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TW201008871A - Method for making a carbon nanotube/conductive polymer composite - Google Patents

Method for making a carbon nanotube/conductive polymer composite Download PDF

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Publication number
TW201008871A
TW201008871A TW97133081A TW97133081A TW201008871A TW 201008871 A TW201008871 A TW 201008871A TW 97133081 A TW97133081 A TW 97133081A TW 97133081 A TW97133081 A TW 97133081A TW 201008871 A TW201008871 A TW 201008871A
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Taiwan
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carbon nanotube
conductive polymer
acid solution
film
carbon
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TW97133081A
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Chinese (zh)
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TWI377171B (en
Inventor
Chui-Zhou Meng
Chang-Hong Liu
Shou-Shan Fan
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Hon Hai Prec Ind Co Ltd
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Priority to TW97133081A priority Critical patent/TWI377171B/en
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Publication of TWI377171B publication Critical patent/TWI377171B/en

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Abstract

The present invention relates to a method for making a carbon nanotube/conductive polymer composite. It includes the steps of: providing a carbon nanotube film; and polymerizing a conductive polymer on the carbon nanotube film by a method of chemical in situ polymerization.

Description

201008871 九、發明說明: 【發明所屬之技術領域】 本技術方案涉及一種複合材料的製備方法,尤其涉及 一種奈米碳管/導電聚合物複合材料的製備方法。 【先前技術】 自1991年日本NEC公司的Iijima發現奈米碳管(Carbon Nanotube,CNT)以來(Iilima S., Nature,1991,354, 56-58), 立即引起科學界及産業界的極大重視。奈米碳管具有優良 @的機械和光電性能,被認爲係複合材料的理想添加物。奈 米碳管/聚合物複合材料已成爲世界科學研究的熱點 (Ajjayan P.M., Stephan O., Colliex C., Tranth D. Science. 1994,265,1212-1215: Calvert P., Nature, 1999, 399, 210-211)。奈米碳管作爲增强體和導電體,形成的複合材料 具有抗靜電,微波吸收和電磁屏蔽等性能,具有廣泛的應 用前景。 先前技術中的奈米碳管/導電聚合物複合材料中的奈米 φ碳管多爲棒狀物,而導電聚合物以顆粒的形式分佈在奈米 碳管之間的間隙中。當所述奈米碳管/導電聚合物複合材料 應用於超級電容器、太陽能電池的電極時,其中的導電聚 合物充放電時會引起體積收縮和膨脹,而奈米碳管的中空 結構可緩解由上述導電聚合物的體積收縮和膨脹引起的奈 米碳管/導電聚合物複合材料的體積收縮和膨脹,而且奈米 碳管的高導電性可降低導電聚合物的電阻。因此,先前技 術中的奈米碳管/導電聚合物複合材料具有較好的導電性和 較高的比電容量(大於200法拉/克)。然而,先前技術中的 6 201008871 奈米碳管/導電聚合物複合㈣通過採料奈米碳管分散於 硫酸及硝酸等强氧化性酸或表面活性劑中進行分散,之後 再與導電聚合物的單體進行電化學反應,並最終在工作電 極上得至'J奈米碳官/導電聚合物複合材料的薄膜。通過强 酸處理,會使得所述奈米碳管受到一定程度的破壞,而使 用表面活性㈣理會使得表面活㈣丨在最終的奈米碳管/導 電聚合物材料中不易除去。因而,經强氧化性酸或表面活 性劑處理後得到的奈米碳管/導電聚合物複合材料的性能會 鲁受到影響。另’由於奈米碳管易團聚,目前一直不能很好 的分散,故,先前技術所製備得到的奈米碳管/導電聚合物 複合材料中的奈米碳管通常無法形成良好的導電網絡,且 有些相鄰奈米碳管之間間距較大,相互間接觸性較差,因 而不能充分發揮奈米碳管的優良導電性及導熱性能,造成 所述奈米碳管/導電聚合物複合材料的内阻較大、比電容量 較低。 有鑒於此,提供一種能夠使奈米碳管均勻分散、並且 • Z破壞奈米碳管結構的奈米碳管/導電聚合物複合材料的 製備方法實為必要。 【發明内容】 種奈米碳管/導電聚合物複合材料的製備方法,其包 括以下步驟··製備-奈米碳管薄膜;及採用化學原位聚合 導電聚合物複合在所述奈米碳管薄膜上,獲得—太: 碳管/導電聚合物複合材料。 不、 人^目^先前技術,本技術方㈣供的奈米碳f/導電聚 “勿複合材料的製備方法具有以下優點:其 7 201008871 碳管薄膜中的多個奈米碳管均勾分散且相互 =物故採用化學原位聚合法將所述奈米碳管薄膜 分=奈=導電聚合物複合材料 • 敢—,由於採用化學原位聚合法將 •=奈米碳管薄膜與導電聚合物單體複合,無需添加表面 、:劑’使得奈米碳管/導電聚合物複合材料中不包含表面 2性劑°其二’本技術方案提供的奈米碳管/導電聚合物複 ^材料的製備方法,不需要用強酸氧化奈米碳管,奈米碳 ❹官的結構完整’在製備過程中不會破壞奈米碳管的結構。 其四,採用化學原位聚合法將所述奈米 合物複合’製備工藝簡單,可實現連續'規模化::電: 成本較低。 【實施方式】 以下將結合附圖詳細說明本技術方案提供的奈米碳管 /導電聚合物複合材料的製備方法。 月參閱圖1本技術方案實施例提供一種奈米碳管/導 ❹電聚合物複合材料的製備方法,具體包括以下步驟: 步驟一,製備一奈米碳管薄膜。 所述製備奈来碳管薄膜的方法包括直接生長法、絮化 法、礙壓〉去及拉膜法等其他方*。所述奈米碳管薄膜包括 複數個均勻分佈的奈米碳管,且該複數個奈米碳管相互連 接形成導電網路結構。 本實施例採用絮化法製備所述奈米碳管薄膜,該方法 具體包括以下步驟: 201008871 (一)提供一奈米碳管原料。 本實施例中,所述奈米碳管原料的製備方法 以下步驟:(a)提供—平整基底,該基底可選用p型或n -型石夕基底,或選用形成有氧化層㈣基底,本實施例 •為採用4英寸的石夕基底;⑴在基底表面均句形成一催化 劑層,該催化劑層材料可選用鐵(Fe)、鈷(c〇)、鎳 或其任意組合的合金之一;(c)將上述形成有催化劑層的 基底在700〜90(TC的空氣中退火約3〇分鐘〜9〇分鐘; 參將處理過的基底置於反應爐中,在保護氣體環境下加熱到 500〜740°C,然後通入碳源氣體反應約5〜3〇分鐘,生長得 到奈米碳管陣列,其高度大於100奈米,優選為1〇〇奈米 〜10毫米;(e )使奈米碳管陣列脫離基底,獲得奈米碳管 原料。 該奈米破管陣列為複數個彼此平行且垂直於基底生長 的奈米碳管形成的純奈米碳管陣列,由於生成的奈米碳管 ❼長度較長’部分奈米碳管會相互纏繞。通過上述控制生長 條件’該超順排奈米碳管陣列中基本不含有雜質,如無定 型碳或殘留的催化劑金屬顆粒等。本實施例中碳源氣可選 用乙炔等化學性質較活潑的碳氫化合物,保護氣體可選用 氮氣、氨氣或惰性氣體。可以理解,本實施例提供的奈米 碳管陣列不限於上述製備方法。本實施例優選採用刀片或 其他工具將奈米碳管從基底刮落,獲得奈米碳管原料,其 中奈米碳管一定程度上保持相互纏繞的狀態。 所述奈米碳管包括單壁奈米碳管、雙壁奈米碳管及多 201008871 壁奈米碳管令的-種或幾種。該單壁奈米碳管的直 奈米〜50奈米,該雙壁奈米碳管的直徑為1〇奈米太 米,該多壁奈米碳管的直徑為1>5奈米,奈米 : .米碳管的長度在100奈米到1〇毫米之間。 过不 (二)將上述奈米碳管原料添加到溶劑t並進 處理獲得奈米碳管絮狀結構。 、 本實施例中,溶劑可選用水、易揮發的有機溶劑等。 絮化處理可通過㈣超聲波分散處理或高強度攪摔等方 ^。優選地’本實施例採用超聲波將奈米碳管在溶财分 散10〜30分鐘。由於奈米碳管具有極大的比表面積,相互 纏繞的奈米碳管之間具有較大的凡德瓦爾力。上述絮化處 =並不會將奈米碳管原料中的奈米碳管完全分散在溶劑 ’奈米碳管之間通過凡德瓦爾力相互吸引 網路狀結構。 风 (三)將上述奈米碳管絮狀結構從溶劑中分離,並對 ❼該奈米碳管絮狀結構定型處理以獲得奈米碳管薄膜。 、本實施例中,分離奈米碳管絮狀結構的方法具體包括 =下步驟:將上述含有奈米碳管絮狀結構的溶劑倒入放有 漏斗中;及靜置乾燥—段時間從而獲得分離的奈米 厌吕各狀結構。 所述疋型處理具體包括以下步驟:將上述奈米碳管絮 t構置於-容器中;將奈米碳管絮狀結構按照預定形狀 :二施加-定壓力於攤開的奈米碳管絮狀結構;及將奈 米奴官絮狀結構中殘留的溶劑烘乾或等溶劑自然揮發後獲 201008871 ,奈米碳管薄膜。可以理解,本實施例可通過控制奈米碳 官絮狀結構攤片的面積來控制奈米碳管薄膜的厚度和麵密 度。攤片的面積越大,則奈米碳管薄膜的厚度和麵密度就 .越j本實轭例中獲得的奈米碳管薄膜的厚度為工微米至 2毫米。 、另,上述分離與定型處理步驟也可直接通過抽濾的方 式獲得奈米碳管薄膜,具體包括以下步驟:提供一微孔滤 膜及-抽氣漏斗;將上述含有奈米碳管絮狀結構的溶劑經 過微孔濾膜倒入抽氣漏斗中;抽濾並乾燥後獲得奈米碳管 薄膜。該微孔遽膜為-表面光滑、孔徑為G 22微米的遽 f °由於抽遽方式本身將提供一較大的氣壓作用于奈米碳 管絮狀結構,該奈米碳管絮狀結構經過抽渡會直接形成一 均勻的奈米碳管薄膜。且,由於微孔滤膜表面光滑,該奈 米碳管薄膜容易剝離。 採用所述絮化法製備的奈米碳管薄膜,其包括複數個 ❼均勻分佈的奈米碳管’該複數個均句分佈的奈米碳管通過 凡德瓦爾力相互連接形成網路結構,從而形成一具有自支 標結構的奈来碳管薄臈,該奈米碳管薄膜具有較好的柔勤 性。 可以理解,所述奈米碳管薄膜的製備方法還可為直接 生長法、碾壓法或拉膜法等其他方法。所述直接生長法 用化學氣相沈積法於一基板上生長奈米碳管薄膜。該奈米 碳管薄膜為無序奈米碳管薄膜,該奈米碳管薄膜包括複數 個無序排列的奈米碳管。所述採用㈣法製備奈米碳管薄 11 201008871 膜的方法具體包括以下步驟:提供一奈米碳管陣列形成於 土底,及提供;I置擠壓上述奈米碳管陣列,從而 得到奈米碳管薄膜。該奈米破管薄膜為無序奈米碳管薄 .膜,且包括複數個沿—個或複數個方向擇優取向排列的夺 ,米碳管〔所述採用拉膜法製備奈米礙管薄膜的方法包括以 7步驟·製備-奈米碳管陣列;從上述奈米碳管陣列中選 疋疋寬度的複數個奈米碳管片斷,優選為採用具有一定 寬度的膠帶接觸奈米碳管陣列以選定一定寬度的複數個奈 ❹米碳管片斷;及以-定速度沿基本垂直于奈米碳管陣列生 長^向拉伸該複數個奈米碳管片斷,以形成一連續的奈米 碳皆溥膜。該奈米碳管薄膜為有序奈米碳管薄膜,其包括 複數個通過凡德瓦爾力首尾相連且沿同一方向排列的奈米 破管。 步驟二,採用化學原位聚合法將導電聚合物複合在所 述奈米碳管薄膜上,獲得一奈米碳管/導電聚合物複合材 料。 本技術方案採用化學原位聚合法將所述奈米碳管薄膜 與導電聚合物複合的方法具體包括以下步驟: 首先,製備一導電聚合物單體的酸溶液,將所述奈米 碳管薄膜浸入所述導電聚合物單體的酸溶液中,形成一包 含奈米碳管薄膜與導電聚合物單體的酸溶液。 所述形成一包含奈米碳管薄膜與導電聚合物單體的酸 溶液的方法具體包括以下步驟:提供2〇〜4〇質量份的導電 t合物单體’配製摩爾濃度為〇·;[〜5摩爾/升的酸溶液;將 12 201008871 所述導電聚合物單體溶於酸溶液中,得到導電聚合物 摩爾濃度為G.1〜5摩爾/升的導電聚合物單體的酸溶液,該 酸溶液中酸的摩爾濃度為〇.1〜5摩爾/升;取5〇〜9〇質量: •的奈米碳管薄膜,將其浸人所述導電聚合物的酸溶液= •形成一包含奈米碳管薄膜與導電聚合物單體的酸溶液;及 將含有奈米碳管薄膜及導電聚合物單體的酸溶液在〇〜5攝 氏度冷藏3〜10小時,以使得導電聚合物單體在奈米碳管 薄膜的奈米碳管形成的網路結構中均勻分散。 