200921970 九、發明說明： .【發明所屬之技術領域】 本發明涉及一種鋰離子電池正極及其製備方法，尤其涉 及一種基於奈米碳管的鋰離子電池正極及其製備方法。 【先前技術】 經離子電池係一種新型的綠色化學電源，與傳統的鎳锅 '電池、鎳氫電池相比具有電壓高、壽命長、能量密度大的優 ^ 點。自1990年日本索尼公司推出第一代鋰離子電池後，它 已經得到迅速發展並廣泛用於各種可檇式設備。 鋰離子電池正極包括正極材料，正極材料主要由正極活 性物質構成。鋰離子電池正極的結構有兩種，一種係直接採 用具有自支撐結構的正極材料作為鋰離子電池正極，一種係 將正極材料塗敷或固定於一集電體上制得。正極活性物質一 般選用嵌入化合物，常見的有氧化鈷鋰、氧化鎳鋰、氧化錳 链等，其他的正極材料的活性物質還包括鐵的氧化物，其他 金屬氧化物等。但，由於這些正極活性物質本身的導電性能 差，電極的内阻較大，放電深度不夠，結果導致正極活性物 質的利用率低，電極的殘餘容量大，因此改善活性物質和集 電體之間以及活性材料顆粒之間的導電性對鋰離子電池正 極的性能至關重要，因此，在實際應用中一般需要加入導電 劑來改善活性材料的導電性能。 導電劑的種類及用量對活性物質的電極比容量及倍率 放電行為有較大的影響。石墨、乙快黑和碳纖維具有導電性 好、密度小、結構穩定以及化學性質穩定等特性，常被用作 7 200921970 鋰離子電池正極材料的導電劑。為了充分利用活性物質，這 些導電劑在正極材料中的重量百分含量通常達到15%甚至 _ 30%，大量的導電劑會導致粘結劑用量的增加，結果會導致 鐘離子電池能量濃度較低。 1991年日本科學家飯島澄男發現一種新型一維奈米材 料奈求碳管（請參見 “ Helical microtubules of graphitic .carbon ，S Iijima，Nature，vol.354，p56(1991))，奈米石户 ,管表現出的奇異的力學、電學和磁學性質使其成為研究工作 者矚目的焦點’奈米碳管的應用研究已滲透到各個領域。由 於具有優異的導電性能以及良好的一維結構，奈米碳管非常 適合用作電極的導電材料。中國科學院的王國平等人將奈米 石厌官粉末作為導電材料加入到正極活性 米碳管用作鐘離子二次電池正極導電劑”，'王中國(;二: 二術應用研討會，謂2 (顏）），通過機械攪拌和 二二：等手段使奈米碳管粉末與正極活性物質混合後制 、料’錢將此正極材料錄”電體上形成链離子 :在正二但’由於奈米碳管本身易團聚的性質，使奈米碳 :的改盖 的分散不均勻，對正極材料的導電性能無明 離子雷因而製備的轉子電池正極内阻較大，使用該链 、: 極的鋰離子電池充放電性能不佳。 正極種具有較低的㈣，綠電性能好⑽離子電池 正極及其製備方法實為必要。 【發明内容】 薄膜。該奈 種鍾離子電池正極，包括—奈米唆管複合 8 200921970 米碳管複合薄膜包括一奈米碳管薄膜結構和正極活性物質。 其中該奈米碳管薄膜結構包括至少兩層重疊且交叉設置的奈 米碳管薄膜，該正極活性物質附著在奈米碳管薄膜結構中的 奈米碳管管壁上或者填充在奈米碳管薄膜結構中的奈米碳管 管腔内。 所述奈米碳管薄膜包括多個首尾相連且擇優取向排列 的奈米碳管束。 所述鋰離子電池正極還可進一步包括一集電體，上述奈 米碳管複合薄膜設置於該集電體之上。所述集電體為金屬基 板。 一種鋰離子電池正極的製備方法，其包括以下步驟··提 供一奈米碳管陣列；採用一拉伸工具從奈米碳管陣列中拉取 獲得一奈米碳管薄膜結構；以及在奈米碳管薄膜結構中複合 正極活性物質形成一奈米碳管複合薄膜，從而得到一鋰離子 電池正極。 相較于先前技術，本技術方案所提供的的鋰離子電池正 極的製備方法將奈米碳管薄膜結構與正極活性物質複合，無 需解決奈米碳管在正極活性物質中的分散問題，因此操作簡 單；本技術方案所提供的裡離子電池正極中，正極活性物質 顆粒附著在奈米碳管薄膜結構中的奈米碳管管壁上或者填充 在奈米碳管薄膜中的奈米碳管管腔内形成奈米碳管複合薄 膜，故，奈米碳管與正極活性物質混合均勻，由於奈米碳管 具有良好的導電性能，因此可明顯提高鋰離子電池正極材料 的導電性能，使鋰離子電池正極具有較低的内阻，使用該正 9 200921970 極的鋰離子電池具有良好的充放電性能。 【實施方式】 方案實施例作 以下將結合附圖及具體實施例對本技術 進一步的詳細說明。 請參閱圖1及圖2,本技财案實_提供了—種链離子 電池正極1G，脑離子電池正極1Q包括—奈米碳管複人薄 該奈米碳管複合薄膜14包括—奈米碳管薄膜結構Μ 夕個正極活性物質18。其中正極活性物f顆粒Μ以顆粒 的形式設置在奈米碳管薄膜結構16中。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive electrode for a lithium ion battery and a method for preparing the same, and more particularly to a lithium ion battery positive electrode based on a carbon nanotube and a preparation method thereof. [Prior Art] The ion battery is a new type of green chemical power source, which has superior voltage, long life and high energy density compared with the traditional nickel pot 'battery and nickel-hydrogen battery. Since Sony introduced the first generation of lithium-ion batteries in 1990, it has been rapidly developed and widely used in a variety of portable devices. The positive electrode of the lithium ion battery includes a positive electrode material, and the positive electrode material is mainly composed of a positive electrode active material. There are two kinds of structures for the positive electrode of a lithium ion battery, one is a positive electrode material having a self-supporting structure as a positive electrode of a lithium ion battery, and the other is obtained by coating or fixing a positive electrode material on a current collector. As the positive electrode active material, an intercalation compound is generally used, and a common one is lithium cobalt oxide, lithium nickel oxide, or a manganese oxide chain, and other active materials of the positive electrode material include iron oxides and other metal oxides. However, since the positive electrode active material itself has poor conductivity, the internal resistance of the electrode is large, and the depth of discharge is insufficient. As a result, the utilization rate of the positive electrode active material is low, and the residual capacity of the electrode is large, thereby improving the relationship between the active material and the current collector. And the conductivity between the active material particles is critical to the performance of the positive electrode of the lithium ion battery. Therefore, in practical applications, it is generally required to add a conductive agent to improve the electrical conductivity of the active material. The type and amount of the conductive agent have a great influence on the specific capacity of the active material and the discharge behavior of the rate. Graphite, B-black