201006762 六、發明說明： 【發明所屬之技術領域】 本發明係有關含有奈米構造中空碳材料與無機粒子， 該奈米構造中空碳材料彼此被該無機粒子所連結之成形體 及其製造方法。本發明更有關由該成形體所成之膜。 【先前技術】 參 碳材料係具有由石墨、金剛石、卡賓等碳之同素異形 體、或此等複合系所構成之極多樣性質之材料。近年，富 勒烯、碳奈米管類、極細碳材料等之奈米構造碳材料，由 於具有不同於先行技術之碳材料（石墨、金剛石、非晶質 碳等）之構造，因此倍受矚目。 又，奈米構造碳材料於多方之應用領域被實用化，因 此務必整備以廉價供應穩定品質之製品的體制。更且，由 於應用製品之特性差異大，故應對各種應用技術之尺寸、 β 構造、定向控制等之形態控制成爲重要的課題。 針對解決此課題的討論中，最近被開發一種新穎的奈 米構造中空碳材料（參考US 2007/0060471 Α1)。而有關 其尺寸、構造爲公知，惟，關於對含有奈米構造中空碳材 ' 料之組成物賦予造形性，應用於何種用途之技術’卻未被 提及。 【發明內容】 本發明目的之一係得到含有奈米構造中空碳材料’具 -5- 201006762 有高導電性之成形體。 一方面，本發明係有關含有奈米構造中空碳材料與無 機粒子，該奈米構造中空碳材料彼此被該無機粒子所連結 之成形體。 理想形態之一，該奈米構造中空碳材料各自具有碳部 - 份及中空部份，具有中空部份全部由碳部份圍繞之構造， _ 中空的一部份由碳部份圍繞之構造，或多數之碳部份進行 連結或成塊，各碳部份圍繞中空部份的全部或一部份的構 ❹ 造。 理想形態之一 ’奈米構造中空碳材料係滿足以下之（ A ) 、 （ B )之要件。 (A) 奈米構造中空碳材料之碳部份的厚度爲lnm〜 20nm之範圍。 (B) 奈米構造中空碳材料之中空部份的直徑爲 〇.5nm〜90nm之範圍。 理想形態之~ ’該奈米構造中空碳材料係藉由順序含 0 有以下（1 ) 、（ 2 ) 、（ 3 )及（4 )步驟的方法所得到的 奈米構造中空碳材料。 (1) 製造模版觸媒奈米粒子之步驟、 (2) 該模版觸媒奈米粒子之存在下，進行碳材料前 驅物之聚合’於該模版觸媒奈米粒子表面，形成碳材料中 間體之步驟。 (3) 使該碳材料中間體進行碳化，形成碳材料，製 造奈米構造複合材料之步驟。 -6- 201006762 (4)由該奈米構造複合材料去除模版觸媒奈米粒子 ，製造奈米構造中空碳材料之步驟。 理想形態之一’該無機粒子爲二氧化矽。 理想形態之一 ’該成形體爲膜狀。 一方面’本發明係該成形體之製造方法，含有： 使奈米構造中空碳材料與無機粒子分散於液體媒介物 中之分散液塗佈於支撐體，形成分散液膜，以及 由該分散液膜去除該液體媒介物，形成含有奈米構造 中空碳材料與無機粒子之膜。 本發明可得到含有奈米構造中空碳材料，具有高導電 性之成形體。如將本發明之成形體作成膜狀，其係可活化 其高導電性’應用於導電膜、靜電防止膜，將本發明之成 形體作成線狀，則可作爲導線應用。 【實施方式】 • [發明實施之最佳形態] 本發明之成形體係含有奈米構造中空碳材料與無機粒 子。 本發明中，奈米構造中空碳材料爲奈米尺寸（〇·5ηιη 〜lym左右）’該奈米構造中空碳材料各自具有碳部份 及中空部份。本發明之奈米構造中空材料爲滿足以下之（ A)要件者宜’進一步滿足以下之（B) 、（C)要件者更 佳。 (A)奈米構造中空碳材料各自具有碳部份及中空部 201006762 份，具有中空部份全部由碳部份圍繞之構造，中空部的— 部份由碳部份圍繞之構造，或多數之碳部份進行連結 '或 成塊，各碳部份圍繞中空部份的全部或一部份的構造。 (B) 奈米構造中空碳材料之碳部份的厚度爲lnm〜 1 OOnm之範圍。 (C) 奈米構造中空碳材料之中空部份的直徑爲 _ 0.5nm〜90nm之範圍。 又，本發明中，奈米構造中空碳材料之其碳部份亦可 @ 爲多層狀，亦可滿足以下之（D)要件。 (D) 奈米構造中空碳材料之碳部份係由2〜200層所 成之多層狀構造。由製造效率之觀點視之，由2〜100層所 成之多層狀構造者較佳。 又，本發明中，奈米構造中空碳材料係藉由順序含有 依以下（1) 、（2) 、（3)及（4)步驟的方法所得到。 (1) 製造模版觸媒奈米粒子之步驟。 (2) 該模版觸媒奈米粒子之存在下，進行碳材料前 〇 驅物之聚合，於該模版觸媒奈米粒子表面，形成碳材料中 間體之步驟。 (3) 使該碳材料中間體進行碳化，形成碳材料，製 造奈米構造複合材料之步驟。 (4) 由該奈米構造複合材料去除模版觸媒奈米粒子 ，製造奈米構造中空碳材料之步驟。 以下，依該（1) 、（2) 、（3)、及（4)之步驟， 進行具體的說明 -8 - 201006762 步驟（1)中，模版觸媒奈米粒子係如以下所製造。 使用1種以上之觸媒前驅物與1種以上之分散劑，接著 使觸媒前驅物與分散劑進行反應或連結，形成觸媒複合體 。通常，將觸媒前驅物與分散劑溶解或分散於適當的溶媒 中，使觸媒與分散劑經由連結後形成此觸媒複合體。其中 使觸媒前驅物與分散劑溶於溶媒所得到的溶液稱爲「觸媒 溶液」，使觸媒前驅物與分散劑分散於溶媒所得到之分散 • 液稱爲「觸媒懸浮液」。 觸媒前驅物只要是促進後述之碳材料前驅物之聚合及 /或後述之碳材料中間體之碳化者即可，並未特別限定， 較佳者爲選自鐵、鈷、鎳等之過渡金屬，更佳者爲鐵。 觸媒複合體係含有1種以上之分散劑。此分散劑係選 自促進具有目的之穩定性、大小均一性之觸媒奈米粒子生 成者。分散劑係指各種有機分子、高分子、低聚物等。此 分散劑溶解或分散於適當的溶媒中使用。 • 作爲觸媒複合體調製用之溶媒者，亦可利用水、含有 機溶媒之各種溶媒。爲使觸媒前驅物與分散劑相互作用， 而使用溶媒。又，溶媒亦可作爲分散劑之作用。溶媒亦可 使觸媒奈米粒子作成懸浮液。作爲理想的溶媒例者，如： 水、甲醇、乙醇、η-丙醇、異丙醇、乙腈、丙酮、四氫呋 喃、乙二醇、二甲基甲醯胺、二甲亞碾、二氯甲烷等例， 亦可混合此等使用。 認爲此觸媒複合體被溶媒分子所圍繞。於觸媒溶液或 觸媒懸浮液中生成觸媒複合體後，去除溶媒，可得到乾燥 -9- 201006762 之觸媒複合體。又，此乾燥之觸媒複合體可藉由加入適當 的溶媒而恢復成懸浮液。 觸媒溶液或觸媒懸浮液中可控制分散劑與觸媒前驅物 之莫耳比。對於分散劑官能基之觸媒原子之比例，理想者 爲0.01: 1〜100: 1左右，更佳者爲0.05: 1〜50: 1左右 〇 分散劑可促進形成極小且均勻粒徑之觸媒奈米粒子。 通常，於分散劑存在下，形成IV m以下大小之觸媒奈米 粒子。觸媒奈米粒子之粒徑爲50ηιη以下者宜，更佳者爲 20nm以下。 該觸媒溶液或觸媒懸浮液亦可含有爲了促進形成觸媒 奈米粒子之添加物。可添加如：無機酸、鹸化合物作爲添 加物。作爲無機酸，例如：鹽酸、硝酸、硫酸、磷酸等， 作爲無機鹸化合物，例如：氫氧化鈉、氫氧化鉀、氫氧化 鈣、氫氧化銨等。爲了將溶液或懸浮液之pH調整爲8〜13 ，亦可添加鹼性物質（如：氨水溶液），更理想係將溶液 或懸浮液之pH調整爲10〜11。高pH値時，觸媒前驅物呈 微細分離，而影響觸媒奈米粒子的粒徑。 又，亦可於觸媒溶液或觸媒懸浮液中加入爲了促進觸 媒奈米粒子形成之固體物質。例如：可於觸媒奈米粒子形 成時加入離子交換樹脂。固體物質可藉由簡單的操作，由 最終的觸媒溶液或觸媒懸浮液去除。 典型者係，將該觸媒溶液或觸媒懸浮液藉由混合0.5 小時〜14天可得到觸媒奈米粒子。混合溫度爲〇°C〜200 t 201006762 左右。混合溫度乃影響觸媒奈米粒子粒徑的重要因素。 使用鐵作爲觸媒前驅物使用時’典型者係鐵於溶媒內 以氯化鐵、硝酸鐵、硫化鐵等之鐵化合物存在之’該鐵化 合物藉由與分散劑進行反應或連結後’作成觸媒奈米粒子 。氯化鐵、硝酸鐵、硫化鐵等之鐵化合物多半溶解於水系 之溶媒。經由使用金屬鹽之觸媒奈米粒子的形成後’產生 副生成物。典型的副生成物’爲使用金屬而調製觸媒時產 • 生之氫氣。典型的實施形態中，觸媒奈米粒子於混合步驟 中被活化，使用氫，更進行還原。 理想的觸媒奈米粒子係以穩定且活性的金屬觸媒奈米 粒子之懸浮液被形成，藉由觸媒奈米粒子之穩定性抑制粒 子彼此凝聚，即使一部份或全部觸媒奈米粒子沈澱，經由 混合仍可輕易再懸浮化。 將上述作法所得到之觸媒奈米粒子作爲模版觸媒奈米 粒子使用。模版觸媒奈米粒子係擔任作爲促進碳材料前驅 ® 物之聚合及/或碳材料中間體之碳化之觸媒的作用。 步驟（2)中，碳材料前驅物只要可分散模版觸媒奈 米粒子者即可，並未特別限定。使模版觸媒奈米粒子分散 於媒介物中，於該模版觸媒奈米粒子之存在下，經由聚合 碳材料前驅物，於奈米粒子表面形成碳材料中間體。作爲 碳材料前驅物之理想的有機材料者，可列舉分子中具有爲 聚合具1個以上芳香族環、具有聚合用的官能基之苯或萘 衍生物。聚合化用之官能基，可列舉C〇〇H、C = 0、ΟΗ、 C = C、S03、NH2、SOH、N = C = 〇等。 -11 · 201006762 作爲理想碳材料前驅物之例’可列舉間苯二酚、苯酚 樹脂、蜜胺-甲醛凝膠、聚糠醇、聚丙烯腈、砂糖、石油 瀝青。 模版觸媒奈米粒子係於其表面與碳材料前驅物混合使 碳材料前驅物進行聚合。由於模版觸媒奈米粒子爲觸媒活 性，於其粒子附近擔任碳材料前驅物之聚合的開始及/或 促進的作用。 對於碳材料前驅物之模版觸媒奈米粒子量可使碳材料 前驅物設定爲形成最大量均勻之奈米碳材料中間體。模版 觸媒奈米粒子之量亦與所使用之碳材料前驅物之種類有關 。（碳材料前驅物）：（模版觸媒奈米粒子）莫耳比爲 0.1: 1〜100: 1者宜，較佳者爲1: 1〜30: 1。該莫耳比 ，觸媒奈米粒子之種類、觸媒奈米粒子之粒徑影響所得奈 米構造中空碳材料之碳部份的厚度。 模版觸媒奈米粒子及碳材料前驅物之混合物於模版奈 米觸媒粒子表面使碳材料中間體充份熟化至完全形成爲止 。形成碳材料中間體所需之時間，係與溫度、觸媒的種類 、觸媒的濃度、溶液的pH，所使用碳材料前驅物之種類 有關。 爲調整pH而加入氨後，可加快聚合速度，增加碳材 料前驅物彼此的交聯量，有效聚合。 可經由熱聚合之碳材料前驅物，通常聚合溫度愈高’ 愈促進加速聚合。理想的聚合溫度爲〇〜200。(：，更佳者爲 2 5°C 〜120T：。 201006762 使用鐵粒子，懸浮液之pH爲1〜14之範圍時，間苯二 酚·甲醛凝膠最理想之聚合條件爲〇〜90 t、熟化時間1〜 72小時。 步驟（3)中，使碳材料中間體碳化，形成碳材料， 得到奈米構造複合材料。碳化通常藉由燒成進行之。典型 的燒成係於500〜2500 °C之溫度下進行。燒成時，釋出碳 材料中間體中之氫原子、氮原子，引起碳原子之再配列， 形成碳材料。理想之碳材料爲石墨狀的層狀構造（多層狀 )’厚度爲1〜10〇nm，更佳者爲1〜20nm之構造。層數可 藉由碳材料中間體之種類、厚度、燒成溫度進行控制。又 ’奈米構造中空碳材料之碳部份的厚度亦可藉由碳材料前 驅物之聚合及/或碳材料中間體之碳化的進行度之調整進 行控制。 步驟（4)中，由奈米構造複合材料去除模版觸媒奈 米粒子’得到奈米構造中空碳材料。典型的去除係藉由使 奈米構造複合材料與硝酸、氟酸溶液等之酸、或氫氧化鈉 等之驗接觸而進行之。去除模版觸媒奈米粒子時，使奈米 構造複合材料與硝酸（例如5當量之硝酸）進行接觸者宜 ’使含有奈米構造複合材料之硝酸進行3〜6小時回流即可 。該去除中，利用不完全破壞奈米中空體構造或奈米環構 造之方法即可。奈米構造中空碳材料中，碳部份之厚度係 與上述步驟（3)之碳材料的厚度有關。 本發明中，奈米構造中空碳材料具特異的形狀、大小 、電氣特性。作爲奈米構造中空碳材料之典型的形狀者， -13- 201006762 爲具有中空部份之略球狀，或含有一部份具有中空部份之 略球狀體的形狀。奈米構造中空碳材料之形狀’粒徑均與 製造時所使用之模版觸媒奈米粒子之形狀、大小有關°奈 米構造中空碳材料之形狀、粒徑係於模版觸媒奈米粒子周 邊形成碳材料，因此亦將影響中空部份之形狀、直徑、奈 米構造中空碳材料之形狀、粒徑。奈米構造中空碳材料亦 可具有中空部份全部由碳部份圍繞之構造，中空部的一部 份由碳部份圍繞之構造，或多數之碳部份進行連結或成塊 @ ，各碳部份圍繞中空部份的全部或一部份的構造。 上述奈米構造中空碳材料中，其形狀、碳部份爲多層 狀時各碳部份的層數、碳部份的厚度、中空部份的直徑可 藉由透光型電子顯微鏡（TEM )進行。又，本發明中奈米 構造中空碳材料之BET比表面積通常爲50〜5 0 0m2/g。 本發明中無機粒子係指不含碳原子之固體粒子。惟， 即使含碳，以一氧化碳、二氧化碳、或碳酸鈣等之金屬碳 酸鹽、氫氰酸、金屬氫氰酸鹽、金屬氰酸鹽、金屬硫代氰 β 酸鹽含於無機粒子中。本發明之成形體中，無機粒子係連 結彼此奈米構造中空碳材料之黏著劑。 無機粒子之粒徑爲O.lnm〜lOOnm之範圍者宜，更佳 者爲0.1 nm〜50nm之範圍。又，無機粒子之粒徑，由其與 奈米構造中空碳材料之連結力之觀點視之，爲奈米構造中 空碳材料之粒徑以下者較爲理想，更理想者又爲奈米構造 中空碳材料之粒徑的10分之1以下。本發明中無機粒子之 粒徑係以激光繞射/散射式粒度分佈測定裝置所測定之平 -14- 201006762 均粒徑。 由與奈米構造中空碳材料之連結力之觀點視之’無機 粒子爲二氧化矽粒子、氧化鋁粒子、或二氧化矽粒子與氧 化鋁粒子之混合粒子者宜，更佳者爲二氧化矽粒子。 本發明中，無機粒子之形狀並未受限，而由其與奈米 構造中空碳材料之連結力之觀點視之，又以球狀、棒狀、 或鏈狀者宜，球狀之粒子所連接成的鏈狀粒子者宜。 具體而言，可列舉作爲球狀之二氧化矽粒子之日產化 學工業（股份）製之Snotex ST-XS (商品名）、Snotex ST-XL (商品名），作爲鏈狀之二氧化矽粒子之日產化學 工業（股份）製之Snotex PS-S、Snotex PS-S0(商品名） 等。 本發明成形體中無機粒子之含量，由奈米構造中空碳 材料彼此之連結效果之觀點視之，對於100重量份之奈米 構造中空碳材料而言，爲1〜100重量份之範圍者宜，由其 成形體強度與穩定性之観點視之，爲10〜7 0重量份之範圍 者較佳，特別爲15〜65重量份之範圍更佳，最佳者爲20〜 60重量份之範圍。 本發明成形體之一形態爲含有奈米構造中空碳材料與 無機粒子之膜。本發明之膜係指即使於成形體中，其厚度 仍未達lcm者。有關成形體，厚度係指成爲成形體之面中 最大面彼此的距離。奈米構造中空碳材料亦具有電氣特異 性，因此本發明之膜亦可應用於作爲防止靜電、電磁波護 罩、紅外線阻隔等之導電膜、或作爲乾電池、原電池、蓄 -15- 201006762 電池、氧化還原電容器、混合電容器、電雙層電容器等之 電極膜。 接著，進行說明本發明之含有奈米構造中空碳材料與 無機粒子之膜的製造方法。 