籲"所述酸溶液的濃度較低,因此不會氧化浸入其申的奈 米破管薄膜,從而避免了對奈米碳管結構的破壞二、所述& 電聚合物單體材料為苯胺、β比咯、噻吩、乙炔、對苯及對 f撐乙烯中的一種或幾種。所述酸溶液為鹽酸溶液、硫酸 溶液、硝酸溶液、磷酸溶液或乙酸溶液中的一種或幾種的 混合。本實施例中,所述導電聚合物單體材料為苯胺,所 述溶液為鹽酸溶液。 ❿ 本實施例中,所述製備一導電聚合物單體的酸溶液, 將所述奈米碳管薄膜浸入所述導電聚合物單體的酸溶液中 的方法具體包括以下步驟:取一容器,於該容器中配製4〇 毫升1摩爾/升的鹽酸溶液;用稱量天平稱量0·74504克的 苯胺單體油狀物( 0.74504克苯胺單體油狀物的物質的量 為0.008摩爾),並放入一容器内,向該容器内注入4〇毫 升1摩爾/升的鹽酸溶液,使所述苯胺單體油狀物溶於所述 鹽酸 >谷液中’製備成苯胺的摩爾濃度為〇.2摩爾/升的苯胺 的鹽酸溶液;用稱量天平稱量質量為401毫克的奈米碳管 13 201008871 薄膜,將其浸入所述0.2摩爾/升的苯胺的鹽酸溶液當中, ,浸有奈米碳管薄膜16的苯胺鹽酸溶液在q攝氏度〜5攝 3㈣,使得麵單財^碳管薄㈣奈米碳 *甚形成的網路結構中均勻分散。 ' 其次’製備氧化劑的酸溶液。 所述氧化劑的酸溶液的仰為將導電聚合物單體氧 ’從而使導電聚合物單體發生氧化聚合 物。製備氧化劑的酸溶液的方法具體包括以下步 =爾/升的酸溶液,配製成氧化㈣摩爾濃度為gi〜5摩爾 /升=化劑㈣溶液;及將所述氧化劑㈣溶 度〜5攝氏度冷藏3〜1〇小時。 僻氏 所述氧化劑為過硫酸胺、高猛酸钟或雙氧水中的一種 =:;:述酸溶液為鹽酸溶液、硫酸溶液、確酸溶液、 乙酸溶液中的—種或幾種的混合。所述導電聚 ❼體的酸溶液的摩爾濃度與所述氧化劑的酸溶液的摩 /辰又之比為1:2〜2:1。本實施例中,所述氧化劑為過硫酸 液2述酸錢為鹽聽液,所料電聚合物單體的酸溶 液的摩爾濃度與所述氧化劑的酸溶液的摩爾濃度之比為 丄11 〇 本實施例中’所述製備氧化劑的酸溶㈣方法具體包 =步驟··用稱量天平稱量1 8256克過硫酸銨粉末,並 芎:置於80晃升的容器内;向盛有過硫酸銨粉末的容 左入40毫升i摩升的鹽酸溶液,將過硫酸錢粉末 201008871 浴解在鹽酸溶液中,製備成過硫酸銨的摩爾濃度為摩 爾/升的過硫酸銨的鹽酸(!摩爾/升)溶液;及將所述過妒 酸銨的鹽酸溶液在〇〜5攝氏度冷藏3小時,使得過硫酸^ -更充分的溶解於鹽酸溶液中。 最後,將所述氧化劑的酸溶液與浸有奈米碳管薄膜的 導電聚合物單體的酸溶液混合,使導電聚合物單體聚合, 獲得奈米碳管/導電聚合物複合材料。 ο 上述導電聚合物單體聚合的方法具體包括以下步驟: 米奴官薄膜的導電聚合物單體的酸溶液置於 冰水混口物中;緩慢逐滴加入氧化劑的 =趙發生聚合反應,形成導電聚合物纖維 =氧_的^液全部滴加完畢,將所述奈米碳管薄膜的 -攝氏度冷藏與氧化劑的酸溶液的混合液在 藏含有奈米碳㈣膜的導電聚合物單體的酸溶 Ϊ聚= W混合液5〜2〇小時,作用係使得導 單體能狗充分均句聚合形Μ^人從而使仔導電聚合物 纖維複合在所述奈米碳管 :物纖:維’導電聚合物 管的管壁上,表或附者在所述奈米碳 複合 管壁上。上述冷藏為可選撰=和附著在所述奈米碳管的 有奈米碳管薄膜的導雷= 也可直接在室溫下將含 溶液的混合液放置52f:,單體的酸溶液與氧化劑的酸 小蚪,若聚合反應為放熱反應, 15 201008871 冷藏條件得到的奈米碳管/導電聚合物複合材料要比室溫 所得到的奈米碳管/導電聚合物複合㈣的導電性能好,因 此本技術領域的技術人員可根據實際情況選擇。所述導電 聚合物纖維的長度為100奈米〜1〇毫米,直徑為3〇夺米 〜120奈米。 ’ 本實施例中,可將所述含有奈米碳管薄膜的導電聚合 物單體的酸溶液與氧化劑的酸溶液的混合液放置於〇〜5攝 =度的環财,冷藏1(M、時,使得聚苯胺纖維複合在所述 不米碳管的表面或/和附著在所述奈求碳管的管壁上,或者 料聚本案纖維射彼此相互連接祕複合在所述奈米碳 官的表面或/和附著在所述奈米碳管的管壁上。 本技術方案奈米碳管/導電聚合物複合材料的製備方 採用將5〇〜90質量份的奈米碳管薄膜與20〜40質量 =聚合物單體配置的酸溶液混合,再加入由 里伤的氧化劑配置的氧化劑的酸溶液單 ❷氧化聚合成導電聚合物,從而與奈米碳管薄膜 :碳管/導電聚合物複合材料。上述奈米碳管薄 合物單體及氧化劑的質詈μ 等電t 製備的太半磁昝/道帝 '關係有利於確保本技術方案 = 聚合物複合材料中聚苯胺纖維複合 麵的表面或/和附著在所述奈 上’或者所述聚本案纖绐、罗&的&壁 述太乎石山其彼此相互連接後再複合在所 ““的表面或,和附著在所述奈米碳管的管壁上。 所㈣備奈米㈣/㈣聚合物複合㈣ 還可進—步⑽—採W液清洗錢乾所述奈米破ΐ 16 201008871 °具體地,該㈣可通過以下 方法實見.百先’將不朱石反管,導電聚合物 液中取出,將其放人財去離子水的容 除去奈米碳管/導電聚合物複合材料中的離子二多:’广 再將其放人盛有乙料容器巾清洗多切去人’ 導電聚合物複合材料中殘留的其他有機雜質 米碳管/導電聚合物複合材料取出,放人烘箱内,在 參 氏度下烘乾4小時,將奈米碳管/導電聚合物複合材料中的 乙醇蒸發出來。通過清洗奈米碳管/導電聚合物複合材料可 有效去除奈米碳管/導電聚合物複合材射存在的盆 子雜質,及殘留其他有機雜質,從而進—步提高奈米碳管/ 導電聚合物複合材料的純度。 請參閱圖2,本技術方案所製備的奈米碳管/導電聚合 物複合材料10包括複數個奈米碳管12及複數個導電聚: 物纖維14。所述複數個奈米碳管12相互連接形成一奈^ 碳管薄膜16,複數個導電聚合物纖維14複合在所述 碳管12的表面或/和附著在所述奈米碳管12的管壁上,所 述導電聚合物纖維14還可彼此相互連接後再複^在所述 奈米碳管12的表面或/和附著在所述奈米碳管12的管壁 上。在上述的奈米碳管/導電聚合物複合材料1〇中,奈米 碳管12形成的奈米碳管薄膜16起到了骨架作用,導電聚 合物纖維14依附在所述的奈米碳管薄膜μ骨架上。進一 步地’所述奈米碳管12和導電聚合物纖維14均勻分佈於 所述奈米碳管/導電聚合物複合材料中。 17 201008871 本技術方案所提供的奈米碳管/導電聚合物複合材料 的製備方法具有以下優點:其一,由於採用化學原位聚合 法將所述奈米碳管薄膜與導電聚合物複合,奈米碳管薄^ •中複數個奈米碳管均勻分散且相互連接形成導電網路’,使 .得制得的奈米碳管/導電聚合物複合材料中奈米碳管均句 分散。其二,由於採用化學原位聚合法將所述奈米碳管薄 膜與導電聚合物複合,無需添加表面活性劑,使得奈米碳 管/導電聚合物複合材料中不包含表面活性劑。其三,本技 術方案提供的奈米碳管/導電聚合物複合材料的製備方 法,不需要用強酸氧化奈米碳管,奈米碳管的結構完整, 在製備過程中不會破壞奈米碳管的結構。其四,採用化學 原位聚合法將所述奈米碳管薄膜與導電聚合物複合,製備 工藝1單’可實現連續、規模化生產,且成本較低。 綜上所述,本技術方案確已符合發明專利之要件,遂 依法,出專利申請。惟,以上所述者僅為本技術方案之較 參=實施例,自不能以此限制本案之申請專利範圍。舉凡熟 悉本案技藝之人士援依本技術方案之精神所作之等效修飾 或變化’皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1為本技辦方案實施例的奈米碳管/導電聚人物 合材料的製備方法的流程圖。 σ 山+圖2為本技術方案實施例的包含無序奈来碳管的奈米 妷管/導電聚合物複合材料的結構示意圖。 【主要元件符號說明】 18 201008871 奈米碳管/導電聚合物複合材料 10 奈米碳管 12 導電聚合物纖維 14 .奈米碳管薄膜 16 參 19201008871 IX. Description of the Invention: [Technical Field] The present technical solution relates to a method for preparing a composite material, and more particularly to a method for preparing a carbon nanotube/conductive polymer composite material. [Prior Art] Since the discovery of Carbon Nanotube (CNT) by Iijima of NEC Corporation in Japan in 1991 (Iilima S., Nature, 1991, 354, 56-58), it has immediately attracted great attention from the scientific community and industry. . Nano carbon tubes have excellent mechanical and electrical properties and are considered to be ideal additives for composites. Nanocarbon tubes/polymer composites have become a hotspot in scientific research worldwide (Ajjayan PM, Stephan O., Colliex C., Tranth D. Science. 1994, 265, 1212-1215: Calvert P., Nature, 1999, 399 , 210-211). As a reinforcement and an electrical conductor, the carbon nanotubes have a composite application with antistatic, microwave absorption and electromagnetic shielding properties, and have broad application prospects. The nano φ carbon tubes in the prior art carbon nanotube/conductive polymer composite are mostly rods, and the conductive polymers are distributed in the form of particles in the gap between the carbon nanotubes. When the carbon nanotube/conductive polymer composite is applied to an electrode of a supercapacitor or a solar cell, the conductive polymer in the charge and discharge causes volume shrinkage and expansion, and the hollow structure of the carbon nanotube can be relieved by The volume shrinkage and expansion of the carbon nanotube/conductive polymer composite caused by the volume shrinkage and expansion of the above conductive polymer, and the high conductivity of the carbon nanotube can reduce the electrical resistance of the conductive polymer. Therefore, the prior art carbon nanotube/conductive polymer composites have better electrical conductivity and higher specific capacitance (greater than 200 farads/gram). However, the prior art 6 201008871 carbon nanotube/conductive polymer composite (4) is dispersed in a strong oxidizing acid or surfactant such as sulfuric acid and nitric acid by a carbon nanotube, and then with a conductive polymer. The monomer undergoes an electrochemical reaction and finally a film of a 'J nanocarbon officer/conductive polymer composite material is obtained on the working electrode. The strong acid treatment will cause the carbon nanotubes to be damaged to some extent, and the use of surface activity (4) will make the surface active (4) enthalpy difficult to remove in the final carbon nanotube/conductive polymer material. Therefore, the performance of the carbon nanotube/conductive