and carbon fiber have good electrical conductivity, low density, stable structure and stable chemical properties. They are often used as conductive agents for the cathode materials of lithium battery in 2009. In order to make full use of the active materials, the weight percentage of these conductive agents in the positive electrode material usually reaches 15% or even -30%, and a large amount of conductive agent causes an increase in the amount of the binder, which results in a lower energy concentration of the ion battery. . In 1991, Japanese scientist Iijima Ichiro discovered a new type of one-dimensional nanomaterials for carbon tubes (see "Helical microtubules of graphitic .carbon , S Iijima, Nature, vol. 354, p56 (1991)), Nishi Shihu, tube The singular mechanical, electrical and magnetic properties that have emerged have made it the focus of research workers. The application research of carbon nanotubes has penetrated into various fields. Due to its excellent electrical conductivity and good one-dimensional structure, nano Carbon tube is very suitable for use as a conductive material for electrodes. Wang Guoping, a member of the Chinese Academy of Sciences, added nano-stone powder as a conductive material to a positive active carbon tube for use as a positive electrode for a positive ion battery. Two: The second application seminar, 2 (yan), through the mechanical stirring and 22: and other means to make the carbon nanotube powder and the positive active material mixed, the material 'money this positive material recorded on the electric body Forming chain ions: in the positive two but 'because of the nature of the carbon nanotubes themselves agglomerating, the dispersing of the nano-carbon: the unevenness of the cover is not uniform, and the conductivity of the positive electrode material is clear. The prepared rotor battery has a large internal resistance, and the lithium ion battery with the chain and the pole has poor charge and discharge performance. The positive electrode species has a low (four), and the green electricity performance is good. (10) The ion battery positive electrode and its preparation method are necessary. The invention relates to a film, a cathode of the nano-ion battery, comprising a nano-tube composite 8 200921970 a carbon nanotube composite film comprising a carbon nanotube film structure and a positive active material. The carbon nanotube film structure Including at least two layers of overlapping and intersecting carbon nanotube films attached to the carbon nanotube wall of the carbon nanotube film structure or the nanocarbon filled in the carbon nanotube film structure The carbon nanotube film comprises a plurality of carbon nanotube bundles arranged end to end and arranged in a preferred orientation. The lithium ion battery positive electrode may further comprise a current collector, and the carbon nanotube composite film is disposed. Above the current collector, the current collector is a metal substrate. A method for preparing a positive electrode of a lithium ion battery, comprising the following steps: providing a carbon nanotube array; The stretching tool extracts a carbon nanotube film structure from the carbon nanotube array; and forms a carbon nanotube composite film by compounding the positive electrode active material in the carbon nanotube film structure, thereby obtaining a lithium ion battery positive electrode. Compared with the prior art, the preparation method of the positive electrode of the lithium ion battery provided by the technical solution combines the structure of the carbon nanotube film with the positive active material, and does not need to solve the problem of dispersion of the carbon nanotube in the positive active material, so The operation is simple; in the anode of the ion battery provided by the technical solution, the positive electrode active material particles are attached to the carbon nanotube tube wall in the carbon nanotube film structure or the carbon nanotubes filled in the carbon nanotube film The carbon nanotube composite film is formed in the lumen, so that the carbon nanotube and the positive active material are uniformly mixed. Since the carbon nanotube has good electrical conductivity, the conductivity of the positive electrode material of the lithium ion battery can be significantly improved, and the lithium is made. The positive electrode of the ion battery has a low internal resistance, and the lithium ion battery using the positive 9 200921970 pole has good charge and discharge performance. