction port of the heat-resistant container, the temperature was set to 300 ° C in the internal temperature of the heat-resistant container. After the cellulose acetate flakes in the heat-resistant container are dissolved into a liquid, carbonization is carried out to form carbides (carbonization step). After the carbide was formed, the internal temperature of the heat-resistant container was raised to 600 ° C, and the temperature was maintained at this temperature for 1 hour to remove the residual acetic acid (acetic acid removal step). After heating, after allowing to cool to room temperature, open the lid and remove the carbide. The amount of iodine absorbed by the carbide after the acetic acid removal step was measured and found to be 580 mg/g. The acetic acid content in the carbide after the acetic acid removal step was 6.0% by mass. The carbide obtained by the acetic acid removal step is placed in a rotary kiln equipped with a nitrogen gas introduction port, a carbon dioxide gas introduction port, and a gas exhaust port. The rotary kiln was rotated at a rotation speed of 1 rpm, and carbon dioxide gas was supplied to the carbon dioxide gas introduction port at a flow rate of 16 L/min, and the temperature in the furnace was raised to 105 (TC). The temperature was maintained at this temperature for 3 hours to carbonize. The material is activated (activation step). Then, it is left to cool, and when the temperature in the furnace becomes 800 ° C, the supply of carbon dioxide gas is stopped, and nitrogen gas is supplied to the nitrogen gas inlet port, and the temperature in the furnace becomes l 〇〇 ° C. The activated carbon (activated carbon) is taken out from the furnace, and the activated carbon obtained by pulverizing the treatment is obtained by using a container made of chrome oxide and a planetary ball mill of a bottle, and then subjected to classification treatment to obtain activated carbon powder. The activated carbon powder has a phosphorus content of 0.56% by mass. Further, the average particle diameter of the activated carbon powder is 3.8 μm. -21 - 201236039 <Evaluation of activated carbon powder> The BET specific surface area, the average pore diameter, the total pore volume, the iodine adsorption amount, and the electrostatic capacity in contact with the electrolytic solution for an electric double layer capacitor of the obtained activated carbon powder. The results (measurement methods of BET specific surface area, average pore diameter, and total pore volume) are shown in Table 1. The adsorption isotherm measured by the BET method using nitrogen gas is used. (Method for measuring iodine adsorption amount) According to J1S The method specified in K- 1 474 (Test Method for Activated Carbon) was carried out. (Method for Measuring Electrostatic Capacity) A coin-type electric double layer capacitor was produced and the capacitance was measured as follows. (1) Coin type electric double layer capacitor Manufactured weighing activated carbon powder l〇mg, acetylene black 4mg and polytetrafluoroethylene (PTFE) 2mg, which were placed in a mortar and kneaded. The obtained kneaded product was formed into a circular flake having a diameter of 16 mm. This is taken as an active material sheet. Next, the active material sheet is pressure-bonded to a mesh-shaped aluminum current collector to prepare an electrode sheet. The electrode sheet is made into two, one is a positive electrode sheet and the other is a negative electrode. Then, the positive electrode sheet and the negative electrode sheet are heated and dried under reduced pressure. -22- 201236039 The heat-dried positive electrode sheet and the negative electrode sheet are placed