本發明之膜可藉由將奈米構造中空碳材料與無機粒子 之混合物使用滾輥成形或加壓成形’作成膜之薄片成形法 、或將液體媒介物中分散該混合物之分散液塗佈於支撐體 上，形成分散液膜，接著由該分散液去除液體媒介物，形 @ 成膜之塗佈法等，公知之方法進行製造。 薄片成形法中，首先將奈米構造中空碳材料與無機粒 子投入混合機，混合得到膏狀混合物。此時，藉由添加少 量的液體媒介物，可提昇混合物的均勻性。接著，使該胥 狀混合物以壓延機成形等之滾輥成形或加壓成形等之成形 方法呈薄片狀成形後，可取得本發明之膜。又，爲了使上 述方法所得之膜作成特定之厚度，亦可進一步藉由滾輥進 行壓延。於膜中殘留液體媒介物時，使液體媒介物進行蒸 馨 發後去除之。 由其可輕易製作均勻膜厚之觀點視之，以藉由塗佈法 進行製膜者宜。針對塗佈法製造本發明膜進行更詳細的說 明。塗佈法係指使奈米構造中空碳材料與無機粒子分散於 液體媒介物中之分散液塗佈於支撐體上，形成分散液膜之 後，由該分散液膜去除液體媒介物，製作含有奈米構造中 空碳材料與無機粒子之膜的方法。塗佈法，係首先調製含 有奈米構造中空碳材料與無機粒子之分散液。作爲分散液 -16- 201006762 之調製方法者，可列舉於液體媒介物中添加特定量之奈米 構造中空碳材料與無機粒子，進行混合之方法，於特定量 奈米構造中空碳材料與無機粒子之混合物中添加液體媒介 物’進行混合之方法，將特定量之無機粒子分散於液體媒 介物之中間分散液中添加特定量之奈米構造中空碳材料， 進行混合之方法’使特定量之無機粒子分散於液體媒介物 中之第1中間分散液與特定量之奈米構造中空碳材料分散 • 於液體媒介物中之第2中間分散液進行混合之方法，使特 定量之奈米構造中空碳材料分散於液體媒介物中之中間分 散液中，添加無機粒子，進行混合之方法。混合時，可使 用公知的混合機。由使無機粒子及奈米構造中空碳材料更 容易均勻分散之面視之，以藉由使無機粒子分散於液體媒 介物中之中間分散液中添加奈米構造中空碳材料進行分散 之方法，調製分散液者宜。又，爲了得到分散性高的膜， 於作爲中間分散液之膠質二氧化矽中使奈米構造中空碳材 胃料分散後，調製分散液者宜。膠質二氧化矽係指二氧化矽 或其水合物之膠質。 本發明之液體媒介物並未特別限定。於形成分散液膜 後去除液體媒介物時，由其去除之容易度、分散液使用之 觀點視之，使用水、醇、水與醇之混合媒介物作爲液體媒 介物者宜，最佳者使用水最爲理想。 作爲用於製作本發明之分散液時之裝置者，可列舉球 磨機或振動混合器等用於一般之濕式粉碎之裝置。使用球 磨機或振動混合器時，特別是球磨機或容器的限定，並未 -17- 201006762 受限，依其作 粒子進行選擇 於支撐體 提式薄膜塗佈 裝置》由所形 體上形成含有 作爲去除 溫度下使液體 作爲中間分散 〜60分鐘後， 由其爲提高奈 性之觀點視之 膜後，爲了調 本發明成 無機粒子之線 性，因此本發 管引導線、半 接著說明 子之線的製造 本發明之 子之混合物由 之方法進行製 擠壓法中 入混合機中進 爲目的之奈米構造中空碳材料、無機粒子之 即可。 上塗佈分散液，形成分散液膜時，可使用手 機、棒塗佈機、塑模塗佈機等之公知之塗佈 成之分散液膜去除液體媒介物後，可於支撐 奈米構造中空碳材料與無機粒子之膜。 液體媒介物之方法，可列舉於5〇〜500 °C之 媒介物進行蒸發之方法。使用膠質二氧化矽 參 液時’首先於50〜80 °C之溫度下進行乾燥1 更100〜200°c之溫度下，乾燥1〜360分鐘， 米構造中空碳材料彼此之連結性，提昇造形 較爲理想。另外’以塗佈法於支撐體上形成 整膜的厚度，亦可加壓支撐體上之膜。 形體之一形態爲含有奈米構造中空碳材料與 。奈米構造中空碳材料於電氣上亦具有特異 明之線亦可應用於作爲電容器引導線、晶體 參 導體引導線、管球用引導線等之導線。 本發明之含有奈米構造中空碳材料與無機粒 方法。 線係可藉由將奈米構造中空碳材料與無機粒 塑模擠壓呈線狀，成形爲線之擠壓法等公知 造之。 ，首先將奈米構造中空碳材料與無機粒子投 行混合，得到膏狀混合物。此時，藉由添加 -18 - 201006762 少量的液體媒介物，可提昇混合物的均勻性。接著使該膏 狀混合物由擠壓機之塑模呈線狀擠壓成形後，可得到本發 明之線。又’將塑模加熱放置後，可使於擠壓成形時存在 於線中之液體媒介物蒸發後去除。 混合物係依該薄片成形法之說明所載之方法所製造者 Φ [實施例] 以下’更依實施例進行本件之具體說明，惟本發明並 未受限於實施例。 [實施例1] 奈米構造中空碳材料係使用上述方法所製造者。所使 用之奈米構造中空碳材料之碳部份爲多層狀，碳部份之厚 度爲16〜20nm，中空部份之直徑爲8〜11 nm，又，BET比 ® 表面積爲l〇6m2/g。使用膠質二氧化矽（日產化學工業之 Snotex PS-S;平均粒徑10〜50nm;球狀二氧化砂連結爲 50〜200nm之長度之鏈狀粒子；固形份濃度：2 0wt% )作 爲無機粒子。又，使用乙炔碳黑（電氣化學工業股份公司 之Denkablack、平均粒徑36nm ; 50%加壓品）作爲提昇導 電性之導電材料。 於32.0g之奈米構造中空碳材料與4.0g之乙炔碳黑中 添加80.0g之膠質二氧化矽，更加入純水，進行調製固形 成份濃度30重量％之漿料。該漿料爲含有32_0g之奈米構 -19- 201006762 造中空碳材料，4.0g之乙炔碳黑，16.〇g之二氧化矽。亦 即，每100重量份之奈米構造中空碳材料之無機粒子量爲 5 0重量份。 於厚度20/zm之鋁箔（支撐體）上，使用手提式薄膜 塗佈機塗佈該漿料，形成漿料膜後，於60 °C下加熱1小時 ，更於1 50 °C下加熱6小時後，將水去除，可於支撐體上形 成膜。 又，亦進行電氣特性之評定。首先，將由所得之支撐 _ 體與形成於該支撐體之膜所成之層合體切取2片1.5 cm X 2.0cm之大小。分別的厚度爲77 μ m與80 y m。將其充份乾 燥後，於工具袋（氮雰圍）中，使不鏽鋼作爲集電極使用 ，組裝成如圖1所示之電雙層電容器。亦即，將該2片層合 體片配置呈彼此電極膜相向，於兩電極膜間配置天然纖維 紙（分離器），形成電池，將此與電解液（富山藥品工業 股份公司之LIPASTE-P/TEMAF14N) —起封入鋁製盒中， 得到電雙層電容器。 _ 以3 00m A/g之定電流將所得之電雙層電容器進行充電 至電壓達到2.8V爲止，以3 00mA/g之定電流進行放電至電 壓爲0V爲止，進行充放電試驗。由此結果槪略算出電阻 ，其結果示於表1。 \ [比較例1] 除未添加膠質二氧化砂之外，與實施例1同法調製獎 料。該漿料爲含有16. Og之奈米構造中空碳材料，2.0§之 -20- 201006762 乙快碳黑。亦即，每100重量份之固體粒子之無機粒子量 爲〇重量份。接著，與實施例1同法於支撐體上形成膜，卻 無法製膜。 [比較例2 ] 使用活性碳取代奈米構造中空碳材料之外，與實施例 1同法調製漿料。該漿料爲含有16.0g之活性碳，2.0g之乙 # 炔碳黑’ 8.0g之二氧化矽。亦即，每1〇〇重量份固體粒子 之無機粒子量爲44.4重量份。於厚度2〇em之鋁箔（支撑 體）上，使用手提式薄膜塗佈機塗佈該漿料，形成漿料膜 後，於60 °C下加熱1小時，更於150 °C下加熱6小時後，去 除水後可於支撐體上形成膜。 另外，亦進行電氣特性之評定。所使用之膜厚分別爲 87/zm、78/zm。與實施例1同法製作電極，組裝電雙層電 容器，進行充放電試驗。由該結果槪略算出電阻，其結果 β 示於表1。 [表1] 實施例1 比較例1 比較例2 活性碳『gl 0 0 32.0 奈米構造中空碳材料[g] 32.0 16.0 0 導電劑『gl 4.0 2.0 4.0 無機粒子fg] 16.0 0 16.0 靜雷容量rF/g] 3.2 一 27.5 雷阻丨Ω 1 1 .Ox 1 0'3 一 3.03x10* -21 - 201006762 藉由實施例1所製作之膜，因爲導電性高’除可用於 乾電池、原電池、蓄電池、氧化還原電容器、混合電容器 、電氣雙層電容器等之電極，亦可應用於作爲防止靜電、 電磁波護罩、紅外線阻隔等之導電膜。 [實施例2] 於36.Og之奈米構造中空碳材料與2.8g之乙炔碳黑中 添加12.〇g之膠質二氧化矽，更添加純水，調製固形成份 參 濃度50重量％之漿料。該漿料爲含有36. Og之奈米構造中 空碳材料，2.8g之乙炔碳黑、2.4g之二氧化矽。亦即’每 100重量份奈米構造中空碳材料之無機粒子量爲6.6重量份 〇[Technical Field] The present invention relates to a molded body comprising a hollow carbon material having a nanostructure and inorganic particles, wherein the nanostructured hollow carbon materials are bonded to each other by the inorganic particles, and a method for producing the same. The invention further relates to a film formed from the shaped body. [Prior Art] The carbonaceous material has a highly diverse material composed of a carbon allotrope such as graphite, diamond or carbene, or a composite of these composites. In recent years, nanostructured carbon materials such as fullerenes, carbon nanotubes, and extremely fine carbon materials have attracted attention because of their different structures from carbon materials (graphite, diamond, amorphous carbon, etc.). . In addition, since the nanostructured carbon material has been put into practical use in various fields of application, it is necessary to prepare a system for supplying stable products at a low price. Further, since the characteristics of the applied products vary greatly, it is an important issue to deal with the shape control of various application technologies, the β structure, and the orientation control. In the discussion to solve this problem, a novel nanostructured hollow carbon material has recently been developed (refer to US 2007/0060471 Α 1). Regarding the size and structure of the material, the technique for imparting shape to the composition containing the nanostructured hollow carbon material is not mentioned. SUMMARY OF THE INVENTION One object of the present invention is to obtain a molded body having a high conductivity of a nanostructured hollow carbon material. In one aspect, the present invention relates to a molded body comprising a hollow carbon material of a nanostructure and inorganic particles which are bonded to each other by the inorganic particles. In one embodiment, the nanostructured hollow carbon material has a carbon portion-part and a hollow portion, and the hollow portion is entirely surrounded by the carbon portion, and the hollow portion is surrounded by the carbon portion. Or a majority of the carbon portions are joined or agglomerated, and the carbon portions are formed around all or a portion of the hollow portion. One of the ideal forms The 'nano-structured hollow carbon material meets the requirements of (A) and (B) below. (A) The carbon portion of the nanostructured hollow carbon material has a thickness ranging from 1 nm to 20 nm. (B) The hollow portion of the nanostructured hollow carbon material has a diameter in the range of 〇.5 nm to 90 nm. The nanostructured hollow carbon material is a nanostructured hollow carbon material obtained by a method comprising the following steps (1), (2), (3), and (4). (1) a step of producing a template catalyst nanoparticle, (2) a polymerization of a carbon material precursor in the presence of the template catalyst nanoparticle to form a carbon material intermediate on the surface of the template catalyst nanoparticle The steps. (3) A step of carbonizing the carbon material intermediate to form a carbon material to produce a nanostructure composite material. -6- 201006762 (4) The step of removing the smectic catalyst nanoparticle from the nanostructure composite material to produce a nanostructured hollow carbon material. One of the ideal forms is that the inorganic particles are cerium oxide. One of the ideal forms is that the formed body is in the form of a film. In one aspect, the present invention relates to a method for producing a molded body comprising: applying a dispersion in which a nanostructure hollow carbon material and inorganic particles are dispersed in a liquid medium to a support to form a dispersion liquid film, and a dispersion liquid The film removes the liquid medium to form a film containing a nanostructured hollow carbon material and inorganic particles. According to the present invention, a molded article having a nanostructure hollow carbon material and having high conductivity can be obtained. When the molded article of the present invention is formed into a film shape, it can be activated by applying high conductivity to the conductive film or the static electricity preventing film. When the molded body of the present invention is formed into a line shape, it can be used as a wire. [Embodiment] [Best Mode for Carrying Out the Invention] The molding system of the present invention contains a nanostructured hollow carbon material and inorganic particles. In the present invention, the nanostructured hollow carbon material has a nanometer size (about 5 ηιη to lym). The nanostructured hollow carbon materials each have a carbon portion and a hollow portion. The nanostructured hollow material of the present invention is preferably one that satisfies the following requirements (B) and further satisfies the following requirements (B) and (C). (A) The nanostructured hollow carbon materials each have a carbon portion and a hollow portion of 201006762 parts, and the hollow portion is entirely surrounded by a carbon portion, and the hollow portion is partially surrounded by a carbon portion, or a majority The carbon portion is joined 'or a block, and each carbon portion surrounds all or a part of the hollow portion. (B) The carbon portion of the nanostructured hollow carbon material has a thickness ranging from 1 nm to 1 00 nm. (C) The hollow portion of the nanostructured hollow carbon material has a diameter in the range of _0.5 nm to 90 nm. Further, in the present invention, the carbon portion of the nanostructured hollow carbon material may also be in the form of a plurality of layers, and may satisfy the following (D) requirements. (D) The carbon portion of the nanostructured hollow carbon material is a multi-layered structure composed of 2 to 200 layers. From the viewpoint of manufacturing efficiency, a multilayer structure composed of 2 to 100 layers is preferred. Further, in the present invention, the nanostructured hollow carbon material is obtained by a method comprising the steps (1), (2), (3) and (4) in the following order. (1) The step of producing a template catalyst nanoparticle. (2) The step of polymerizing the carbon material precursor in the presence of the template catalyst nanoparticle to form a carbon material intermediate on the surface of the template catalyst nanoparticle. (3) A step of carbonizing the carbon material intermediate to form a carbon material to produce a nanostructure composite material. (4) A step of removing the smectic catalyst nanoparticle from the nanostructure composite material to produce a nanostructured hollow carbon material. Hereinafter, the steps of (1), (2), (3), and (4) will be specifically described. -8 - 201006762 In the step (1), the smectic contact nanoparticle is produced as follows. One or more kinds of catalyst precursors and one or more kinds of dispersing agents are used, and then the catalyst precursor and the dispersing agent are reacted or linked to form a catalyst composite. Usually, the catalyst precursor and the dispersing agent are dissolved or dispersed in a suitable solvent to form a catalyst composite by linking the catalyst and the dispersing agent. The solution obtained by dissolving the catalyst precursor and the dispersant in a solvent is referred to as a "catalyst solution", and the dispersion obtained by dispersing the catalyst precursor and the dispersant in a solvent is referred to as a "catalyst suspension". The catalyst precursor is not particularly limited as long as it promotes polymerization of a carbon material precursor to be described later and/or carbonization of a carbon material intermediate to be described later, and is preferably a transition metal selected from the group consisting of iron, cobalt, and nickel. The better is iron. The catalyst composite system contains one or more kinds of dispersants. The dispersant is selected from those which promote the development of a catalyst nanoparticle having a desired stability and size uniformity. The dispersant refers to various organic molecules, polymers, oligomers, and the like. This dispersant is dissolved or dispersed in a suitable solvent for use. • As a solvent for the modulation of the catalyst complex, various solvents such as water and organic solvent can be used. A solvent is used to allow the catalyst precursor to interact with the dispersant. Further, the solvent can also function as a dispersing agent. The solvent can also be used as a suspension of the catalyst nanoparticles. As an ideal solvent, such as: water, methanol, ethanol, η-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, ethylene glycol, dimethylformamide, dimethyl amide, dichloromethane, etc. For example, you can mix these uses. This catalyst complex is believed to be surrounded by solvent molecules. After the catalyst complex is formed in the catalyst solution or the catalyst suspension, the solvent is removed to obtain a catalyst complex of dried -9-201006762. Further, the dried catalyst composite can be recovered into a suspension by the addition of a suitable solvent. The molar ratio of the dispersant to the catalyst precursor can be controlled in the catalyst solution or catalyst suspension. The proportion of the catalyst atom of the dispersant functional group is preferably from 0.01:1 to 100:1, more preferably from 0.05:1 to 50:1. The dispersant promotes the formation of a catalyst having a very small and uniform particle size. Nano particles. Usually, the catalyst nanoparticles having a size of IV m or less are formed in the presence of a dispersant. The particle diameter of the catalytic nanoparticle is preferably 50 nm or less, and more preferably 20 nm or less. The catalyst solution or catalyst suspension may also contain additives to promote the formation of catalytic nanoparticles. For example, an inorganic acid or a ruthenium compound may be added as an additive. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Examples of the inorganic ruthenium compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide. In order to adjust the pH of the solution or suspension to 8 to 13, an alkaline substance (e.g., an aqueous ammonia solution) may be added, and it is more desirable to adjust the pH of the solution or suspension to 10 to 11. At high pH, the catalyst precursor is finely separated and affects the particle size of the catalyst nanoparticles. Further, a solid substance for promoting the formation of the contact nanoparticle may be added to the catalyst solution or the catalyst suspension. For example, an ion exchange resin can be added when the catalyst nanoparticles are formed. The solid material can be removed from the final catalyst solution or catalyst suspension by a simple operation. Typically, the catalyst solution or the catalyst suspension is obtained by mixing the catalyst nanoparticles for 0.5 hours to 14 days. The mixing temperature is about 〇 °C~200 t 201006762. The mixing temperature is an important factor affecting the particle size of the catalyst nanoparticles. When iron is used as a catalyst precursor, 'typically iron is present in the solvent as an iron compound such as ferric chloride, iron nitrate or iron sulfide. 'The iron compound is reacted or linked by a dispersant. Nylon particles. Iron compounds such as ferric chloride, iron nitrate, and iron sulfide are mostly dissolved in a water-based solvent. By-products are produced after the formation of the catalyst nanoparticles using a metal salt. A typical by-product is a hydrogen produced when a catalyst is used to modulate a catalyst. In a typical embodiment, the catalytic nanoparticles are activated in the mixing step and further reduced using hydrogen. The ideal catalyst nanoparticle is formed by a suspension of stable and active metal catalyst nanoparticles, which inhibits the aggregation of particles by the stability of the catalyst nanoparticles, even if some or all of the catalyst nanoparticles The particles precipitate and can be easily resuspended via mixing. The catalyst nanoparticle obtained by the above method was used as a template catalyst nanoparticle. The template catalyst nanoparticle serves as a catalyst for promoting the carbonization of the polymerization of carbonaceous precursors and/or carbon material intermediates. In the step (2), the carbon material precursor is not particularly limited as long as it can disperse the template catalyst nanoparticles. The template catalyst nanoparticle is dispersed in a vehicle, and a carbon material intermediate is formed on the surface of the nanoparticle via the polymeric carbon material precursor in the presence of the template catalyst nanoparticle. The benzene or a naphthalene derivative which has a functional group which has one or more aromatic rings and has a polymerization function in the molecule is exemplified as the organic material of the carbon material precursor. Examples of the functional group for polymerization include C〇〇H, C = 0, ΟΗ, C = C, S03, NH2, SOH, and N = C = 〇. -11 · 201006762 As an example of a precursor of an ideal carbon material, resorcin, a phenol resin, a melamine-formaldehyde gel, a polydecyl alcohol, a polyacrylonitrile, a sugar, and a petroleum pitch may be mentioned. The template catalyst nanoparticle is mixed on the surface with a carbon material precursor to polymerize the carbon material precursor. Since the template catalyst nanoparticle is a catalytic activity, it acts as a starting and/or promoting action for the polymerization of the carbon material precursor in the vicinity of the particles. The amount of smectic nanoparticle for the carbon material precursor allows the carbon material precursor to be set to form the largest amount of uniform nanocarbon material intermediate. The amount of smectic catalyst nanoparticles is also related to the type of carbon material precursor used. (Carbon material precursor): (template catalyst nanoparticle) Mohr ratio is 0.1: 1~100: 1 is preferred, preferably 1: 1~30: 1. The molar ratio, the type of the catalytic nanoparticle, and the particle size of the catalytic nanoparticle affect the thickness of the carbon portion of the obtained nanostructured hollow carbon material. The mixture of the template catalyst nanoparticle and the carbon material precursor is used to fully mature the carbon material intermediate to the surface of the template nanoparticle catalyst particle. The time required to form the carbon material intermediate depends on the temperature, the type of catalyst, the concentration of the catalyst, the pH of the solution, and the type of carbon material precursor used. When ammonia is added to adjust the pH, the polymerization rate can be increased, the amount of cross-linking of the carbon material precursors can be increased, and the polymerization can be carried out efficiently. Carbonaceous material precursors, which can be thermally polymerized, generally have a higher polymerization temperature, which promotes accelerated polymerization. The ideal polymerization temperature is 〇~200. (:, better is 2 5 ° C ~ 120T: 201006762 When using iron particles, the pH of the suspension is in the range of 1 to 14, the most ideal polymerization conditions for resorcinol / formaldehyde gel is 〇 ~ 90 t The curing time is 1 