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. Referring to FIG. 1 and FIG. 2, the present invention provides a positive ion 1G of a chain ion battery, and a positive electrode 1Q of a brain ion battery includes a carbon nanotube composite thinner. The carbon nanotube composite film 14 includes a nanometer. The carbon nanotube film structure is a cathode active material 18. Wherein the positive electrode active material f particles are disposed in the form of particles in the carbon nanotube film structure 16.
Jt-步地，所述奈来碳管薄膜結構16包括至少兩層重疊 且又又。又置的奈米石反官薄膜，奈米碳管薄膜之間通過凡择瓦 爾力緊密結合。該奈Μ管薄膜包括多個首尾相連且擇^取 向排列的奈米碳管束’相鄰的奈米碳管束之間通過凡德瓦爾 力連接。所述奈米碳管薄膜的寬度可為i厘米〜1Q厘米，厚 度為^).01微米〜100微米。奈米碳管薄膜結構16具有多個微 孔H亥微孔孔徑分佈均勻，其大小一般小於100奈米。該奈 二笞溥膜結構16中的奈米碳管薄膜的層數不限，且相鄰兩 :奈米碳官薄膜之間交又的角度不限，具體可依據實際需求 :備π參閱圖2和圖4，本技術方案實施例優選提供了一 '1 f ^官薄膜結構16，包括重疊且交叉設置的200層奈米碳 ^薄膜，所述奈米碳管薄膜之間交叉的角度為90度。其中， 為二来兔官薄膜結構16所具有的微孔孔徑大小為60奈米， 不米兔官薄膜結構16中奈米碳管薄膜的寬度為5厘米，厚 度為50微米。 200921970 .進-步地，所述正極活性物質Μ 薄膜結構16中的夸米破其艿辟L 1也附者在不未石厌吕 内。正極活性物質18為夺米極 t*厌吕吕腔 〜1Γ1太止*、丨， 卞枝的顆粒，粒徑大小為3奈米 〜0不未。奈米級正極活性物 m , 物貝18與奈米碳管薄膜結構16 之間通過凡德瓦爾力相έ士人。 T ^ 1 〇 、D σ本技術方案實施例優選的奈米 級正極活性物質18的粒徑大小為6奈米。 物或mtrt·物質18可選自鐘的氧化物、其他金屬氧化 鋰…:/ S °所述鐘的氧化物包括氧化姑鐘、氧化鎳 鐘、氧化猛鋰。所述发仙’ 氧化物等。所料他物包括域氧化物、鐵的 構LiM λΛ 物質包括5V正極材料如央晶石結 本I 子的正極材料如_亞鐵鐘等。 本實知例中制氧化料做為正極活性物質Μ。 另外’該轉子電池正極Μ進—步還可以包括—集電體Jt-step, the carbon nanotube film structure 16 comprises at least two layers overlapping and yet again. The set of nano-stone anti-official film, the carbon nanotube film is closely combined by the Valent force. The natrix film comprises a plurality of carbon nanotube bundles connected end to end and arranged in an orientation. The adjacent carbon nanotube bundles are connected by a van der Waals force. The carbon nanotube film may have a width of from i cm to 1 Q cm and a thickness of from .01 μm to 100 μm. The carbon nanotube film structure 16 has a plurality of micropores, and has a uniform pore size distribution, and its size is generally less than 100 nm. The number of layers of the carbon nanotube film in the naphthalene film structure 16 is not limited, and the angle between the two adjacent carbon nano-films is not limited, and may be according to actual needs: 2 and FIG. 4, the embodiment of the present technical solution preferably provides a '1 f ^ official film structure 16, including overlapping and intersecting 200-layer nano carbon films, and the angles of intersection between the carbon nanotube films are 90 degrees. Among them, the microporous pore size of the rabbit film structure 16 is 60 nm, and the width of the carbon nanotube film in the buffalo film structure 16 is 5 cm and the thickness is 50 μm. 200921970. Further, the quarti in the positive electrode active material 薄膜 film structure 16 is also attached to the L1. The positive active material 18 is a rice-killing pole t* 厌吕吕 cavity ~1Γ1 too long*, 丨, lychee particles, the particle size is 3 nm ~0 not. The nano-scale positive active material m, between the shellfish 18 and the carbon nanotube film structure 16 passes through the van der Waals force. T ^ 1 〇 , D σ The preferred nano-sized positive electrode active material 18 of the embodiment of the present invention has a particle size of 6 nm. The material or mtrt substance 18 may be selected from the group consisting of an oxide of a bell, other metal lithium oxide...: / S ° The oxide of the clock includes an oxidation bell, a nickel oxide clock, and lithium oxide oxide. The scented oxide or the like. It is expected that the material includes a domain oxide, an iron-structured LiM λ Λ material including a 5V positive electrode material such as a positive electrode material of a cristobalite structure such as a ferrous iron. In the present embodiment, the oxidized material is used as the positive electrode active material Μ. In addition, the positive electrode of the rotor battery may further include a current collector