polymer composite obtained by treatment with a strong oxidizing acid or a surfactant may be affected. In addition, since the carbon nanotubes are easily agglomerated, they have not been well dispersed at present. Therefore, the carbon nanotubes in the carbon nanotube/conductive polymer composite prepared by the prior art generally cannot form a good conductive network. Moreover, some of the adjacent carbon nanotubes have a large spacing between each other, and the mutual contact between them is poor, so that the excellent electrical conductivity and thermal conductivity of the carbon nanotubes cannot be fully utilized, resulting in the carbon nanotube/conductive polymer composite material. The internal resistance is large and the specific capacitance is low. In view of the above, it is necessary to provide a method for preparing a carbon nanotube/conductive polymer composite capable of uniformly dispersing a carbon nanotube and a Z-destroying a carbon nanotube structure. SUMMARY OF THE INVENTION A method for preparing a carbon nanotube/conductive polymer composite material, comprising the steps of: preparing a carbon nanotube film; and chemically in-situ polymerizing a conductive polymer in the carbon nanotube On the film, obtain - too: carbon tube / conductive polymer composite. No, the person ^ ^ ^ previous technology, the technical side (four) for the preparation of nano carbon f / conductive poly "Do not composite material has the following advantages: its 7 201008871 carbon nanotube film in the carbon nanotubes are scattered And mutually = the physical chemical in-situ polymerization method to divide the carbon nanotube film into n = = conductive polymer composite material • Dare - due to the use of chemical in-situ polymerization method = = carbon nanotube film and conductive polymer Monomer recombination, no need to add surface, agent: so that the carbon nanotube / conductive polymer composite does not contain surface 2 agents. The second carbon nanotube / conductive polymer composite material provided by the technical solution The preparation method does not require oxidation of the carbon nanotubes with a strong acid, and the structural integrity of the nanocarbons does not destroy the structure of the carbon nanotubes during the preparation process. Fourth, the nanoparticles are chemically in situ polymerized. The composite preparation process is simple, and can be continuously 'scaled up': electricity: lower cost. [Embodiment] Hereinafter, the preparation of the carbon nanotube/conductive polymer composite material provided by the technical solution will be described in detail with reference to the accompanying drawings. method Referring to FIG. 1 , an embodiment of the present technical solution provides a method for preparing a carbon nanotube/conductive carbon polymer composite material, which specifically includes the following steps: Step one: preparing a carbon nanotube film. The method of the tube film includes a direct growth method, a flocculation method, an impeding pressure, a pull-out method, and the like. The carbon nanotube film includes a plurality of uniformly distributed carbon nanotubes, and the plurality of nanoparticles are The carbon tubes are connected to each other to form a conductive network structure. In this embodiment, the carbon nanotube film is prepared by a flocculation method, and the method specifically includes the following steps: 201008871 (1) Providing a carbon nanotube raw material. In this embodiment, The method for preparing the carbon nanotube raw material comprises the following steps: (a) providing a flat substrate, the substrate may be selected from a p-type or n-type stone substrate, or a substrate formed with an oxide layer (4), which is adopted in the embodiment. a 4-inch stone base; (1) forming a catalyst layer on the surface of the substrate, the catalyst layer material may be selected from iron (Fe), cobalt (c), nickel or any combination thereof; (c) Formed with a catalyst The substrate of the layer is annealed in air of 700~90 (TC for about 3 minutes to 9 minutes; the treated substrate is placed in a reaction furnace, heated to 500~740 ° C under a protective gas atmosphere, and then passed through The carbon source gas reacts for about 5 to 3 minutes, and grows to obtain a carbon nanotube array having a height greater than 100 nm, preferably 1 nm to 10 mm; (e) the carbon nanotube array is detached from the substrate to obtain The carbon nanotube raw material is a pure carbon nanotube array formed by a plurality of carbon nanotubes which are parallel to each other and perpendicular to the substrate, and the length of the formed carbon nanotubes is longer. The carbon nanotubes are intertwined. The growth conditions are controlled by the above. The super-sequential carbon nanotube array contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, etc. In the present embodiment, the carbon source gas may be selected from acetylene. For chemically active hydrocarbons, the protective gas may be nitrogen, ammonia or an inert gas. It can be understood that the carbon nanotube array provided in the embodiment is not limited to the above preparation method. In this embodiment, it is preferred to use a blade or other tool to scrape the carbon nanotubes from the substrate to obtain a carbon nanotube raw material, wherein the carbon nanotubes are kept in a state of being entangled to some extent. The carbon nanotubes include single-walled carbon nanotubes, double-walled carbon nanotubes, and many or more types of 201008871 wall-nanocarbon tubes. The single-walled carbon nanotube has a diameter of nanometer ~50 nm, and the double-walled carbon nanotube has a diameter of 1 〇 nanometer, and the diameter of the multi-walled carbon nanotube is 1 > 5 nm, Nai Meter: The length of the carbon tube is between 100 nm and 1 mm. (2) The above carbon nanotube raw materials are added to the