in a glove box in an argon atmosphere, and manufactured in the glove box. A coin-type electric double layer capacitor shown in Fig. 1. That is, a positive electrode sheet is laminated in a positive electrode container so that a bottom surface of the positive electrode container is in contact with an aluminum current collector of the electrode sheet, and then laminated on the positive electrode sheet. Glass wool separator. Next, the electrolyte (containing 1.5 mol/L triethylmethylammonium hexafluorophosphate carbonate propyl ester solution) was directly dropped on the glass wool separator to fully infiltrate the electrolyte. After the separator, the negative electrode sheet is laminated on the separator so that the surface of the separator contacts the active material sheet of the negative electrode sheet. Finally, the negative electrode container is covered from the negative electrode sheet and sealed with a gasket. (2) Electrostatic capacity A constant current of 1 mA (current density per electrode area: 0.5 mA/cm 2 ) was measured, and the coin-type electric double layer capacitor was charged until the voltage became 3.0 V. Next, the charged coin type electric double layer capacitor is discharged at a constant current of 1 mA until the voltage becomes 0 V, and the relationship between the discharge voltage and the discharge time of the coin type electric double layer capacitor is plotted, and a discharge curve and a gradient of the self-discharge curve are formed. A common method is used to calculate the electrostatic capacity of the activated carbon powder. [Example 2] An activated carbon powder was produced in the same manner as in Example 1 except that the heating temperature of the acetic acid removal step was changed to 400 °C in the production of the activated carbon powder of Example 1. Further, the amount of carbide-based iodine adsorption after the acetic acid removal step was 386 mg/g, and the acetic acid content was 6.0% by mass. The obtained -23-201236039 carbon powder has a phosphorus content of 0.58% by mass and an average particle diameter of 3.7 μm. The BET specific surface area, the average pore diameter, the total pore volume, the iodine adsorption amount, and the electrostatic capacity of the obtained activated carbon powder were measured in the same manner as in Example 1. Table 1 shows no results. [Comparative Example 1] The electrostatic capacity was measured in the same manner as in Example 1 for a commercially available activated carbon powder for an electric double layer capacitor. Table 1 shows the results, the specific surface area of the activated carbon powder, the total pore volume, and the iodine adsorption amount.
表1 BET比表面積 (m2/g) 平均細孔直徑 (nm) 細孔全容積 (cm3/g) 碘吸附量 (mg/g) 靜電容量 (F/g) 實施例1 2732 2.64 1.80 2100 61.9 實施例2 2314 2.33 1.35 1858 55.1 比較例1 1800-2000 不明 0.70-1.00 1800-2000 53.1 由表1的結果可明知，依照本發明的活性碳粉末，與 市售的活性碳粉末比較下，係顯示高的BET比表面積與細 孔全容積，作爲雙電層電容器的電極活性物質使用時，確 認顯示高的靜電容量。 [實施例3] 除了代磷酸三苯酯，使用以10〜15質量％的範圍含有 苯二甲酸與乙二醇的聚酯之醋酸纖維素以外，與實施例j -24 - 201236039 同樣地處理而得到活性碳粉末。醋酸去除步驟後的碳化物 係姚吸附量爲500mg/g，醋酸含量爲5.0質量％。所得之 活性碳粉末係BET比表面積爲2200m2/g，平均細孔直徑 爲2.3nm ’細孔全容積爲1 ·3 0cm3/g，而且碘吸附量爲1800 mg/g。 [實施例4] 將含有磷酸三苯酯的醋酸纖維素（磷量：1.5質量％)之 鱗片狀粉碎品置入耐熱容器內，於爐內溫度經調整至圖2 所示的溫度分布之輥道窯（長度l〇m)內以lm/小時的速度 搬送，而連續地進行碳化步驟與醋酸去除步驟。再者，於 圖2中，橫軸表示與輥道窯的入口之距離，縱軸表示在該 距離的溫度》所得之碳化物係碘吸附量爲476mg/g，醋酸 含量爲5.4質量％。將所得之碳化物置入電爐中，一邊對 該電爐以〇.5mL/分鐘的速度導入作爲水蒸氣的水，一邊以 850t的溫度加熱3小時而進行活化步驟。與實施例1同 樣地粉碎處理活化步驟後的碳化物，接著進行分級處理而 得到活性碳粉末。所得之活性碳粉末係BET比表面積爲 2100m2/g，平均細孔直徑爲2.32nm，細孔全容積爲1.19 cm3/g，而且碘吸附量爲1 803mg/g。 [實施例5] 除了於活化步驟中，使加熱時間成爲4小時以外，與 實施例4同樣地處理而得到活性碳粉末。所得之活性碳粉 -25- 201236039 末係BET比表面積爲2435m2/g，平均細孔直徑爲2·44ηπι ，細孔全容積爲1.48cm3/g，而且碘吸附量爲1 8 3 7mg/g。 [實施例6] 除了於活化步驟中，一邊對電爐以200mL/分鐘的速 度導入二氧化碳氣體，一邊以95 (TC的溫度加熱3小時以 外，與實施例4同樣地處理而得到活性碳粉末。所得之活 性碳粉末係BET比表面積爲2775m2/g，平均細孔直徑爲 3.77nm，細孔全容積爲2.61cm3/g，而且碘吸附量爲2111 mg/g。 [實施例7](起始原料之醋酸纖維素中所含有的磷化合物之 影響） 於實施例3所使用之以10〜15質量％的範圍含有苯二 甲酸與乙二醇的聚酯之醋酸纖維素的鱗片狀粉碎物100質 量份中，添加混合100質量份的實施例1所使用之含有磷 酸三苯酯的醋酸纖維素（磷量：0.1〜5質量％)之鱗片狀粉 碎物。使用所得之混合物（磷含量：0.05〜2.5質量％)於起 始原料，以外係與實施例1同樣地處理，而得到活性碳粉 末。所得之活性碳粉末的BET比表面積、平均細孔直徑、 細孔全容積及碘吸附量係與實施例3所得之活性碳粉末的 結果~起顯示於表2中。 [實施例8](起始原料之醋酸纖維素中所含有的磷化合物之 -26- 201236039 影響） 於將實施例3所使用之以10〜15質量％的範圍含有苯 二甲酸與乙二醇的聚酯之醋酸纖維素粉碎成鱗片狀而得之 粉碎物100質量份中，添加混合10質量份的磷酸三苯酯 。使用所得之混合物（磷含量：1質量％)於起始原料，以外 係與實施例1同樣地處理，而得到活性碳粉末。表2中顯 示所得之活性碳粉末的BET比表面積、平均細孔直徑、細 孔全容積及碘吸附量。Table 1 BET specific surface area (m2/g) Average pore diameter (nm) Full pore volume (cm3/g) Iodine adsorption amount (mg/g) Electrostatic capacity (F/g) Example 1 2732 2.64 1.80 2100 61.9 Implementation Example 2 2314 2.33 1.35 1858 55.1 Comparative Example 1 1800-2000 Unknown 0.70-1.00 1800-2000 53.1 It is apparent from the results of Table 1 that the activated carbon powder according to the present invention is compared with a commercially available activated carbon powder. When the high BET specific surface area and the total pore volume were exhibited, it was confirmed to exhibit a high electrostatic capacitance when used as an electrode active material of an electric double layer capacitor. [Example 3] The treatment was carried out in the same manner as in Example j-24 - 201236039 except that the cellulose triphenyl phosphate was used in the form of cellulose acetate containing a polyester of phthalic acid and ethylene glycol in a range of 10 to 15% by mass. An activated carbon powder is obtained. The carbide amount after the acetic acid removal step was 500 mg/g, and the acetic acid content was 5.0% by mass. The obtained activated carbon powder had a BET specific surface area of 2,200 m 2 /g, an average pore diameter of 2.3 nm ′, a pore volume of 1,300 cm 3 /g, and an iodine adsorption amount of 1,800 mg/g. [Example 4] A flaky pulverized product of cellulose acetate (phosphorus content: 1.5% by mass) containing triphenyl phosphate was placed in a heat-resistant container, and the temperature in the furnace was adjusted to the temperature distribution roller shown in Fig. 2 The kiln (length l〇m) is conveyed at a speed of lm/hour, and the carbonization step and the acetic acid removal step are continuously performed. Further, in Fig. 2, the horizontal axis represents the distance from the inlet of the roller kiln, and the vertical axis represents the temperature at the distance. The obtained carbide-based iodine adsorption amount was 476 mg/g, and the acetic acid content was 5.4% by mass. The obtained carbide was placed in an electric furnace, and water was introduced into the electric furnace at a rate of 0.5 mL/min, and heated at 850 t for 3 hours to carry out an activation step. The carbide after the activation step was pulverized in the same manner as in Example 1, and then classified to obtain an activated carbon powder. The obtained activated carbon powder had a BET specific surface area of 2,100 m 2 /g, an average pore diameter of 2.32 nm, a total pore volume of 1.19 cm 3 /g, and an iodine adsorption amount of 1,803 mg / g. [Example 5] An activated carbon powder was obtained in the same manner as in Example 4 except that the heating time was changed to 4 hours in the activation step. The obtained activated carbon powder -25- 201236039 The final BET specific surface area was 2435 m 2 /g, the average pore diameter was 2·44 ηπι , the total pore volume was 1.48 cm 3 /g, and the iodine adsorption amount was 1 8 3 7 mg / g. [Example 6] An activated carbon powder was obtained in the same manner as in Example 4 except that the carbon dioxide gas