12。所述的奈米碳營满人J 隹恭髀191¾ 5溥膜14設置於該集電體12上。該 木电體12可為一今Μ宜 落。 、，屬基板，本實施例優選的集電體12為銅 因所述奈米碳管薄膜結構16 的導電性能，且奈W管·h ^&賴具有良好 ，官稷合溥膜14本身已經具有-定的自支撑性及二： 性。實際應用時’可直接 性及％疋 子電池正極1〇。另管複合薄膜14用作鋰離 的比表面積，故使用該正極 、有極大 晉的妄、士叫as 電'也可改善電池存儲办 里的农減問過，且該鐘離子電池具有良好的高速充^^ 進一步地，正極活性物暂 兒特性。 料物f18均勻地附著在料導電劑的 11 200921970 奈米妷官薄膜結構16中的奈米碳管 碳管管腔内，從而有效地提高正極活 次=在奈米 •顯著提高了轉子電池正⑴㈣、^物貝18的活性’同時 離丁电池正極10的導電性能。 備方法主要包括以下幾個步驟： 10的衣 步驟一、提供—奈米碳管陣列，優ig妯，^ + 排奈米碳管陣列。 W也，該陣列為超順 所述奈米碳管_為單壁奈米碳 陣列及多壁奈㈣管_中的—種。 〃本實_巾’超獅奈米碳料關製備方法採用化學 乳相沉積法，其具辭驟包括..⑴提供—平整基底，該基 ，可選用P型或N型梦基底，或選用形成有氧化層的石夕^ 底’本實施例優選為採用4英寸的石夕基底；（b)在基底表面 均勻形成-催化劑層’該催化劑層材料可選用鐵（仏）、始 (0 )錄（Νι )或其任意組合的合金之一；（〇 )將上述形 成有催化劑層的基底在wot〜_。⑽空氣中退火約3〇分鐘 =〇分知，（d)將處理過的基底置於反應爐巾，在保護氣體 兄下加熱到500C〜740C，然後通入碳源氣體反應約5分 鐘〜30分鐘，生長得到超順排奈米碳管陣列’其高度為2〇〇 微米〜400微米。該超順排奈米碳管陣列為多個彼此平行且垂 直於基底生長的奈米碳管形成的純奈米碳管陣列。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。該奈米碳管陣列中 的奈米碳管彼此通過凡德瓦爾力接觸形成陣列。 12 200921970 • '本實施例巾碳源氣可_乙快、乙稀、甲料化學性質 較活潑的碳氫化合物，本實施例優選的碳源氣為乙炔；保護 氣體為氮氣或惰性氣體，本實施例優選的保護氣體為氬氣二 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，還可以包括其他方法如鐳射伽法、等離子體^ 法等。 步驟二、制-拉伸工具從奈米碳管陣列中拉取 奈米碳管薄膜結構16。 該奈米碳管薄膜結構16包括至少兩層重疊且交又 奈米碳管薄膜。該奈米碳管薄膜的製備具體包括以下=驟、 ⑴從上述奈米碳管陣財選定—定寬度㈣ =，本實施例優選為採用具有^寬度的勝帶接财= 定寬度的多嶋碳管束;(b)以一定速度二 ^本垂直于奈米碳管陣列的生長方向拉伸多個該奈米碳管 束，以形成一連續的奈米碳管薄膜。 拉述拉伸過程中，該多個奈米碳管束在拉力作用下沿 定的多個太〗蚊凡力仙，該選 地^ t 分顺其他奈米碳管束首尾相連地連續 =相Γ形成—奈米碳管薄膜。該奈米碳管薄膜包括 之間通軌排列的奈米碳管束，相鄰的奈来碳管束 心间逍過凡德瓦爾力連 列方向基本平行于太賴中奈米碳管的排 丁卞不未石反官溥膜的拉伸方向。 —=有所=驟：中製備的奈米碳管薄臈結構16還可進 1定用有機溶劑處理。 13 200921970 八體的，可通過試管將有機溶劑滴落在奈米碳管薄膜钟 構16表面反潤整個奈米碳管薄膜結構μ。該 發性有機溶劑，如乙醇、甲醇m乙料氣;;= =二f採用乙醇。該奈米碳管_結構16經_二 處理後，在揮發性有機溶㈣表面張力的仙下，1 平灯的奈米碳f>5斷會部分聚集成奈米碳管束，因此，該大 米碳管薄膜結構16表面體積比小，無粘性， μ不 =度及祕，制有機溶财理後的奈米碳管㈣結^^ :::便地應用於宏觀領域。另外，該處理後的奈米碳管薄膜 、-。構Ιό中的奈米碳管聚集成束， ^ 、 Μ中平行的奈米碳管束之二膜結構 微孔結構。 权間基本相互間隔，且交叉排列形成 本技術賴技術W應㈣，本實_ 理後的奈米碳管薄膜結構16中的微孔結構鮮米 的層數有關，當層數越多時，&#& …、S溥膜 所形成的微孔結構的孔徑越小。 本兴施例中，該奈米碳管薄膜結構16的 一 陣列所生長的基底的尺寸有關，，亥太 /又”不米石及官 ，不限，可根據實際需求制得。本實施例中採用二= 米碳管薄膜部分重疊且交又設置❹^化例還可利用將奈 又人叹置形成具有任意寬 奈米碳管薄膜結構1广不受本實施例步驟二中從：米：陣 列直接拉出的奈米碳管薄膜的寬度_。 ’、κ 步驟三、將奈米碳管薄獏結構16鱼 進行複人，形成一夺f碏忠、-人 /、後。正極活性物質18 丁複° ^兔官设合薄膜…從而得到本實施例 14 200921970 的鋰離子電池正極ίο。 所述奈米級的正極活性物質18附著在奈米碳管薄膜結 構16中的奈米碳管管壁上或者填充在奈米碳管管腔内。 具體地，正極活性物質18與奈米碳管薄膜結構16複合 的方法包括以下步驟： 首先，提供一正極活性物質預製體或正極活性物質反應 前驅體。 所述正極活性物質18可選自鋰的氧化物、其他金屬氧化 物或其他活性物質。本實施例中選用氧化鈷鋰做為正極活性 物質18。 所述正極活性物質預製體為正極活性物質18的飽和溶 液、液態的正極活性物質18或氣態的正極活性物質18。 所述正極活性物質溶液為將固態正極活性物質18溶解於 溶劑中制得。所述溶劑可為水、乙醇、丙酮等。優選地，所 述正極活性物質溶液為飽和溶液。 所述正極物質反應前驅體為兩種或兩種以上可以通過化 學反應生成正極活性物質18的反應物，該反應物可以為氣 態、液態或處於溶液中，反應完成後所生成的正極活性物質 18為固態形式，並可以通過一定方法如洗滌、過濾等從反應 體系中分離出來。 其次，將奈米碳管薄膜結構16置於正極活性物預製體或 者正極活性物質反應前驅體中進行複合。 當正極活性物質預製體為正極活性物質溶液時，將奈米 碳管薄膜結構16浸入到正極活性物質溶液中，在一定溫度下 15 200921970 放置至溶劑揮發後，取出奈米碳管薄膜結構16，此時，正極 活性物質18以晶體顆粒的形式形成于奈米碳管薄膜結構16 中的奈米碳管管壁周圍與奈米碳管管腔内。 當正極活性物質預製體為液態或氣態的正極活性物質18 時，將奈米碳管薄膜結構16置於液態或氣態的正極活性物質 18中，放置0.5-2小時，得一奈米碳管複合薄膜14，在保護 氣體存在下室溫冷卻後，正極活性物質以晶體顆粒的形式形 成于奈米碳管薄膜結構16中奈米碳管管壁周圍與奈米碳管 管腔内。 當採用正極活性物質反應前驅體時，將奈米碳管薄膜結 構16置於反應體系中一段時間，待反應充分進行之後，奈米 碳管薄膜結構16的奈米碳管管壁周圍形成含有正極活性物 質18晶體顆粒的物質，然後通過洗滌或者過濾的方法將奈米 碳管薄膜結構16的奈米碳管管壁周圍的除正極活性物質18 以外的其他物質除去，形成奈米碳管複合薄膜14。 可以理解，奈米碳管薄膜結構16與不同的正極活性物質 18複合可以依據具體情況選擇上述製備方法。 本實施例中，將奈米碳管薄膜結構16浸入作為正極活 性物質18的氧化鈷鋰的飽和水溶液中，室溫下放置將水溶劑 揮發掉，形成奈米碳管複合薄膜14，氧化鈷鋰以晶體顆粒的 形式存在于奈米碳管薄膜結構16中奈米碳管管壁周圍和奈 米碳管管腔内。該奈米碳管複合薄膜14可直接用作鋰離子電 池正極10。 另外，所述鋰離子電池正極10的製備方法進一步還可以 16 200921970 包括將該奈米碳管複合薄膜14粘附於一集電體12上。所述 集電體12為金屬基板，本實施例優選的集電體12為銅箔。 可以理解，本實施例也可將奈米碳管薄膜結構16粘附於 一集電體12上，再將上述形成有奈米碳管薄膜結構16的集 電體12整個浸入盛有有機溶劑的容器中浸潤，接著使奈米碳 管薄膜結構16與正極活性物質進行複合形成鋰離子電池正 極10 〇 由於本實施例步驟一中提供的超順排奈米碳管陣列中的 奈米碳管非常純淨，且由於奈米碳管本身的比表面積非常 大，所以該奈米碳管薄膜結構16本身具有較強的粘性。所以 本實施例可不需要粘結劑直接將奈米碳管複合薄膜14或者 奈米碳管薄膜結構16直接粘附於集電體表面12上。 可以理解，本實施例中該奈米碳管複合薄膜14可根據實 際需要使用鐳射在空氣中切割成任意形狀或尺寸，以利於組 裝成微型的鋰離子電池，擴大其應用範圍。進一步地，還可 將上述具有任意形狀或尺寸的奈米碳管複合薄膜14直接粘 附於一集電體表面12上，得到一鋰離子電池正極10。 請參閱圖5,本技術方案進一步提供一種應用上述鋰離子 電池正極的鋰離子電池20，其包括：一殼體22及置於殼體 22内的鋰離子電池正極24，負極26，電解液28和隔膜30， 其中，所述的正極24為採用上述方法製備的鋰離子電池正 極。鋰離子電池20中，電解液28置於殼體22内，正極24、 負極26和隔膜30置於電解液28中，隔膜30置於正極24 與負極26之間，將殼體22内部空間分為兩部分，正極24 17 200921970 與隔膜30及負極26與隔膜30之間保持間隔。正極24包括 一正極集電體32與一層奈米碳管複合薄膜34，負極包括一 負極集電體38與一層石墨化碳材料36。正極接線端40與負 極接線端42分別連接在正極集電體32與負極集電體38的頂 端。充電時，加在電池20兩極的電勢迫使正極24中的活性 物質釋放出鋰離子和電子，鋰離子嵌入負極26中的石墨結構 的碳中，石墨結構與此同時得到一個電子；放電時，鋰離子 和電子從負極26的石墨結構的碳中析出，鋰離子與正極24 中活性物質結合，同時活性物質得到一個電子。由於正極24 中奈米碳管複合薄膜中的活性物質與奈米碳管薄膜結構緊密 且均勻的結合，明顯提高了正極24的導電性能，從而為電子 在電極的運輸提供了方便的通道，改善了鋰離子電池20的充 放電性能。 綜上所述，本發明確已符合發明專利之要件，遂依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施例，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 士援依本發明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為本技術方案實施例鋰離子電池正極的結構示意 圖。 