solvent t and processed to obtain a nano carbon tube floc structure. In this embodiment, the solvent may be selected from water, a volatile organic solvent, or the like. The flocculation treatment can be carried out by (4) ultrasonic dispersion treatment or high-strength stirring. Preferably, the present embodiment uses ultrasonic waves to disperse the carbon nanotubes in the melt for 10 to 30 minutes. Due to the extremely large specific surface area of the carbon nanotubes, there is a large Van der Waals force between the intertwined carbon nanotubes. The above flocculation = does not completely disperse the carbon nanotubes in the carbon nanotube raw material between the solvent 'nanocarbon tubes' and attracts the network structure through the van der Waals force. Wind (3) The above-mentioned nano carbon tube floc structure is separated from the solvent, and the nano carbon tube floc structure is shaped to obtain a carbon nanotube film. In the embodiment, the method for separating the carbon nanotube floc structure comprises the following steps: pouring the solvent containing the nano carbon tube floc structure into a funnel; and standing still for a period of time to obtain The isolated nano-analyzed structure. The 疋 type treatment specifically comprises the steps of: arranging the above-mentioned carbon nanotubes in a container; and placing the carbon nanotubes in a predetermined shape: two application-fixing pressure to the unfolded carbon nanotubes The floc structure; and the solvent remaining in the nano-frozen floc structure or the solvent is naturally volatilized to obtain 201008871, a carbon nanotube film. It will be understood that this embodiment can control the thickness and surface density of the carbon nanotube film by controlling the area of the nanocarbon floc structure. The larger the area of the tile, the thickness and the areal density of the carbon nanotube film. The thickness of the carbon nanotube film obtained in the example of the yoke is from micron to 2 mm. In addition, the separation and sizing treatment step can also directly obtain the carbon nanotube film by suction filtration, specifically comprising the steps of: providing a microporous membrane and a pumping funnel; and the above-mentioned carbon nanotube containing flocculation The solvent of the structure is poured into a suction funnel through a microporous membrane; after suction filtration and drying, a carbon nanotube film is obtained. The microporous membrane is a smooth surface with a pore diameter of G 22 μm. Since the pumping method itself provides a large gas pressure to the carbon nanotube floc structure, the nano carbon tube floc structure passes. The extradition will directly form a uniform carbon nanotube film. Moreover, since the surface of the microporous membrane is smooth, the carbon nanotube film is easily peeled off. The carbon nanotube film prepared by the flocculation method comprises a plurality of carbon nanotubes uniformly distributed, and the plurality of carbon nanotubes distributed in a uniform sentence are interconnected by a van der Waals force to form a network structure. Thereby, a carbon nanotube having a self-supporting structure is formed, and the carbon nanotube film has good flexibility. It can be understood that the preparation method of the carbon nanotube film can also be other methods such as direct growth method, rolling method or film drawing method. The direct growth method uses a chemical vapor deposition method to grow a carbon nanotube film on a substrate. The carbon nanotube film is a disordered carbon nanotube film, and the carbon nanotube film comprises a plurality of randomly arranged carbon nanotubes. The method for preparing a carbon nanotube thin 11 201008871 film by the method (4) specifically comprises the steps of: providing a carbon nanotube array formed on the soil bottom, and providing; and placing the carbon nanotube array on the first surface to obtain the naphthalene Carbon tube film. The nano tube-breaking film is a thin film of disordered carbon nanotubes, and comprises a plurality of carbon nanotubes arranged in a preferred orientation along a direction or a plurality of directions (the method for preparing a nano tube film by using a film method) The method comprises the steps of: preparing a carbon nanotube array in 7 steps; selecting a plurality of carbon nanotube segments of a width from the carbon nanotube array, preferably contacting the carbon nanotube array with a tape having a certain width; Selecting a plurality of nanometer carbon nanotube segments of a certain width; and stretching the plurality of carbon nanotube segments at a constant velocity along a substantially perpendicular to the carbon nanotube array to form a continuous nanocarbon All are enamel membranes. The carbon nanotube film is an ordered carbon nanotube film comprising a plurality of nanotubes connected end to end by van der Waals force and arranged in the same direction. In the second step, a conductive polymer is composited on the carbon nanotube film by chemical in-situ polymerization to obtain a carbon nanotube/conductive polymer composite. The method for chemically in-situ polymerization of the carbon nanotube film and the conductive polymer comprises the following steps: First, preparing an acid solution of a conductive polymer monomer, and the carbon nanotube film Immersion in the acid solution of the conductive polymer monomer forms an acid solution comprising a carbon nanotube film and a conductive polymer monomer. The method for forming an acid solution comprising a carbon nanotube film and a conductive polymer monomer specifically comprises the steps of: providing 2 to 4 parts by mass of the conductive t-monomer monomer's molar concentration of 〇·; ~5 mol / liter of acid solution; 12 201008871 said conductive polymer monomer dissolved in an acid solution, to obtain a conductive polymer molar concentration of G. 1 ~ 5 mole / liter of the conductive polymer monomer acid solution, The molar concentration of the acid in the acid solution is 〇.1~5 mol/liter; taking 5 〇~9 〇 mass: • a carbon nanotube film, which is immersed in the acid solution of the conductive polymer = • forming a An acid solution comprising a carbon nanotube film and a conductive polymer monomer; and an acid solution containing a carbon nanotube film and a conductive polymer monomer is chilled at 〇 5 ° C for 3 to 10 hours to make a conductive polymer The body is uniformly dispersed in the network structure formed by the carbon nanotubes of the carbon nanotube film. The concentration of the acid solution is low, so it will not oxidize and immerse into the nano tube breaking film, thereby avoiding the damage to the structure of the carbon nanotube. 