was introduced into the electric furnace at a rate of 200 mL/min in the activation step, and the mixture was heated at a temperature of 95 (TC for 3 hours). The obtained activated carbon powder had a BET specific surface area of 2775 m 2 /g, an average pore diameter of 3.77 nm, a total pore volume of 2.61 cm 3 /g, and an iodine adsorption amount of 2111 mg / g. [Example 7] The effect of the phosphorus compound contained in the cellulose acetate of the starting material) The flaky pulverized material of the cellulose acetate containing the polyester of the phthalic acid and ethylene glycol in the range of 10 to 15% by mass used in Example 3. 100 parts by mass of 100 parts by mass of a flaky pulverized product of cellulose acetate (phosphorus: 0.1 to 5 mass%) containing triphenyl phosphate used in Example 1 was added, and the obtained mixture (phosphorus content: 0.05 to 2.5% by mass of the starting material was treated in the same manner as in Example 1 to obtain an activated carbon powder. The BET specific surface area, average pore diameter, total pore volume, and iodine of the obtained activated carbon powder were obtained. Adsorption amount and embodiment 3 The results of the obtained activated carbon powder are shown in Table 2. [Example 8] (Part II of the phosphorus compound contained in the cellulose acetate of the starting material) - 201236039 Effect) The use of Example 3 was used. 10 parts by mass of triphenyl phosphate was added and mixed in 100 parts by mass of the pulverized product obtained by pulverizing cellulose acetate of a polyester containing phthalic acid and ethylene glycol in a range of 10 to 15% by mass. The mixture (phosphorus content: 1% by mass) was treated in the same manner as in Example 1 except for the starting material, to obtain an activated carbon powder. Table 2 shows the BET specific surface area and average pores of the obtained activated carbon powder. Diameter, full pore volume and iodine adsorption capacity.
表2 起始材料的磷含量 BET比表面積平均細孔直徑細孔全容積 碘吸附量 憤量％) (m2/g) (nm) (cm3/g) (mg/R) 實施例7 0.05 〜2.5 2839 3.02 2.14 2113 實施例8 1 2589 2.63 1.70 2021 實施例3 0 2200 2.3 1.30 1800 由上述表2的結果可知，當起始原料的醋酸纖維素含 有磷化合物時，所得之活性碳粉末的BET比表面積 '平均 細孔直徑、細孔全容積及碘吸附量皆有顯示高的値之傾向 【圖式簡單說明】 圖1係依照本發明之硬幣型雙電層電容器之一例的截 面圖。 圖2係顯示實施例3〜5的活性碳粉末之製造中所使 -27- 201236039 用的輥道窯內之溫度分布的圖。 【主要元件符號說明】 1 :正極容器 2 :正極集電體 3 :正極活性物質薄片 4 :正極薄片 5 :隔板 6 :負極活性物質薄片 7 :負極集電體 8 :負極薄片 9 :負極容器 1 0 :墊圈 -28-Table 2 Phosphorus content of starting material BET specific surface area average pore diameter pore volume full volume iodine adsorption amount inversion amount) (m2 / g) (nm) (cm3 / g) (mg / R) Example 7 0.05 ~ 2.5 2839 3.02 2.14 2113 Example 8 1 2589 2.63 1.70 2021 Example 3 0 2200 2.3 1.30 1800 From the results of Table 2 above, it is understood that when the cellulose acetate of the starting material contains a phosphorus compound, the BET ratio of the obtained activated carbon powder The surface area 'average pore diameter, the total pore volume, and the iodine adsorption amount all have a tendency to exhibit high enthalpy. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a coin-type electric double layer capacitor according to the present invention. Fig. 2 is a graph showing the temperature distribution in the roller kiln used in the production of activated carbon powders of Examples 3 to 5 in -27 to 201236039. [Description of main component symbols] 1 : Positive electrode container 2 : Positive electrode current collector 3 : Positive electrode active material sheet 4 : Positive electrode sheet 5 : Separator 6 : Negative electrode active material sheet 7 : Negative electrode collector 8 : Negative electrode sheet 9 : Negative electrode container 1 0 : Washer-28-