圖2為本技術方案實施例奈米碳管複合薄膜的結構示意 圖。 圖3為本技術方案實施例鋰離子電池正極的製備方法的 18 200921970 流程圖。 圖4為本技術方案實施例奈米碳管複合薄膜的掃描電鏡 •照片。 圖5為採用本技術方案實施例所提供的鋰離子電池正極 所製備的鋰離子。 【主要元件符號說明】 鋰離子電池正極 10 集電體 12 奈米碳管複合薄膜 14 奈米碳管薄膜結構 16 正極活性物質 18 1912. The nano carbon campman J 隹 髀 1919⁄4 5 溥 film 14 is disposed on the current collector 12. The wood electric body 12 can be suitable for today. Preferably, the current collector 12 of the present embodiment is made of copper because of the electrical conductivity of the carbon nanotube film structure 16, and the N-tube · h ^ & 赖 赖 has good, the official 稷 film 14 itself Already have a certain self-supporting and two: sex. In practical applications, the directness and %疋 of the battery are positive. In addition, the composite film 14 is used as the specific surface area of lithium ion, so the use of the positive electrode, the great 妄, 士叫 as electric ' can also improve the agricultural storage in the battery storage office, and the clock ion battery has a good High-speed charging ^^ Further, the positive active material has a temporary characteristic. The material f18 is evenly attached to the carbon nanotube tube cavity in the conductive material of the 11 200921970 nano-film structure 16 , thereby effectively improving the positive electrode activity = in the nanometer • significantly improving the rotor cell positive (1) (4), the activity of the object 18 is simultaneously at the same time as the conductivity of the positive electrode 10 of the butadiene battery. The preparation method mainly includes the following steps: 10 clothes Step 1. Provide - carbon nanotube array, excellent ig妯, ^ + row of carbon nanotube array. W, the array is super-smoothed with the carbon nanotubes _ being a single-walled nanocarbon array and a multi-walled naphthene (four) tube. 〃本实_巾 'Super lion nano carbon material preparation method using chemical emulsion phase deposition method, its remarks include: (1) provide - flat base, the base, you can choose P-type or N-type dream base, or choose The embodiment in which the oxide layer is formed is preferably a 4-inch stone base; (b) uniformly formed on the surface of the substrate - a catalyst layer. The catalyst layer material may be iron (仏), start (0) Recording one of the alloys of (Νι) or any combination thereof; (〇) the substrate on which the catalyst layer is formed is in wot~_. (10) Annealing in air for about 3 minutes = 〇 know, (d) place the treated substrate in a reaction towel, heat it to 500C~740C under the protective gas, and then react with carbon source gas for about 5 minutes~30 Minutes, growth results in a super-sequential carbon nanotube array 'with a height of 2 μm to 400 μm. The super-sequential carbon nanotube array is a plurality of pure carbon nanotube arrays formed of carbon nanotubes that are parallel to each other and are grown perpendicular to the substrate. The super-sequential carbon nanotube array is substantially free of impurities such as amorphous carbon or residual catalyst metal particles by controlling the growth conditions as described above. The carbon nanotubes in the array of carbon nanotubes are in contact with each other by van der Waals force to form an array. 12 200921970 • 'The carbon source gas of this embodiment can be _ B, B, and the chemically active hydrocarbons. The preferred carbon source gas in this embodiment is acetylene; the shielding gas is nitrogen or inert gas. The preferred shielding gas of the embodiment is argon. The carbon nanotube array provided in this embodiment is not limited to the above preparation method, and may include other methods such as laser gamma, plasma, and the like. Step 2. The stretching-stretching tool pulls the carbon nanotube film structure 16 from the carbon nanotube array. The carbon nanotube film structure 16 includes at least two layers of overlapping and alternating carbon nanotube films. The preparation of the carbon nanotube film specifically includes the following steps: (1) selecting from the above-mentioned carbon nanotube array - the fixed width (four) =, in this embodiment, it is preferable to use a multi-turn carbon having a width