1238555 五、發明說明（1) 【發明所屬之技術領域】 本發明係關於鐘二次電池，尤指鋰二次電池負極。 【先前技術】 電池係將化學能轉化為電能之裝置，電池產品從早期 之錯酸電池、鎳編電池與鎳氫電池發展到現在的鋰電池。 其中，錯酸電池及鎳鎘電池因為環境污染問題漸漸被鋰電 池取代。目刚Μ電池亦有一次鐘電池及可充電池之分，可 充鋰電池即鋰二次電池，與傳統電池最大區別在於使用有 機溶劑而非水溶液做為電解液。 仿凋w 电十 腦（Computer) 般簡稱為3C產 發展方向包 量密度；（3) 極材料之開 隧道結構等開 此類結構提供 可增加電池之 料作為負極材 然而，就能量 墨之理論值為 他幾種材料之 經二次電池應用範圍相當廣泛，主要包 產口σ(Consumer Electronic Products)、電 及通訊產品（Communication Products), — 品。為滿足各種產品之需要，鋰二次電池之 括：（1)延長電池使用壽命；（2)增加電池容 體積要求微型化；（4 )去除容量記憶效應。 提高能量密度關鍵在於高負載容量之電 發’對於可逆之電極材料而言，具有層狀或 放性結構材料為最適用。在鋰二次電池中， 了經離子容易進出之管道與快速之遷移率， 循環壽命。目前商用化產品大多使用碳素材 如天然石墨，類石墨，焦碳，碳黑等。 名度而5 ’上述幾種碳素材料仍屬較低，石 372 mAh/g ’實際值約為32〇〜34〇 ，其 能量密度更低。1238555 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a clock secondary battery, especially a negative electrode of a lithium secondary battery. [Previous technology] Batteries are devices that convert chemical energy into electrical energy. Battery products have evolved from early acid batteries, nickel-based batteries, and nickel-metal hydride batteries to current lithium batteries. Among them, acid batteries and nickel-cadmium batteries have gradually been replaced by lithium batteries due to environmental pollution. Mekong M batteries also have primary clock batteries and rechargeable batteries. Rechargeable lithium batteries are lithium secondary batteries. The biggest difference from traditional batteries is that they use organic solvents instead of aqueous solutions as the electrolyte. Imitation w Electric Computer (Computer) is referred to as the bulk density of the development direction of the 3C; (3) the tunnel structure of the electrode material, such as opening the structure to provide materials that can increase the battery as the anode material. However, the theory of energy ink The value of the secondary battery for his several materials is quite extensive. It mainly produces σ (Consumer Electronic Products), electrical and communication products (Communication Products), and other products. To meet the needs of various products, lithium secondary batteries include: (1) extending battery life; (2) increasing battery capacity and miniaturizing volume requirements; (4) removing capacity memory effects. The key to increasing the energy density is high-capacity electricity. For reversible electrode materials, layered or radioactive structural materials are the most suitable. In lithium secondary batteries, the ions have a pipeline that can easily enter and exit, fast mobility, and cycle life. At present, most commercial products use carbon materials such as natural graphite, graphite-like, coke, and carbon black. However, the 5 ′ carbon materials mentioned above are still relatively low. The actual value of the stone 372 mAh / g 'is about 32 ~ 34, and its energy density is lower.
1238555 五、發明說明（2) 理論上，鋰金屬為負極材料可得約9 0 0 mAh/g之高能 量密度，遠高於上述碳素材料。惟，經金属作為負極時易 與基材發生反應，並無法直接運用於電池製作過程。 有鑒於此，提供一種具有高能量密度，大電容量，且 使用壽命長之鋰二次電池實為必要。 【内容】 本發明之目的係提供一種具有高能量密度及高電容量 之經二次電池。1238555 V. Description of the invention (2) Theoretically, lithium metal as a negative electrode material can obtain a high energy density of about 900 mAh / g, which is much higher than the above carbon material. However, when metal is used as the negative electrode, it easily reacts with the substrate and cannot be directly used in the battery manufacturing process. In view of this, it is necessary to provide a lithium secondary battery having a high energy density, a large electric capacity, and a long service life. [Content] The object of the present invention is to provide a secondary battery with high energy density and high electric capacity.