to 72 hours. In the step (3), the carbon material intermediate is carbonized to form a carbon material to obtain a nanostructure composite material. Carbonization is usually carried out by firing. Typical firing is performed at 500 to 2500. At the temperature of °C, the hydrogen atoms and nitrogen atoms in the carbon material intermediate are released during the firing, and the carbon atoms are rearranged to form a carbon material. The ideal carbon material is a graphite-like layered structure (multilayer The structure has a thickness of 1 to 10 〇 nm, more preferably 1 to 20 nm. The number of layers can be controlled by the type, thickness and firing temperature of the carbon material intermediate. The thickness of the carbon portion can also be controlled by the polymerization of the carbon material precursor and/or the progress of the carbonization of the carbon material intermediate. In the step (4), the template catalyst nanoparticle is removed from the nanostructure composite material. 'Get nanostructured hollow carbon material. Typical The removal is carried out by contacting the nanostructure composite with an acid such as nitric acid or a hydrofluoric acid solution, or sodium hydroxide, etc. When the smectite nanoparticle is removed, the nanostructure composite is made with nitric acid ( For example, if the contact is carried out with 5 equivalents of nitric acid, the nitric acid containing the nanostructured composite material should be refluxed for 3 to 6 hours. In this removal, the method of incompletely destroying the nano hollow structure or the nanoring structure is used. In the nanostructured hollow carbon material, the thickness of the carbon portion is related to the thickness of the carbon material in the above step (3). In the present invention, the nanostructured hollow carbon material has a specific shape, size, and electrical characteristics. The typical shape of the nanostructured hollow carbon material, -13-201006762 is a slightly spherical shape having a hollow portion, or a shape containing a portion of a slightly spherical body having a hollow portion. The nanostructured hollow carbon material The shape 'particle size is related to the shape and size of the template nanoparticle used in the manufacture. The shape and particle size of the nanostructured hollow carbon material form carbon around the periphery of the template catalyst nanoparticle. The material, therefore, will also affect the shape and diameter of the hollow portion, the shape and particle size of the nanostructured hollow carbon material. The nanostructured hollow carbon material may also have a hollow portion surrounded by a carbon portion, the hollow portion a portion surrounded by a carbon portion, or a plurality of carbon portions joined or agglomerated @, each carbon portion surrounding all or a part of the hollow portion. In the above nanostructured hollow carbon material, The shape and the carbon portion are multi-layered, and the number of layers of each carbon portion, the thickness of the carbon portion, and the diameter of the hollow portion can be performed by a transmission electron microscope (TEM). Further, in the present invention, the nanometer is used. The BET specific surface area of the hollow carbon material is usually 50 to 500 m 2 /g. The inorganic particles in the present invention are solid particles containing no carbon atoms. However, even if carbon is contained, a metal such as carbon monoxide, carbon dioxide or calcium carbonate is used. Carbonate, hydrocyanic acid, metal hydrocyanate, metal cyanate, metal thiocyanate beta are contained in the inorganic particles. In the molded article of the present invention, the inorganic particles are bonded to each other to form an adhesive of a hollow carbon material. The particle diameter of the inorganic particles is preferably in the range of 0.1 nm to 100 nm, and more preferably in the range of 0.1 nm to 50 nm. Further, the particle diameter of the inorganic particles is preferably from the viewpoint of the bonding strength to the hollow carbon material of the nanostructure, and is preferably a particle diameter of the hollow structure of the nanostructure, and more preferably a hollow structure of the nanostructure. One tenth or less of the particle diameter of the carbon material. The particle diameter of the inorganic particles in the present invention is the average particle diameter measured by a laser diffraction/scattering particle size distribution measuring apparatus. From the viewpoint of the bonding force with the hollow carbon material of the nanostructure, it is considered that the inorganic particles are cerium oxide particles, alumina particles, or mixed particles of cerium oxide particles and alumina particles, and more preferably cerium oxide. particle. In the present invention, the shape of the inorganic particles is not limited, and it is preferably a spherical shape, a rod shape, or a chain shape from the viewpoint of the bonding force with the nanostructured hollow carbon material, and the spherical particles are used. It is preferred to connect the chain-like particles. Specifically, Snotex ST-XS (trade name) and Snotex ST-XL (trade name) manufactured by Nissan Chemical Industries Co., Ltd., which are spherical cerium oxide particles, are mentioned as chain cerium oxide particles. Snotex PS-S, Snotex PS-S0 (trade name), etc. manufactured by Nissan Chemical Industry Co., Ltd. The content of the inorganic particles in the molded article of the present invention is preferably in the range of 1 to 100 parts by weight based on the viewpoint of the effect of bonding the nanostructured hollow carbon materials to each other, and 100 parts by weight of the nanostructured hollow carbon material. From the viewpoint of the strength and stability of the molded body, it is preferably in the range of 10 to 70 parts by weight, particularly preferably in the range of 15 to 65 parts by weight, and most preferably in the range of 20 to 60 parts by weight. . One form of the molded body of the present invention is a film containing a hollow carbon material of a nanostructure and inorganic particles. The film of the present invention means a thickness of less than 1 cm even in a molded body. Regarding the