2. The & electropolymer monomer material is One or more of aniline, β-pyrrol, thiophene, acetylene, p-benzene and p-ethylene. The acid solution is a mixture of one or more of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution or an acetic acid solution. In this embodiment, the conductive polymer monomer material is aniline, and the solution is a hydrochloric acid solution. ❿ In this embodiment, the method for preparing an acid solution of a conductive polymer monomer, and immersing the carbon nanotube film in an acid solution of the conductive polymer monomer comprises the following steps: taking a container, 4 ml of a 1 mol/L hydrochloric acid solution was prepared in the vessel; 0. 74504 g of the aniline monomer oil was weighed by a weighing balance (the amount of the substance of 0.74504 g of the aniline monomer oil was 0.008 mol) And placed in a container, and injected into the container with 4 ml of a 1 mol/L hydrochloric acid solution to dissolve the aniline monomer oil in the hydrochloric acid > trough solution to prepare a molar concentration of aniline Is a 2 mol/L aniline hydrochloric acid solution; a 401 mg carbon nanotube 13 201008871 film is weighed by a weighing balance, immersed in the 0.2 mol/L aniline hydrochloric acid solution, dipped The aniline hydrochloric acid solution having the carbon nanotube film 16 is uniformly dispersed in the network structure formed by the thin (four) nanocarbon* of the surface of the carbon tube at q degrees Celsius ~ 5 to 3 (4). 'Second' prepares an acid solution of the oxidizing agent. The acid solution of the oxidant is raised to oxidize the conductive polymer monomer to cause the conductive polymer monomer to oxidize. The method for preparing an acid solution of an oxidizing agent specifically comprises the following steps: an acid solution of argon/liter, which is formulated into a oxidized (tetra) molar concentration of gi~5 mol/liter = a chemical (iv) solution; and a solubility of the oxidizing agent (tetra) of ~5 degrees Celsius Refrigerate for 3 to 1 hour. The oxidizing agent is a kind of persulphate, high acid clock or hydrogen peroxide. =:;: The acid solution is a mixture of hydrochloric acid solution, sulfuric acid solution, acid solution, acetic acid solution or several kinds. The ratio of the molar concentration of the acid solution of the conductive polyorganism to the molar ratio of the acid solution of the oxidizing agent is 1:2 to 2:1. In this embodiment, the oxidizing agent is a persulfate solution, and the ratio of the molar concentration of the acid solution of the electropolymer monomer to the molar concentration of the acid solution of the oxidizing agent is 丄11 〇. In the present embodiment, the acid solute (four) method for preparing the oxidizing agent is specifically packaged = step · Weighing 1 8256 g of ammonium persulfate powder by a weighing balance, and 芎: placed in a container of 80 liters; The ammonium sulfate powder is allowed to enter a 40 ml i-liter hydrochloric acid solution, and the persulfate money powder 201008871 is dissolved in a hydrochloric acid solution to prepare ammonium persulfate having a molar concentration of ammonium per liter of ammonium persulfate (! mole / liter) solution; and the hydrochloric acid solution of ammonium perrhenate is chilled at 〇 5 ° C for 3 hours, so that the persulfate is more fully dissolved in the hydrochloric acid solution. Finally, the acid solution of the oxidizing agent is mixed with an acid solution of a conductive polymer monomer impregnated with a carbon nanotube film to polymerize the conductive polymer monomer to obtain a carbon nanotube/conductive polymer composite. ο The method for polymerizing the above conductive polymer monomer specifically comprises the following steps: the acid solution of the conductive polymer monomer of the Minou film is placed in an ice-water mixture; the polymerization of the oxidant is slowly added dropwise to the oxidizing agent to form a polymerization reaction. The conductive polymer fiber=oxygen_all liquid is completely added, and the mixture of the nano-tube film and the acid solution of the oxidizing agent is stored in the conductive polymer monomer containing the nano-carbon (tetra) film. Acid-soluble ruthenium polymerization = W mixture for 5~2 hrs, the action system is such that the monomer can be fully polymerized in the shape of the dog so that the conductive polymer fiber is compounded in the carbon nanotube: material fiber: dimension On the wall of the conductive polymer tube, the surface or attached to the wall of the nanocarbon composite tube. The above refrigeration is optional = and the guide tube attached to the carbon nanotubes of the carbon nanotube film can also be placed directly at room temperature to the solution containing the mixture 52f:, the monomer acid solution and The acid oxidizing agent is small, if the polymerization reaction is exothermic, 15 201008871 The carbon nanotube/conductive polymer composite obtained under refrigeration conditions has better conductivity than the carbon nanotube/conductive polymer obtained at room