of 2 a tube bundle; (b) stretching a plurality of the carbon nanotube bundles at a constant speed perpendicular to the growth direction of the carbon nanotube array to form a continuous carbon nanotube film. During the drawing process, the plurality of carbon nanotube bundles are slid under the force of a plurality of taiyue mosquitoes, and the selected stalks are continuously connected to the other carbon nanotube bundles in an end-to-end manner. - Nano carbon tube film. The carbon nanotube film comprises a bundle of carbon nanotubes arranged in a track-to-rail arrangement, and the adjacent Nyed carbon tube bundles are crossed by the van der Waals force and are substantially parallel to the row of the carbon nanotubes of the Tailai carbon nanotubes. The direction of stretching of the stone anti-burst film. -= Some = Step: The prepared carbon nanotube thin crucible structure 16 can also be treated with an organic solvent. 13 200921970 Eight-body, the organic solvent can be dripped on the surface of the carbon nanotube film structure 16 through the test tube to reproduce the entire nano-carbon nanotube film structure μ. The organic solvent, such as ethanol, methanol, methane gas;; = = two f, using ethanol. After the carbon nanotube _ structure 16 is treated by _ two, under the surface tension of the volatile organic solvent (four), the light carbon nanoparticle of the flat lamp is partially integrated into the carbon nanotube bundle, so the rice is The carbon nanotube film structure 16 has a small surface volume ratio, no viscosity, μ is not the degree and secret, and the carbon nanotubes after the organic solvent is dissolved (4) is used in the macroscopic field. In addition, the treated carbon nanotube film, -. The carbon nanotubes in the structure are aggregated into bundles, and the two membrane structures of the parallel carbon nanotube bundles in the crucible are microporous. The weights are basically spaced apart from each other, and the cross-alignment forms the technology of the technology. (4), the actual number of layers of the microporous structure of the carbon nanotube film structure 16 is related to the number of layers, when the number of layers is larger, The smaller the pore size of the microporous structure formed by the &#& ..., S film. In the embodiment of the present invention, the size of the substrate on which the array of the carbon nanotube film structure 16 is grown is related to the size of the substrate, and is not limited to the size of the substrate. In the second embodiment, the two-meter carbon nanotube film is partially overlapped and disposed, and the ruthenium can also be used to form a film structure having an arbitrarily wide carbon nanotube film. : Width of the carbon nanotube film directly pulled out by the array _. ', κ Step 3, the carbon nanotubes of the thin carbon nanotube structure 16 fish are re-established, forming a 碏 碏 碏 、, - human /, after. Positive activity The material 18 is a compound of a film, thereby obtaining a positive electrode of the lithium ion battery of the present embodiment 14 200921970. The nano-sized positive electrode active material 18 is attached to the nanocarbon of the carbon nanotube film structure 16 The tube wall is filled in the lumen of the carbon nanotube. Specifically, the method of recombining the cathode active material 18 with the carbon nanotube film structure 16 comprises the following steps: First, providing a positive electrode active material preform or a positive electrode active material Reaction precursor The material 18 may be selected from the group consisting of lithium oxide, other metal oxides or other active materials. In the present embodiment, lithium cobalt oxide is used as the positive electrode active material 18. The positive electrode active material preform is a saturated solution of the positive electrode active material 18, The liquid positive electrode active material 18 or the gaseous positive electrode active material 18. The positive electrode active material solution is prepared by dissolving the solid positive electrode active material 18 in a solvent, and the solvent may be water, ethanol, acetone, or the like. The positive electrode active material