molded body, the thickness means the distance between the largest faces in the faces of the molded body. The nanostructured hollow carbon material is also electrically specific. Therefore, the film of the present invention can also be applied as a conductive film for preventing static electricity, an electromagnetic wave shield, an infrared ray barrier, or the like, or as a dry battery, a primary battery, a battery, -15-201006762, An electrode film of a redox capacitor, a hybrid capacitor, an electric double layer capacitor, or the like. Next, a method for producing a film containing a hollow carbon material of a nanostructure and inorganic particles of the present invention will be described. The film of the present invention can be formed by a sheet forming method in which a mixture of a nanostructured hollow carbon material and inorganic particles is formed by roll forming or press forming, or a dispersion in which a mixture is dispersed in a liquid medium is applied. A dispersion liquid film is formed on the support, and then the liquid medium is removed from the dispersion, and the coating method of forming a film is formed by a known method. In the sheet forming method, a nanostructured hollow carbon material and inorganic particles are first introduced into a mixer and mixed to obtain a paste mixture. At this time, the uniformity of the mixture can be improved by adding a small amount of liquid vehicle. Then, the enamel mixture is formed into a sheet shape by a forming method such as roll forming or press forming such as calender molding, and the film of the present invention can be obtained. Further, in order to make the film obtained by the above method a specific thickness, it may be further rolled by a roll. When the liquid vehicle remains in the membrane, the liquid vehicle is evaporated and removed. From the standpoint that it is easy to produce a uniform film thickness, it is preferred to form a film by a coating method. The film of the present invention is produced by a coating method in more detail. The coating method is a method in which a dispersion in which a nanostructure hollow carbon material and inorganic particles are dispersed in a liquid medium is applied onto a support to form a dispersion liquid film, and then the liquid medium is removed from the dispersion liquid film to prepare a nano-containing material. A method of constructing a film of a hollow carbon material and inorganic particles. In the coating method, a dispersion containing a hollow carbon material of a nanostructure and inorganic particles is first prepared. As a preparation method of the dispersion liquid-16-201006762, a method of mixing a specific amount of a nanostructure hollow carbon material and inorganic particles in a liquid medium, and mixing the hollow carbon material and the inorganic particles in a specific amount of nanostructure can be mentioned. Adding a liquid medium to the mixture for mixing, adding a specific amount of inorganic particles to the intermediate dispersion of the liquid medium, adding a specific amount of the nanostructured hollow carbon material, and mixing the method to make a specific amount of inorganic a method in which a first intermediate dispersion in which a particle is dispersed in a liquid medium is dispersed with a specific amount of a nanostructured hollow carbon material and a second intermediate dispersion in a liquid medium is used to form a hollow carbon of a specific amount of nanostructure A method in which a material is dispersed in an intermediate dispersion in a liquid medium, and inorganic particles are added and mixed. When mixing, a known mixer can be used. By dispersing the inorganic particles and the nanostructured hollow carbon material more easily and uniformly, the dispersion is prepared by adding a nanostructured hollow carbon material to the intermediate dispersion in which the inorganic particles are dispersed in the liquid medium. Dispersing liquid is suitable. Further, in order to obtain a film having high dispersibility, it is preferred to disperse the nanostructured hollow carbon material in the colloidal ceria as an intermediate dispersion, and then prepare a dispersion. The colloidal cerium oxide refers to a colloid of cerium oxide or a hydrate thereof. The liquid vehicle of the present invention is not particularly limited. When the liquid medium is removed after the formation of the dispersion film, it is preferable to use the mixed medium of water, alcohol, water and alcohol as a liquid medium from the viewpoint of ease of removal and use of the dispersion. Water is ideal. As the apparatus for producing the dispersion liquid of the present invention, a device for general wet pulverization such as a ball mill or a vibrating mixer can be cited. When using a ball mill or a vibrating mixer, especially the definition of a ball mill or a container, it is not limited to -17-201006762, and it is selected as a particle-removing film coating device according to its shape as a removal temperature. After dispersing the liquid as an intermediate for ～60 minutes, the film is viewed as a film for improving the nephelability, and in order to adjust the linearity of the inorganic particles in the present invention, the manufacturing line of the hair tube guide line and the line of the second half is described. The mixture of the invention is prepared by a method in which a hollow carbon material or inorganic particles of a nanostructure for the purpose of being extruded into a mixer is used. When the dispersion liquid is applied to form a dispersion liquid film, the liquid medium can be removed by using a known dispersion film formed by a mobile phone, a bar coater, a mold coater or the like, and the hollow structure can be supported. A film of carbon material and inorganic particles. The method of the liquid medium can be exemplified by evaporation of a medium of from 5 Torr to 500 °C. When using colloidal cerium oxide ginseng liquid, 'firstly dry at a temperature of 50 to 80 ° C. 1 at a temperature of 100 to 200 ° C, dry for 1 to 360 minutes, and the structure of the hollow carbon materials of the rice structure is connected to each other to enhance the shape. More ideal. Further, the thickness of the entire film formed