本發明之奈米碳管鋰二次電池，其包括一含有正極活 性材料之正極，一負極，及一置於該正極與負極間之多孔 隔離膜，其中，該負極包括一導電基底，形成於該導電基 底表面之奈米碳管層，及形成於該奈米碳管層表面之經金 屬層。 與習知技術相較，本發明充分利用鋰金屬高能量密度 之優點，並以奈米碳管層隔開鋰金屬層與基底，可避免其 發生反應，從而延長電池使用壽命，提高能量密度及電容 量。 【實施方式】The nano carbon nanotube lithium secondary battery of the present invention includes a positive electrode containing a positive electrode active material, a negative electrode, and a porous separator interposed between the positive electrode and the negative electrode, wherein the negative electrode includes a conductive substrate formed on A nano carbon tube layer on the surface of the conductive substrate, and a metal layer formed on the surface of the nano carbon tube layer. Compared with the conventional technology, the present invention makes full use of the advantages of the high energy density of lithium metal, and separates the lithium metal layer from the substrate by a nano carbon tube layer, which can prevent the reaction from occurring, thereby prolonging the service life of the battery, increasing the energy density and capacitance. [Embodiment]
請先參閱第一圖，本發明奈米碳管經二次電池包括一 負極10，一正極20，置於負極10與正極20間之隔離膜30， 及非水電解液（圖未示）。其中，該負極10包括一導電之基 底100，該基底100係金屬材料，常用之金属材料包括銅、 鋁等，根據需要可製造形成一定之形狀，具有一平坦表 面；一奈米碳管層11 0形成於該基底1 0 0之表面，該奈米碳Please refer to the first figure. The secondary carbon nanotube battery according to the present invention includes a negative electrode 10, a positive electrode 20, a separator 30 interposed between the negative electrode 10 and the positive electrode 20, and a non-aqueous electrolyte (not shown). Wherein, the negative electrode 10 includes a conductive substrate 100. The substrate 100 is a metallic material. Commonly used metallic materials include copper, aluminum, etc., and can be manufactured into a certain shape as required, and has a flat surface. A nano-carbon tube layer 11 0 is formed on the surface of the substrate 100, and the nano carbon
第6頁 1238555 五、發明說明（3) 管層1 0 0係由複數互相平行之奈米碳管排列構成，各奈米 碳管垂直該基底100之表面；一鋰金屬層120形成於該奈米 碳管層110之表面，從而鋰金屬層120與基底100之間以奈 米碳管層1 1 0為間隔緩衝層，避免直接接觸，該鋰金屬層 1 2 0係由鋰金屬構成。正極2 0含有過渡金屬之氧化物或硫 化物為正極活性材料，所述過渡金屬包括了 i，V，Cr， Μη，Fe，Co，Ni或Cu等；隔離膜30通常由不織布 (nonwoven fabric)構成，或者以聚丙烯 (Polypropylene)、聚乙烯（Polyethylene)、氟化樹脂等 有機材料製成多孔結構而成；而電解液為非水電解液，分 為溶劑與溶質二部分，溶劑包括：破酸丙烯g旨（p r 〇 p y 1 e n e Carbonate)、碳酸乙稀醋（Ethylene Carbonate)、碳酸二 甲酯（Dimethyl Carbonate)等，溶質包括 LiPF6、LiBF4、 LiC104、LiAsF6、LiCF3S03 等。 請一併參閱第二圖及第三圖，本發明奈米碳管鋰二次 電池之負極10製備過程包括：首先，提供一金屬導電基底 1 〇〇，根據需要製成一定形狀，其具有一平坦表面；以化 學氣相沈積法（CVD)於該表面形成一奈米碳管層11〇，或通 過移植法將製備之奈米碳管移植至該表面，各奈米碳管垂 直於該基底100之表面；再進一步通過物理或化學方法將 鋰金屬形成於該奈米碳管層110表面，形成一鋰金屬層 120，從而，經金屬層120與基底100之間以奈米碳管層iiQ 隔開，避免鋰金屬層120與基底100直接接觸。 製備負極10之後，與其他部分，包括正極20，隔離膜Page 6 1238555 V. Description of the invention (3) The tube layer 100 is composed of a plurality of carbon nanotubes arranged in parallel with each other, each carbon nanotube is perpendicular to the surface of the substrate 100; a lithium metal layer 120 is formed on the carbon nanotube The surface of the rice carbon tube layer 110, so that the lithium metal layer 120 and the substrate 100 use the nano carbon tube layer 110 as a buffer layer to avoid direct contact. The lithium metal layer 120 is made of lithium metal. The positive electrode 20 contains an oxide or a sulfide of a transition metal as a positive electrode active material, and the transition metal includes i, V, Cr, Mn, Fe, Co, Ni, or Cu; and the separator 30 is usually made of a non-woven fabric. Structure, or made of porous materials such as polypropylene (Polypropylene), polyethylene (Polyethylene), fluorinated resin and other organic materials; and the electrolyte is a non-aqueous electrolyte, divided into two parts: solvent and solute. The solvent includes: Acid propylene (pr py 1 ene Carbonate), ethylene carbonate (Ethylene Carbonate), dimethyl carbonate (Dimethyl Carbonate), etc., solutes include LiPF6, LiBF4, LiC104, LiAsF6, LiCF3S03 and so on. Please refer to the second and third figures together. The