solution is a saturated solution. The positive electrode material reaction precursor is a reactant of two or more kinds of positive electrode active materials 18 which can be chemically reacted, and the reactant may be in a gaseous state, in a liquid state or in a solution. The positive electrode active material 18 formed after completion is in a solid form and can be separated from the reaction system by a certain method such as washing, filtration, etc. Next, the carbon nanotube film structure 16 is placed in the positive electrode active preform or the positive electrode active. Recombination in the material reaction precursor. When the positive electrode active material preform is a positive electrode active material solution The carbon nanotube film structure 16 is immersed in the positive electrode active material solution, and after being placed at a certain temperature for 15 200921970 until the solvent is volatilized, the carbon nanotube film structure 16 is taken out. At this time, the positive electrode active material 18 is formed in the form of crystal particles. In the inner wall of the carbon nanotube tube in the carbon nanotube film structure 16 and in the lumen of the carbon nanotube. When the positive electrode active material preform is a liquid or gaseous positive active material 18, the carbon nanotube film structure 16 is placed in a liquid or gaseous positive electrode active material 18, and left for 0.5-2 hours to obtain a carbon nanotube composite film 14, which is formed in the form of crystal particles in the form of crystal particles after being cooled at room temperature in the presence of a shielding gas. The carbon nanotube film structure 16 is surrounded by the inner wall of the carbon nanotube tube and the inner surface of the carbon nanotube tube. When the positive electrode active material is used to react the precursor, the carbon nanotube film structure 16 is placed in the reaction system for a period of time. After the reaction is sufficiently carried out, a substance containing crystal particles of the positive electrode active material 18 is formed around the wall of the carbon nanotube tube of the carbon nanotube film structure 16, and then washed or filtered. M carbon nanotube film structure other than a positive electrode active material 18. Other material 16 is removed around the wall nanotubes, nanotube composite film 14 is formed. It can be understood that the carbon nanotube film structure 16 is compounded with different positive electrode active materials 18, and the above preparation method can be selected according to specific conditions. In the present embodiment, the carbon nanotube film structure 16 is immersed in a saturated aqueous solution of lithium cobalt oxide as the positive electrode active material 18, and the aqueous solvent is volatilized at room temperature to form a carbon nanotube composite film 14, which is a lithium cobalt oxide film. It is present in the form of crystal particles in the carbon nanotube membrane structure 16 around the wall of the carbon nanotube tube and in the lumen of the carbon nanotube. The carbon nanotube composite film 14 can be directly used as the lithium ion battery positive electrode 10. In addition, the method for preparing the positive electrode 10 of the lithium ion battery may further include adhering the carbon nanotube composite film 14 to a current collector 12 according to 2009200970. The current collector 12 is a metal substrate, and the current collector 12 preferred in the present embodiment is a copper foil. It can be understood that, in this embodiment, the carbon nanotube film structure 16 can also be adhered to a current collector 12, and the current collector 12 having the carbon nanotube film structure 16 formed thereon can be entirely immersed in an organic solvent. The container is wetted, and then the carbon nanotube film structure 16 is combined with the positive electrode active material to form a positive electrode of the lithium ion battery. 