temperature (4). Therefore, those skilled in the art can select according to actual conditions. The conductive polymer fibers have a length of from 100 nm to 1 mm and a diameter of from 3 to 120 nm. In the present embodiment, a mixture of the acid solution of the conductive polymer monomer containing the carbon nanotube film and the acid solution of the oxidizing agent may be placed in a ring of 〇 5 5 = kWh, and refrigerated 1 (M, When the polyaniline fibers are composited on the surface of the carbon nanotubes or/and attached to the wall of the carbon nanotubes, or the fibers of the present invention are interconnected to each other and secretly compounded in the nanocarbon The surface or / and attached to the wall of the carbon nanotube. The technical solution of the carbon nanotube / conductive polymer composite is prepared by using 5 to 90 parts by mass of the carbon nanotube film and 20 ~40 mass = polymer monomer configuration of the acid solution is mixed, and then added by the acid solution of the oxidant disposed of the oxidant, the monoacid is oxidized and polymerized into a conductive polymer, thereby reacting with the carbon nanotube film: carbon tube / conductive polymer Composite material. The above-mentioned carbon nanotube thinner monomer and oxidant 詈μμ isoelectric t prepared too much magnetic 昝/Dao Di' relationship is beneficial to ensure the technical solution = polyaniline fiber composite surface in polymer composite Surface or / and attached to the nai 'or The polychambers, the genus &&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& Nano (four) / (four) polymer compound (four) can also enter - step (10) - pick W liquid cleaning money dry the nano-breaking 16 201008871 ° specifically, the (four) can be seen through the following methods. Bai Xian 'will not Zhu Shi Back-pipe, the conductive polymer liquid is taken out, and it is released into the capacity of the ionized water to remove the ions in the carbon nanotube/conductive polymer composite: 'Guangzhou then puts it in the container of the container Washing the multi-cutting person's other organic impurities remaining in the conductive polymer composite, the carbon tube/conductive polymer composite material is taken out, placed in an oven, and dried at a temperature of 4 hours, and the carbon nanotubes/conducting Ethanol in the polymer composite evaporates. By cleaning the carbon nanotube/conductive polymer composite material, the boron impurities in the carbon nanotube/conductive polymer composite can be effectively removed, and other organic impurities remain, thereby Step to increase the carbon nanotube / conductive polymer complex The purity of the material. Referring to FIG. 2, the carbon nanotube/conductive polymer composite 10 prepared by the technical solution includes a plurality of carbon nanotubes 12 and a plurality of conductive poly-fibers 14. The plurality of nanometers The carbon tubes 12 are connected to each other to form a carbon nanotube film 16, and a plurality of conductive polymer fibers 14 are composited on the surface of the carbon tube 12 or/and adhered to the tube wall of the carbon nanotube 12, the conductive The polymer fibers 14 may also be interconnected to each other and then to the surface of the carbon nanotubes 12 or/and to the tube walls of the carbon nanotubes 12. In the above-mentioned carbon nanotubes/conductive polymerization In the composite material, the carbon nanotube film 16 formed by the carbon nanotube 12 functions as a skeleton, and the conductive polymer fiber 14 is attached to the μ carbon nanotube film μ skeleton. Further The carbon nanotubes 12 and the conductive polymer fibers 14 are uniformly distributed in the carbon nanotube/conductive polymer composite. 17 201008871 The preparation method of the carbon nanotube/conductive polymer composite provided by the technical solution has the following advantages: First, since the carbon nanotube film is combined with a conductive polymer by chemical in-situ polymerization, The carbon nanotubes are thin. • The plurality of carbon nanotubes are uniformly dispersed and interconnected to form a conductive network, so that the carbon nanotubes in the obtained carbon nanotube/conductive polymer composite are uniformly dispersed. Second, since the carbon nanotube film is combined with the conductive polymer by chemical in-situ polymerization, no surfactant is added, so that the carbon nanotube/conductive polymer composite does not contain a surfactant. Thirdly, the preparation method of the carbon nanotube/conductive polymer composite provided by the technical solution does not require the oxidation of the carbon nanotubes with a strong acid, and the structure of the carbon nanotubes is intact, and the nanocarbon is not destroyed during the preparation process. The structure of the tube. Fourthly, the carbon nanotube film is combined with the conductive polymer by chemical in-situ polymerization, and the preparation process can be realized in a continuous and large-scale production with low cost. In summary, the technical solution has indeed met the requirements of the invention patent, and the patent application is issued according to law. However, the above is only a comparative example of the technical solution, and it is not possible to limit the scope of patent application in this case. Equivalent modifications or variations made by those who are familiar with the skill of the present invention in the spirit of this technical solution shall be covered by the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of preparing a carbon nanotube/conductive poly-constitutive material according to an embodiment of the present invention. σ山+图2 is a schematic structural view of a nanotube/conductive polymer composite comprising a disordered carbon nanotube according to an embodiment of the present technical solution. [Main component symbol description] 18 201008871 Carbon nanotube/conductive polymer composite 10 Carbon nanotube 12 Conductive polymer fiber 14. Carbon nanotube film 16 Reference 19

