1331817 099年06月29日接正替换頁 六、發明說明： 【發明所屬之技術頜域】 _]本發明關於一種_子€池陰極及其製備方法。 _2]本發明還關於^種快速充放電之麟子電池。 【先前技術】 [0003]1331817 On June 29, 099, the replacement page is replaced. 6. Description of the invention: [Technical jaw region to which the invention belongs] _] The present invention relates to a cathode of a cathode and a preparation method thereof. _2] The present invention also relates to a lining battery for rapid charge and discharge. [Prior Art] [0003]
隨著視聽、資訊及通訊等電子產品均朝向無線化、便攜 化方向發展，大量便攜式電器如移動電話、攝像機 '筆 記型電腦、照相機等普及使用，增大了對具有高壓、大 容量之可充電電池之需求。鋰離子電池係一種新型可充 電之理想的高能輕塑電池，因其具有高工作電壓與比能 量、高放電電容量、工作電壓平穩、循環壽命長等優點 ，成為行動電話、筆記型電腦及數位相機的重要電能供 應來源。 [0004] 一般而言，鋰離子電池包括一陰極 '一陽極及連接陰極 與陽極並將其分隔開之滲透隔離膜。上述之陰極、陽極 及滲透隔離膜置於一金屬罐内’並將電解液注入金屬罐 内，浸泡正極、負極，以發生電化學反應，將電能與化 學能互相轉換。 [0005] 094119205 其中’渗透隔離膜係多孔結構’可使離子通過，卻對電 子絕緣，一般為聚乙烯、聚丙烯或聚笨乙缔。陰極材料 一般為嵌鐘過渡金屬氧化物，如LiM〇2(M=c0、Ni ) ’係電子供給者，陰極材料之原子在氧化過程中變成離 子’並釋放出電子，離子通過滲透隔離膜在 — ^ 、 为電極還 原，電子則傳輸至外電路中形成電流。陽, 啼極材料一般為 可嵌鋰化合物，如各種碳材料包括石墨、 灭纖維及仝凰 矣罝总妹Ainm 第3頁/共13頁 •"久至屬 0993229577-0 1331817 _L· 099年06月29日修正替換頁 氧化物等。 [0006] 鋰離子電池之電解液一般常用液態電解液，其係以有機 非水溶液如碳酸乙烯酯（Ethylene Carbonate, EC)、 碳酸二乙酯（Diethyl Carbonate, DEC)之混合物為溶 劑，以链鹽（如LiPFe)為溶質，並添加少量添加劑組成。 0 [0007] 該種鋰離子電池係以鋰離子之嵌入與遷出反應實現充放 電，取代鋰電池内鋰金屬沈積與溶解反應。在充電過程 中，鋰離子會由陰極氧化物中遷出，再嵌入至陽極化合With the development of audio-visual, information and communication electronic products in the direction of wireless and portable, a large number of portable electrical appliances such as mobile phones, video cameras, notebook computers, cameras, etc. have been widely used, which has increased the charging capacity with high voltage and large capacity. Battery demand. Lithium-ion battery is a new type of high-energy light plastic battery that can be charged. It has the advantages of high working voltage and specific energy, high discharge capacity, stable working voltage and long cycle life. It has become a mobile phone, notebook computer and digital. An important source of electrical energy for the camera. [0004] In general, a lithium ion battery includes a cathode 'an anode and a permeation separator that connects the cathode to the anode and separates it. The cathode, the anode and the permeable separator are placed in a metal canister, and the electrolyte is injected into the metal can, and the positive electrode and the negative electrode are immersed to cause an electrochemical reaction to convert electrical energy and chemical energy. [0005] 094119205 wherein 'permeating separator-based porous structure' allows ions to pass through but is electrically insulated, typically polyethylene, polypropylene or polystyrene. The cathode material is generally a chimes transition metal oxide, such as LiM〇2 (M=c0, Ni) 'system electron supplier, the atoms of the cathode material become ions in the oxidation process and release electrons, and the ions pass through the permeable separator. — ^ , for electrode reduction, electrons are transferred to an external circuit to form a current. Yang, bungee materials are generally lithium-intercalable compounds, such as various carbon materials including graphite, fiber and auspicious sister Ainm Page 3 of 13 •"Long-term to 0993229577-0 1331817 _L· 099 On June 29th, the replacement page oxide was corrected. [0006] The electrolyte of a lithium ion battery generally uses a liquid electrolyte, which is a mixture of an organic non-aqueous solution such as ethylene carbonate (EC), diethyl carbonate (DEC), and a chain salt. (such as LiPFe) is a solute and is added with a small amount of additives. 0 [0007] This kind of lithium-ion battery is charged and discharged by the insertion and removal reaction of lithium ions, which replaces the deposition and dissolution reaction of lithium metal in lithium batteries. During the charging process, lithium ions are removed from the cathode oxide and embedded in the anode.