preparation process of the negative electrode 10 of the nano carbon tube lithium secondary battery of the present invention includes: First, a metal conductive substrate 100 is provided, and a certain shape is made according to needs, which has a A flat surface; a carbon nanotube layer 11 is formed on the surface by chemical vapor deposition (CVD), or the prepared carbon nanotubes are transplanted to the surface by a transplantation method, each carbon nanotube is perpendicular to the substrate The surface of 100; and lithium metal is further formed on the surface of the carbon nanotube layer 110 by a physical or chemical method to form a lithium metal layer 120. Thus, a carbon nanotube layer iiQ is formed between the metal layer 120 and the substrate 100. It is separated to avoid direct contact between the lithium metal layer 120 and the substrate 100. After the negative electrode 10 is prepared, it is separated from other parts including the positive electrode 20 and the separator.
第7頁 1238555 五、發明說明（4) 3 0，一起封裝並注入電解液，即可完成本發明奈米碳管鋰 二次電池。 本發明之奈米碳管鋰二次電池中，因鋰金屬層120與 基底1 0 0間隔有奈米碳管層1 1 0，故，可避免鋰金屬層1 2 0 與基底100之金屬發生反應，從而延長使用壽命；另外， 本發明可充分利用鋰金屬之能量密度非常高之優點，提高 電池之能量密度及電容量；而且，奈米碳管係一種管徑為 幾奈米至十幾奈米之中空管狀石墨層結構，藉由其中空特 性，於電池充電或放電過程中，鋰離子能夠更容易遷移， 有利於電池反應進行。 本發明之奈米碳管鋰二次電池可製成各種形狀，如圓 柱形、紐扣式、方形等，以適應各種設備之外形需要。 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。Page 7 1238555 V. Description of the invention (4) 30, the carbon nanotube lithium secondary battery of the present invention can be completed by encapsulating and injecting the electrolyte together. In the nano-carbon tube lithium secondary battery of the present invention, since the lithium metal layer 120 and the substrate 100 are separated by the nano-carbon tube layer 1 1 0, the occurrence of metal between the lithium metal layer 120 and the substrate 100 can be avoided. Reaction, thereby prolonging the service life; in addition, the present invention can make full use of the advantage of the very high energy density of lithium metal to improve the energy density and capacity of the battery; moreover, the carbon nanotube system has a diameter of several nanometers to a dozen The structure of the hollow tubular graphite layer of nanometers, due to its hollow nature, allows lithium ions to migrate more easily during the charging or discharging process of the battery, which is beneficial to the battery reaction. The nano carbon tube lithium secondary battery of the present invention can be made into various shapes, such as cylindrical shape, button type, square shape, etc., to meet the external shape requirements of various devices. In summary, the present invention has indeed met the requirements for an invention patent, and a patent application was filed in accordance with the law. However, the above is only a preferred embodiment of the present invention, and it cannot be used to limit the scope of patent application in this case. All equivalent modifications or changes made by those skilled in the art of the case with the aid of the spirit of the present invention shall be covered by the scope of the following patent applications.
1238555 圖式簡單說明 第一圖係本發明之奈米碳管鋰二次電池之剖面示意圖。 第二圖係本發明之奈米碳管層形成於導電基底之示意 圖。 第三圖係於第二圖之奈米碳管表面形成鋰金屬層之示意 圖。 【主要元件符號說明】 負極 10 正極 20 隔離膜 30 基底 100 奈米碳管層 110 經金屬層 1201238555 Brief description of the drawings The first diagram is a schematic cross-sectional view of a nano carbon tube lithium secondary battery of the present invention. The second figure is a schematic view of the nano carbon tube layer of the present invention formed on a conductive substrate. The third diagram is a schematic diagram of forming a lithium metal layer on the surface of the carbon nanotube of the second diagram. [Description of main component symbols] Negative electrode 10 Positive electrode 20 Separation film 30 Substrate 100 Nanometer carbon tube layer 110 Via metal layer 120
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