on the support by the coating method can also pressurize the film on the support. One of the forms is a hollow carbon material containing nanostructures. The nanostructured hollow carbon material is also electrically specific and can be applied to a conductor such as a capacitor guide wire, a crystal reference conductor guide wire, a guide wire for a pipe ball, or the like. The method of the present invention comprising a nanostructured hollow carbon material and an inorganic particle. The wire system can be formed by extruding a nanostructured hollow carbon material and an inorganic particle mold into a linear shape, and forming it into a line extrusion method. First, the nanostructured hollow carbon material and the inorganic particles are firstly mixed to obtain a paste mixture. At this point, the homogeneity of the mixture can be improved by adding a small amount of liquid vehicle from -18 to 201006762. Then, the paste mixture is linearly extruded from a mold of an extruder to obtain the yarn of the present invention. Further, after the mold is heated, the liquid medium present in the wire at the time of extrusion molding can be removed by evaporation. The mixture is manufactured according to the method described in the description of the sheet forming method. Φ [Examples] The following is a more detailed description of the present invention, but the present invention is not limited to the examples. [Example 1] A nanostructure hollow carbon material was produced by the above method. The carbon structure of the nanostructured hollow carbon material used is multi-layered, the carbon portion has a thickness of 16 to 20 nm, the hollow portion has a diameter of 8 to 11 nm, and the BET ratio® surface area is l〇6 m 2 / g. Using colloidal cerium oxide (Snotex PS-S of Nissan Chemical Industry; average particle diameter of 10 to 50 nm; spherical silica sand with a length of 50 to 200 nm; solid concentration: 20% by weight) as inorganic particles . Further, acetylene black (Denkablack of Electric Chemical Industry Co., Ltd., average particle diameter: 36 nm; 50% pressurized product) was used as a conductive material for improving conductivity. To 32.0 g of the nanostructured hollow carbon material and 4.0 g of acetylene black, 80.0 g of colloidal cerium oxide was added, and pure water was further added to prepare a slurry having a solid concentration of 30% by weight. The slurry was a hollow carbon material containing 32_0 g of nanostructure -19-201006762, 4.0 g of acetylene black, and 16. g of cerium oxide. That is, the amount of the inorganic particles of the hollow carbon material per 100 parts by weight of the nanostructured material is 50 parts by weight. The slurry was applied onto an aluminum foil (support) having a thickness of 20/zm using a portable film coater to form a slurry film, which was heated at 60 ° C for 1 hour and further heated at 150 ° C. After an hour, the water is removed and a film can be formed on the support. Also, the evaluation of electrical characteristics is also performed. First, two sheets of 1.5 cm X 2.0 cm were cut out from the laminate of the obtained support body and the film formed on the support. The thicknesses are 77 μm and 80 μm, respectively. After it was sufficiently dried, stainless steel was used as a collector in a tool bag (nitrogen atmosphere), and an electric double layer capacitor as shown in Fig. 1 was assembled. In other words, the two laminated sheets are arranged to face each other with an electrode film, and a natural fiber paper (separator) is placed between the two electrode films to form a battery, and this is combined with an electrolyte (LIPASTE-P/ of Toyama Pharmaceutical Industries Co., Ltd.) TEMAF14N) - Sealed into an aluminum case to obtain an electric double layer capacitor. _ The obtained electric double layer capacitor was charged at a constant current of 300 m A/g until the voltage reached 2.8 V, and discharged at a constant current of 300 mA/g until the voltage was 0 V, and a charge and discharge test was performed. From this result, the resistance was roughly calculated, and the results are shown in Table 1. [Comparative Example 1] A prize was prepared in the same manner as in Example 1 except that the colloidal silica sand was not added. The slurry is a hollow carbon material containing 16.0 g of nanostructure, 2.0 § -20-201006762 B fast carbon black. That is, the amount of the inorganic particles per 100 parts by weight of the solid particles is 〇 by weight. Next, a film was formed on the support in the same manner as in Example 1, but the film could not be formed. [Comparative Example 2] A slurry was prepared in the same manner as in Example 1 except that activated carbon was used instead of the nanostructure hollow carbon material. The slurry was cerium oxide containing 16.0 g of activated carbon and 2.0 g of acetylene black 8.0 g. That is, the amount of the inorganic particles per 1 part by weight of the solid particles was 44.4 parts by weight. The slurry was applied onto an aluminum foil (support) having a thickness of 2 〇em using a portable film coater to form a slurry film, which was heated at 60 ° C for 1 hour and further at 150 ° C for 6 hours. Thereafter, after removing water, a film can be formed on the support. In addition, the evaluation of electrical characteristics is also performed. The film thicknesses used were 87/zm and 78/zm, respectively. An electrode was fabricated in the same manner as in Example 1, and an electric double layer capacitor was assembled to carry out a charge and discharge test. From this result, the resistance was roughly calculated, and the result β is shown in Table 1. [Table 1] Example 1 Comparative Example 1 Comparative Example 2 Activated carbon "gl 0 0 32.0 nanostructured hollow carbon material [g] 32.0 16.0 0 Conductive agent "gl 4.0 2.0 4.0 inorganic particle fg] 16.0 0 16.0 Static lightning capacity rF /g] 3.2 a 27.5 lightning resistance 丨 Ω 1 1 .Ox 1 0'3 a 3.03x10* -21 - 201006762 The film produced by the first embodiment, because of high conductivity 'except for dry batteries, primary batteries, batteries An electrode such as a redox capacitor, a hybrid capacitor, or an electric double layer capacitor can also be used as a conductive film for preventing static electricity, an electromagnetic wave shield, an infrared ray barrier, or the like. [Example 2] In a 36.Og nanostructured hollow carbon material and 2.8 g of acetylene carbon black, 12. g of colloidal cerium oxide was added, and pure water was further added to prepare a slurry having a solid concentration of 50% by weight. material. The slurry was a hollow carbon material containing 30.6 g of nanostructure, 2.8 g of acetylene black, and 2.4 g of cerium oxide. That is, the amount of inorganic particles per 100 parts by weight of the nanostructured hollow carbon material is 6.6 parts by weight.