物中；在放電過程中，陽極材料中已存在的鋰離子遷出 I ，再行嵌入陰極氧化物中。如此反覆進行，達到充放電 的目的，可避免鋰在電極表面的枝狀晶化問題，使鋰離 子電池之壽命及安全性能更優。 [0008] 鋰離子二次電池雖然已被廣泛使用，但仍存有部份問題 尚待解決。鋰離子遷出或嵌入陰極材料時，都是在固體 中進行擴散反應，當鋰離子離開陰極材料進入電解液後 ，則是在液體中進行擴散反應。一般而言，固體中之擴· ^ 散係數較液體中之擴散係數小得多，因此鋰離子於陰極 端所遭受之擴散阻力主要來自於陰極固體材料中。這種 阻力的存在，使鋰離子電池充電與放電有一定的速度限 制，無法進行快速的充放電。為增加電池導電性，需於 陰極固體材料中添加助導劑，使得製程繁瑣。 [0009] 有鑑於此，提供一種阻力較小之鋰離子電池陰極及其製 備方法以及可快速充放電之鋰離子電池實為必需。 【發明内容】 094119205 表單編號A0101 第4頁/共13頁 0993229577-0 1331817 099年06月29日按正替换頁 [0010] 以下，將以實施例說明一種阻力較小之鋰離子電池陰極 及其製備方法。 [0011] 以及，通過這些實施例提供一種快速充放電之鋰離子電 池。 [0012] 該種鋰離子電池陰極包括複數奈米顆粒，該奈米顆粒係 由奈米碳材及包覆於其表面之氧化物組成。 [0013] 該氧化物為嵌鋰過渡金屬氧化物。該嵌鋰過渡金屬氧化 物為LiM〇2，Μ為Co、Ni 或Μη 〇 [0014] 一種鋰離子電池陰極之製備方法，該陰極包括複數奈米 顆粒，該奈米顆粒係以如下步驟製備：將含所需氧化物 之水溶液加入一密閉容器内；將奈米碳材加入該水溶液 内；加熱。 [0015] 該種鋰離子電池包括一陰極、一陽極及一滲透隔離膜， 該滲透隔離膜連接陰極與陽極並將其分隔開，該陰極包 括複數奈米顆粒，該奈米顆粒係由奈米碳材及包覆於其 ^ 表面之氧化物組成。 [0016] 與先前技術相比，本實施例鋰離子電池之優點在於：其 鋰離子電池陰極以奈米碳材為嵌鋰過渡金屬氧化物之載 體，可以減小鋰離子電池陰極之粒徑，縮短鋰離子在陰 極中所需之擴散時間，加快電池充放電速度，大幅縮短 充放電時間。 [0017] 該鋰離子電池陰極及其製備方法之優點在於：提供了一 種結晶性佳、奈米級粒徑之鋰離子電池陰極，且奈米碳 0993229577-0 094119205 表單編號Α0101 第5頁/共13頁 1331817 099年06月29日修正替換頁 材之特性提高了鋰離子電池陰極本身之導電性及熱穩定 性，並縮短了固體陰極材料中添加助導劑之製程。 【實施方式】 [0018] 為減小鋰離子電池陰極的阻力，縮短鋰離子在陰極中所 需之擴散時間，加快電池充放電速度，本實施例考慮減 少鋰離子電池陰極之粒徑。將鋰離子電池陰極奈米化對 減少其粒徑具有重要作用。 [0019] Cn(俗稱奈米碳球）包含60個碳原子，係由20個六角形和During the discharge process, the lithium ions already present in the anode material migrate out of I and are then embedded in the cathode oxide. By repeating this and achieving the purpose of charge and discharge, the problem of dendrite crystallization of lithium on the surface of the electrode can be avoided, and the life and safety performance of the lithium ion battery can be improved. [0008] Although lithium ion secondary batteries have been widely used, some problems remain to be solved. When lithium ions migrate out or are embedded in the cathode material, diffusion reaction occurs in the solid. When the lithium ions leave the cathode material and enter the electrolyte, the diffusion reaction proceeds in the liquid. In general, the diffusion coefficient in solids is much smaller than the diffusion coefficient in liquids, so the diffusion resistance of lithium ions at the cathode end is mainly from the cathode solid material. The existence of such resistance has a certain speed limit for charging and discharging lithium-ion batteries, and it is impossible to perform rapid charging and discharging. In order to increase the conductivity of the battery, it is necessary to add a promoter to the cathode solid material, which makes the process cumbersome. In view of the above, it is necessary to provide a lithium ion battery cathode having a small resistance and a preparation method thereof, and a lithium ion battery which can be rapidly charged and discharged. SUMMARY OF THE INVENTION 094119205 Form No. A0101 Page 4 / Total 13 Page 0993229577-0 1331817 June 29, 1999, according to the replacement page [0010] Hereinafter, a lithium ion battery cathode with less resistance and its description will be described by way of example Preparation. [0011] Also, a lithium ion battery that is rapidly charged and discharged is provided by these embodiments. [0012] The lithium ion battery cathode includes a plurality of nano particles composed of a nano carbon material and an oxide coated on the surface thereof. [0013] The oxide is a lithium intercalation transition metal oxide. The lithium intercalation