Claims (1)

201008871 十、申請專利範圍 碳&/導電聚合物複合材料的製備方法 栝以下步驟: * 製備一奈米碳管薄膜;及 管薄膜2原:,二法將導電聚合物複合在所述奈米碳 2如得—奈米碳管/導電聚合物複合材料。 專利第1項所述的奈米碳管/導電聚人物複 口材料的製備方法,其中 "稷 方法包括直接生長法、:壓奈米碳管薄膜的製傷 3.如申喑專利銘… 拉膜法及絮化法。 ,直接生長法製備奈米 管薄=膜為用化學氣相沈積法於一基板上生長奈米碳 4· ^請專利第3項所料 合材料的製備方法,其中 ::::::複 米碳營薄膜,β ϋ 〇· /不水石厌管薄膜為無序奈 奈=管4膜5亥奈未碳管薄媒包括複數個無序排列的 5. 請專利範圍第2項所述的奈米碳 合材料的製備方法,其中,路、“導電I物複 碳管薄膜的方法包括以下步驟f採用拉膜法製備奈米 製備一奈米碳管陣列; 從上述奈米碳管陣列中選定— 管片斷,優選為採用具有 ^、硬數個奈米碳 陣列以選定—定寬度的複數個奈米好Λ r 20 201008871 二:定速度沿基本垂直于奈米碳管陣列生長方向拉伸 複數個不米石反管片斷’以形成一連續的奈米碳管薄 膜。 6·=申請專利範圍第5項所述的奈米碳管/導電聚合物複 :材料的製備方法,其中,所述奈米碳㈣膜為有序 、不未碳管薄膜,其包括複數個通過凡德瓦爾力首尾相 連且沿同一方向排列的奈米碳管。 ❹ ❹ 7. =申請專利範圍第2項所述的奈米碳管/導電聚合物複 石的製備方法’其中,所述採用碾壓法製備奈米 反&薄膜的方法具體包括以下步驟: 提供—奈米碳管陣列形成於一基底;及 提施壓裝置擠壓上述奈米碳管陣列,從而得到奈米 奴管薄膜。 8. 二請專利範圍第7項所述的奈米碳管/導電聚合物複 I本t!的製備方法’其中’所述奈米碳管薄膜為無序 二;;碳管薄膜’且包括複數個沿-個或複數個方向擇 優取向排列的奈米碳管。 人2專利ia圍第2項所述的奈米破管/導電聚合物複 签腺料的製備方法’其中’所述絮化法製備奈米碳管 溥膜包括以下步驟: 提供一奈米碳管原料; =述奈米碳管原料添加到溶劑中並進行絮化處理獲 仔不米碳管絮狀結構;及 述不米石厌官絮狀結構從溶劑中分離,並對該奈米碳 201008871 管絮狀結構定型處理。 10.如申4專利範圍第9項所述的奈米碳管/導電聚合物複 t材料的製備方法,其中,所述絮化法製備的奈米碳 U膜包括複數個均句分佈的奈米碳管,該複數個均 勻刀佈的奈米石厌官通過凡德瓦爾力相互連接形成網路 結構,從而形成一具有自支樓結構的奈来碳管薄膜。 α如申請專利範㈣i項所述的奈采碳管/導電聚合物複201008871 X. Patent application range Carbon & / Conductive polymer composite preparation method 栝 The following steps: * Preparation of a carbon nanotube film; and tube film 2 original:, two methods of the conductive polymer composite in the nano Carbon 2 is obtained as a carbon nanotube/conductive polymer composite. The method for preparing a carbon nanotube/conductive polymantic material according to the first item of the patent, wherein the method includes a direct growth method, a wound of a carbon nanotube film, and the like. Pull film method and flocculation method. The direct growth method is used to prepare the nano tube thin film: the film is formed by chemical vapor deposition on a substrate to grow nano carbon 4 · ^ Please prepare the material of the material of the third item, wherein:::::: Rice carbon camp film, β ϋ 〇 · / non-hydrated anatomical film is disordered Nana = tube 4 film 5 Heiner carbon tube thin medium including a plurality of disordered arrangement 5. Please refer to the rice described in item 2 of the patent scope The method for preparing a carbonaceous material, wherein the method for “conducting the carbon film of the conductive material comprises the following steps f: preparing a nano carbon nanotube array by using a pull film method; selecting from the above carbon nanotube array- The tube segment is preferably a plurality of nanometers having a constant number of nano carbon arrays selected to have a constant width. r 20 201008871 2: the constant velocity is stretched substantially perpendicularly to the growth direction of the carbon nanotube array. a non-meterite reverse tube segment' to form a continuous carbon nanotube film. 6·=Application of the carbon nanotube/conductive polymer complex described in claim 5: a method for preparing a material, wherein the nai The m-carbon (four) film is an ordered, non-carbon tube film, A plurality of carbon nanotubes connected end to end in the same direction by van der Valli force. ❹ ❹ 7. = Preparation method of carbon nanotube/conductive polymer boulder as described in claim 2 The method for preparing a nano-anti-film by a rolling method comprises the following steps: providing a carbon nanotube array formed on a substrate; and applying a pressing device to extrude the carbon nanotube array to obtain a naphthalene The film of the mino tube. 8. The preparation method of the carbon nanotube/conductive polymer complex described in item 7 of the patent scope, wherein the carbon nanotube film is disordered; carbon The tube film 'and includes a plurality of carbon nanotubes arranged in a preferred orientation along a direction or a plurality of directions. The preparation method of the nano tube/conductive polymer check-in gland described in the second item of the patent 2 Wherein the preparation of the carbon nanotube membrane by the flocculation method comprises the following steps: providing a carbon nanotube raw material; = adding the carbon nanotube raw material to the solvent and performing the flocculation treatment to obtain the floc Structure; and the description of the glutinous structure of the glutinous rice The method for preparing a nano carbon tube/conductive polymer complex t material according to the invention of claim 4, wherein The nano-carbon U film prepared by the flocculation method comprises a plurality of carbon nanotubes with a uniform sentence distribution, and the nano-stones of the plurality of uniform knives are interconnected by a van der Waals force to form a network structure, thereby forming a The carbon nanotube film of the self-supporting structure. α The carbon nanotube/conductive polymer complex described in the application of the patent (4) item i 合材料的製備方法,其中,所述採用化學原位聚合法 製備奈米碳管/導電聚合物複合材料的方法具體包括以 下步驟: 製備-冑電聚合物單體的酸溶液,將所述奈米碳管薄膜 浸入所述導電聚合物單體的酸溶液中,形成一包含夺米 碳管薄膜與導電聚合物單體的酸溶液; 不 製備一氧化劑的酸溶液;及 將所述氧化劑的酸溶液與浸有奈米碳管薄臈的導電聚 ❹ 合物單體的酸溶液混合,使導電聚合物單體聚合。 12. 如申請專利範圍第11項所述的奈米碳管/導電3聚合物 複合材料的製備方法,其中,所述酸溶液為鹽酸溶^、 硫酸溶液、硝酸溶液、磷酸溶液及乙酸溶液中的一種 或幾種的混合。 13. 如申請專利範圍第11項所述的奈米碳管/導電聚入物 複合材料的製備方法,其中,所述形成一包含奈来碳 管薄膜與導電聚合物單體的酸溶液的方法具體包括2 下步驟:提供20〜40質量份導電聚合物單體,配製摩= 22 201008871 浪度為0.1〜5摩爾/升的酸溶液; 將所述導電聚合物單體溶於酸溶液中,得到導電聚合物 單體摩爾濃度為0.1〜5摩爾/升的導電聚合物單體的酸 - 溶液; =50〜90質量份的奈米碳管薄膜,將其浸入所述導電 聚合物的酸溶液中,形成一包含奈米碳管薄膜與導電聚 合物單體的酸溶液;及 將3有奈米碳管薄膜的導電聚合物單體的酸溶液在 Ό 0〜5攝氏度冷藏3〜10小時。 14.如申睛專利範圍第13項所述的奈米碳管/導電聚合物 ’复。材料的製備方法’其中’所述導電聚合物單體材 料為苯胺、料、嗟吩、乙块、對苯及對苯撐乙婦中 的一種或幾種。 =申π專利圍第11項所述的奈米碳管/導電聚合物 ;合材料的製備方法,其中,所述製備-氧化劑的酸 ❹ 浴液的方法具體包括以下步驟: 稱量20〜40質量份的氧化劑於一容器中; 爾濃度為W〜5摩爾7升的酸溶液,配製成氧化 觫爾/辰度為〇·1〜5摩爾/升的氧化劑的酸溶液;及 16氧化劑的酸溶液在0〜5攝氏度冷藏小時。 專利範圍第15項所述的奈米複管/導電聚合物 料的製備方法,其中,所述氧化劑包括過硫酸 取:、兩錳酸鉀及雙氧水。 申》月專利$&圍第11項所述的奈米碳管/導電聚合物 23 201008871 所述導電聚合物單體的 劑的酸溶液的摩爾濃度 複合材料的製備方法,其中, 酸溶液的摩爾濃度與所述氧化 之比為1:2〜2:1。 