於厚度20 μιη之鋁箔（支撐體）上，利用手提式薄膜 塗佈機塗佈該漿料，形成漿料膜後，於60 °C下加熱1小時 ，更於150 °C下加熱6小時，將水去除後可於支撐體上形成 膜。所得到膜的厚度爲1 〇 8 y m。 G 由所得之膜切取1片大小爲3.0cmx3.0cm之膜片，測定 膜的表面電阻。表面電阻的測定係使用Lorester (股份公 司diainstruments製）。由重量與膜厚所算出之密度與表 面電阻之結果示於表2。 [實施例3] 於36.Og之鈷酸鋰（正極材料）與2.8g之奈米構造中 空碳材料中添加12. Og之膠質二氧化矽，更添加純水，調 -22- 201006762 製固形成份濃度50重量％之漿料。該漿料爲含有36.0g之 鈷酸鋰，2.8g之奈米構造中空碳材料，2.4g之二氧化矽。 亦即，每100重量份奈米構造中空碳材料之無機粒子量爲 85.7重量份。 於厚度20 μ m之鋁箔（支撐體）上，利用手提式薄膜 塗佈機，塗佈該漿料，形成漿料膜後，於60 °C下加熱1小 時，更於150°C下加熱6小時，將水去除後可支撐體上形成 0 膜。所得到之膜厚度爲75.0 /z m。 由所得膜切取1片大小爲3.0crnx3.0ein之膜片，測定膜 的表面電阻。表面電阻之測定係使用Lorester (股份公司 diastriiments製）。由重量與膜厚所算出之密度與表面電 阻之結果示於表2。 又，所使用之鈷酸鋰爲日本化學股份公司之商品名「 cellseed C-10N」（平均粒徑：12·0μ m)。 [比較例3] 於36.0g之鈷酸鋰（cellseed C-10N)與2.8g之乙炔碳 黑中添加12.0g之膠質二氧化矽，更添加純水，調製固形 成份濃度50重量％之漿料。該漿料爲含有36.0g之鈷酸鋰 ，2.8g之乙炔碳黑，2.4g之二氧化矽。亦即，奈米構造中 空碳材料爲〇重量份。 於厚度20/im之鋁箔（支撐體）上，利用手提式薄膜 塗佈機塗佈該漿料，形成漿料膜後，於6(TC下加熱1小時 ，更於150°C下加熱6小時，將水去除後，可於支撐體上形 -23- 201006762 成膜。所得到之膜厚度爲85.3/zm。 由所得到之膜切取1片大小爲3.0cmx3.0cm之膜片’測 定膜的表面電阻。表面電阻的測定係使用Loresten (股份 公司diainstruments製）。由重量與膜厚所算出之密度與 表面電阻之結果示於表2。 [表2] 實施例2 實施例3 比較例3 正極材料[g] 0 36.0 36.0 奈米構造中空碳材料[g] 36.0 2.8 0 導電劑[g] 2.8 0 2.8 無機粒子[g] 2.4 2.4 2.4 表面電阻[Ω /□] 1.9 1X10.1 4.67x101 5.14χ102 [產業上可利用性] 本發明可取得含有奈米構造中空碳材料，具高度導電 性之成形體。如：將本發明成形體作成膜狀，其可活化其 高導電性、應用於導電膜、靜電防止膜，將本發明成形體 作成線狀，可應用於導線。 【圖式簡單說明】 圖1係代表本發明實施例及比較例所製作之層合型電 雙層電容器的槪略圖。圖中，分別顯示：符號1爲加壓板 、2爲集電極、3爲極、4爲分離器、5爲絕緣材料。 【主要元件符號說明】 -24- 201006762 ❿The slurry was applied onto an aluminum foil (support) having a thickness of 20 μm by a hand-held film coater to form a slurry film, which was then heated at 60 ° C for 1 hour and further at 150 ° C for 6 hours. After the water is removed, a film can be formed on the support. The thickness of the obtained film was 1 〇 8 y m. G A film having a size of 3.0 cm x 3.0 cm was cut out from the obtained film, and the surface resistance of the film was measured. The surface resistance was measured using Lorester (manufactured by the company diainstruments). The results of the density and surface resistance calculated from the weight and the film thickness are shown in Table 2. [Example 3] The lithium cobalt oxide (positive electrode material) and the 2.8 g of nanostructured hollow carbon material were added with 1.0 g of colloidal ceria, and pure water was added thereto, and the solid form was adjusted to -22-201006762. A slurry having a concentration of 50% by weight. The slurry was composed of 36.0 g of lithium cobaltate, 2.8 g of a nanostructured hollow carbon material, and 2.4 g of cerium oxide. Namely, the amount of the inorganic particles per 100 parts by weight of the nanostructured hollow carbon material was 85.7 parts by weight. The slurry was applied onto an aluminum foil (support) having a thickness of 20 μm by a portable film coater to form a slurry film, which was then heated at 60 ° C for 1 hour and further heated at 150 ° C. After the water is removed, a 0 film can be formed on the support. The resulting film thickness was 75.0 /z m. A film having a size of 3.0 crnx 3.0 ein was cut out from the obtained film, and the surface resistance of the film was measured. The surface resistance was measured using Lorester (manufactured by the company diastriiments). The results of the density and surface resistance calculated from the weight and the film thickness are shown in Table 2. Further, the lithium cobalt oxide used was a product name "celleed C-10N" (average particle diameter: 12·0 μm) of Nippon Chemical Co., Ltd. [Comparative Example 3] 12.0 g of colloidal cerium oxide was added to 36.0 g of lithium cobaltate (cellseed C-10N) and 2.8 g of acetylene black, and pure water was further added thereto to prepare a slurry having a solid concentration of 50% by weight. . The slurry was 36.0 g of lithium cobaltate, 2.8 g of acetylene black, and 2.4 g of cerium oxide. That is, the carbon material in the nanostructure is 〇 by weight. The slurry was coated on a 20/μm aluminum foil (support) by a hand-held film coater to form a slurry film, and then heated at 6 (TC for 1 hour, and further heated at 150 ° C for 6 hours). After removing the water, the film can be formed on the support shape -23-201006762. The obtained film thickness is 85.3/zm. One piece of the film having a size of 3.0 cm x 3.0 cm is cut out from the obtained film. Surface resistance. The surface resistance was measured by Loresten (manufactured by diainstruments). The results of the density and surface resistance calculated from the weight and the film thickness are shown in Table 2. [Table 2] Example 2 Example 3 Comparative Example 3 Positive electrode Material [g] 0 36.0 36.0 Nanostructured hollow carbon material [g] 36.0 2.8 0 Conductive agent [g] 2.8 0 2.8 Inorganic particles [g] 2.4 2.4 2.4 Surface resistance [Ω /□] 1.9 1X10.1 4.67x101 5.14χ102 [Industrial Applicability] The present invention can obtain a molded article having a highly conductive structure containing a hollow carbon material of a nanostructure. For example, the formed body of the present invention can be made into a film, which can activate its high conductivity and be applied to a conductive film. , the static electricity prevention film, the shaped body of the present invention is formed into a line shape, and is applicable BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a laminated electric double layer capacitor produced by an embodiment of the present invention and a comparative example, in which: symbol 1 is a pressure plate and 2 is a collector. 3 is the pole, 4 is the separator, and 5 is the insulating material. [Main component symbol description] -24- 201006762 ❿
1 :加壓板 2 :集電極 3 :極 4 :分離器 5 :絕緣材料 -25-1 : Pressurizing plate 2 : Collector 3 : Pole 4 : Separator 5 : Insulating material -25-