10 The carbon nanotubes in the super-sequential carbon nanotube array provided in the first step of the present embodiment are very Pure, and because the specific surface area of the carbon nanotube itself is very large, the carbon nanotube film structure 16 itself has a strong viscosity. Therefore, in this embodiment, the carbon nanotube composite film 14 or the carbon nanotube film structure 16 can be directly adhered to the current collector surface 12 without using an adhesive. It can be understood that in the embodiment, the carbon nanotube composite film 14 can be cut into any shape or size in the air according to actual needs, so as to facilitate assembly into a miniature lithium ion battery, and expand the application range thereof. Further, the above-mentioned carbon nanotube composite film 14 having any shape or size can be directly adhered to a current collector surface 12 to obtain a lithium ion battery positive electrode 10. Referring to FIG. 5 , the technical solution further provides a lithium ion battery 20 using the above positive electrode of a lithium ion battery, comprising: a casing 22 and a lithium ion battery positive electrode 24 disposed in the casing 22 , a negative electrode 26 , and an electrolyte 28 . And the separator 30, wherein the positive electrode 24 is a positive electrode of a lithium ion battery prepared by the above method. In the lithium ion battery 20, the electrolyte 28 is placed in the casing 22, and the positive electrode 24, the negative electrode 26, and the separator 30 are placed in the electrolyte 28, and the separator 30 is placed between the positive electrode 24 and the negative electrode 26, and the internal space of the casing 22 is divided. In two parts, the positive electrode 24 17 200921970 is spaced apart from the separator 30 and the negative electrode 26 and the separator 30. The positive electrode 24 includes a positive electrode collector 32 and a layer of carbon nanotube composite film 34, and the negative electrode includes a negative electrode collector 38 and a layer of graphitized carbon material 36. The positive electrode terminal 40 and the negative electrode terminal 42 are connected to the top ends of the positive electrode collector 32 and the negative electrode collector 38, respectively. During charging, the potential applied to the two poles of the battery 20 forces the active material in the positive electrode 24 to release lithium ions and electrons, and the lithium ions are embedded in the carbon of the graphite structure in the negative electrode 26, and the graphite structure simultaneously obtains an electron; Ions and electrons are precipitated from the carbon of the graphite structure of the negative electrode 26, and lithium ions are combined with the active material in the positive electrode 24, while the active material acquires one electron. Since the active material in the carbon nanotube composite film of the positive electrode 24 is closely and uniformly combined with the structure of the carbon nanotube film, the conductivity of the positive electrode 24 is obviously improved, thereby providing a convenient passage for the transportation of electrons in the electrode, and improving The charge and discharge performance of the lithium ion battery 20 is obtained. In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those who are familiar with the skill of the present invention in accordance with the spirit of the present invention are intended to be included in the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a positive electrode of a lithium ion battery according to an embodiment of the present invention. Fig. 2 is a schematic view showing the structure of a carbon nanotube composite film according to an embodiment of the present invention. 3 is a flow chart of a method for preparing a positive electrode of a lithium ion battery according to an embodiment of the present invention. 4 is a scanning electron microscope photograph of a carbon nanotube composite film according to an embodiment of the present technology. Fig. 5 is a lithium ion prepared by using a positive electrode of a lithium ion battery provided by an embodiment of the present technical solution. [Main component symbol description] Lithium-ion battery positive electrode 10 Current collector 12 Carbon nanotube composite film 14 Carbon nanotube film structure 16 Positive active material 18 19