I::專利卿U項所述的奈米碳管/導電聚合物 二料的製備方法’其中,所述使導電聚合物單體 二t備奈米碳管/導電聚合物複合材料的方法具體 包括以下步騾: 署你、Γ又有丁、米♦管薄膜的導電聚合物單體的酸溶液 置於冰水混合物t;及 2滴加人氧化劑的酸溶液,使得導電聚合物單體發生聚 :反應’形成導電聚合物纖維,導電聚合物纖維直接或 ::連!後複合在所述奈米碳管的表面或/和附著在所 述奈米碳管的管壁上。 申請專利範圍帛18項所述的奈米碳管/導電聚合物 T口材料的製備方法’其中’所述使導電聚合物單體 聚合’製備奈米碳管/導電聚合物複合材料的方法進一 步包括-待所述氧化劑的酸溶液滴加完$,將所述含 有奈米碳管薄膜的導電聚合物單體的酸溶液與氧化劑 的酸溶液的混合液在〇〜5攝氏度冷藏5〜2〇小時的步 周窓。 20.如申”月專利範圍帛11項所述的奈米碳管/導電聚合物 複合材料的製備方法,其中,所述製備奈米碳管/導電 聚合物複合材料的方法進—步包括用清洗溶劑清洗所 述奈米碳管/導電聚合物複合材料並烘乾,其具體包括 24 201008871 以下步驟: 將奈米碳管/導電聚合物複合材料從混合液中取出,將 其放入盛有去離子水的容器内清洗多次; - 再將其放入盛有乙醇的容器中清洗多次;及 取出奈米碳管/導電聚合物複合材料,放入烘箱内,在 80攝氏度下烘乾2〜6小時。The method for preparing a composite material, wherein the method for preparing a carbon nanotube/conductive polymer composite by chemical in-situ polymerization comprises the following steps: preparing an acid solution of a ruthenium polymer monomer, a carbon nanotube film is immersed in an acid solution of the conductive polymer monomer to form an acid solution comprising a rice carbon nanotube film and a conductive polymer monomer; an acid solution not preparing an oxidizing agent; and an acid of the oxidizing agent The solution is mixed with an acid solution of a conductive polycondensate monomer impregnated with a thin carbon nanotube to polymerize the conductive polymer monomer. 12. The method for preparing a carbon nanotube/conductive 3 polymer composite according to claim 11, wherein the acid solution is a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution, and an acetic acid solution. One or a mixture of several. 13. The method for preparing a carbon nanotube/conductive polymer composite according to claim 11, wherein the method of forming an acid solution comprising a carbon nanotube film and a conductive polymer monomer Specifically, the method includes the following steps: providing 20 to 40 parts by mass of a conductive polymer monomer to prepare an acid solution having a wave degree of 0.1 to 5 mol/liter; and dissolving the conductive polymer monomer in an acid solution, Obtaining an acid-solution of a conductive polymer monomer having a molar concentration of the conductive polymer monomer of 0.1 to 5 mol/liter; a film of a carbon nanotube of 50 to 90 parts by mass, immersing it in an acid solution of the conductive polymer An acid solution comprising a carbon nanotube film and a conductive polymer monomer is formed; and an acid solution of the conductive polymer monomer of the 3 carbon nanotube film is chilled at Ό 0 to 5 ° C for 3 to 10 hours. 14. The carbon nanotube/conductive polymer as described in claim 13 of the scope of the patent application. The preparation method of the material 'wherein the conductive polymer monomer material is one or more of aniline, material, porphin, ethyl bromide, p-phenylene and p-phenylene bromide. The method for preparing a composite material according to the invention, wherein the method for preparing the acid hydrazine bath of the oxidizing agent specifically comprises the following steps: weighing 20 to 40 a mass of the oxidizing agent in a container; an acid solution having a concentration of W 5 to 5 moles of 7 liters, and an acid solution having an oxidizing agent having an oxidizing enthalpy of 1 to 5 moles per liter; and 16 oxidizing agents The acid solution is chilled at 0 to 5 degrees Celsius. The method for producing a nanotube/conductive polymer according to claim 15, wherein the oxidizing agent comprises: persulfate: potassium dimanganate and hydrogen peroxide. The invention relates to a method for preparing a molar concentration composite material of an acid solution of a conductive polymer monomer according to the invention, wherein the acid solution is The ratio of the molar concentration to the oxidation is 1:2 to 2:1. I: The preparation method of the carbon nanotube/conductive polymer di-material described in the patent U, wherein the method for making the conductive polymer monomer two t-prepared carbon nanotube/conductive polymer composite is specific The following steps are included: an acid solution of a conductive polymer monomer having a film of butyl and butyl tubes is placed in an ice water mixture t; and 2 drops of an acid solution of a human oxidant are added to cause a conductive polymer monomer to occur. Poly: Reaction 'forms conductive polymer fibers, conductive polymer fibers directly or:: even! It is then composited on the surface of the carbon nanotube or/and attached to the wall of the carbon nanotube. A method for preparing a carbon nanotube/conductive polymer T-port material as described in claim 18, wherein the method of polymerizing a conductive polymer monomer to prepare a carbon nanotube/conductive polymer composite further Including - the acid solution of the oxidizing agent is added dropwise, and the mixture of the acid solution of the conductive polymer monomer containing the carbon nanotube film and the acid solution of the oxidizing agent is chilled at 〇 5 ° C for 5 to 2 〇 Hours of the hour. 20. The method for preparing a carbon nanotube/conductive polymer composite according to claim 11, wherein the method for preparing a carbon nanotube/conductive polymer composite further comprises The cleaning solvent cleans the carbon nanotube/conductive polymer composite and dried, and specifically includes 24 201008871. The following steps: the carbon nanotube/conductive polymer composite is taken out from the mixture, and placed in the containing Wash the container in deionized water several times; - Wash it in a container filled with ethanol for several times; and take out the carbon nanotube/conductive polymer composite, place it in an oven, and dry at 80 °C 2 to 6 hours. 2525
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TWI686969B (en) * 2018-04-16 2020-03-01 鴻海精密工業股份有限公司 Method for making polymer solar cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI686969B (en) * 2018-04-16 2020-03-01 鴻海精密工業股份有限公司 Method for making polymer solar cell

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