transition metal oxide is LiM〇2, and Μ is Co, Ni or Μη〇 [0014] A method for preparing a cathode of a lithium ion battery, the cathode comprising a plurality of nano particles, which are prepared by the following steps: The aqueous solution containing the desired oxide is added to a closed vessel; the nanocarbon material is added to the aqueous solution; and heated. [0015] The lithium ion battery comprises a cathode, an anode and a permeable separator, the permeable membrane connecting the cathode and the anode and separating the cathode, the cathode comprising a plurality of nano particles, the nano granules being composed of nano A carbon material and an oxide layer coated on the surface thereof. [0016] Compared with the prior art, the lithium ion battery of the embodiment has the advantages that the cathode of the lithium ion battery is a carrier of a lithium intercalation transition metal oxide, and the particle size of the cathode of the lithium ion battery can be reduced. Shorten the diffusion time required for lithium ions in the cathode, accelerate the charge and discharge rate of the battery, and significantly shorten the charge and discharge time. [0017] The lithium ion battery cathode and the preparation method thereof have the advantages of providing a lithium ion battery cathode with good crystallinity and nanometer size, and the carbon carbon 0993229577-0 094119205 form number Α0101 page 5 / total 13 pages 1331817 On June 29, 099, the characteristics of the replacement sheet material were improved to improve the conductivity and thermal stability of the cathode of the lithium ion battery, and to shorten the process of adding a promoter to the solid cathode material. [Embodiment] [0018] In order to reduce the resistance of the cathode of the lithium ion battery, shorten the diffusion time required for lithium ions in the cathode, and accelerate the charge and discharge rate of the battery, this embodiment considers reducing the particle size of the cathode of the lithium ion battery. Nanocrystallization of lithium ion battery cathodes plays an important role in reducing particle size. [0019] Cn (commonly known as nanocarbon sphere) contains 60 carbon atoms and is composed of 20 hexagons and
b U 12個五角形所圍成，外形像一顆足球，是目前已知對稱 性最高的球狀分子。其分子直徑為7. 1埃，密度為1. 68克 /立方釐米，在室溫下呈紫紅色固態分子晶體。它與鑽石 一樣常溫下不具導電性，但在18K時具有超導性。 [0020] 由化學性質來看，CRn具有近似石墨之sp2雜化軌道，每b U 12 pentagons, shaped like a football, is the most symmetrical spherical molecule known. The molecular diameter is 7.1 angstroms, and the density is 1.68 g / cm 3 , which is a purple-red solid molecular crystal at room temperature. It is as non-conductive at room temperature as diamonds, but superconducting at 18K. [0020] From the chemical point of view, CRn has a sp2 hybrid orbit similar to graphite, each
〇 U 個碳原子與相鄰的三個碳原子鍵合，具有三個δ鍵和一 個π鍵。其碳一碳鍵有兩種長度，分別為1. 38埃和1. 45 埃；兩個相鄰六角形所共用的碳一碳鍵較短，接近雙鍵 (C = C)的性質（由一個<5鍵及一個τι鍵所組成），而六角環 和五角環共用的鍵較長，接近單鍵（C-C)的性質。這種獨 特的化學結構使奈米碳球之化學性質相當穩定。 [0021] 利用奈米碳球之上述性質奈米化電極材料顆粒，使減小 鋰離子電池陰極之粒徑、進一步提升鋰離子電池之功能 、增大充放電容量以及加快充放電速度成為可能。 [0022] 本實施例之鋰離子電池包括一陰極、一陽極及連接陰極 與陽極並將其分隔開之滲透隔離膜。上述之陰極、陽極 0993229577-0 094119205 表單編號Α0101 第6頁/共13頁 隔離膜置於_金屬罐内，並將電解液注入金屬罐 ::泡正極、負極’以發生電化學反應，將電能與化 予月《=·互相轉換。其t ’滲透隔離膜係多孔結構，可使離 \部對電子絕緣，-般為聚乙婦、聚丙烯或聚笨 陽極材料為可嵌鐘化合物，如各種碳材料包括石 墨、碳纖維及金屬氧化物等。 [0023] ^實施例之鐘離子電池陰極包含複數奈米顆粒，其中該 只顆粗係以嵌朗渡金屬氧化物如l (m=c〇、^ 二—）等氧化物包覆奈米碳材製備而成。由於奈米碳材之 ^為不求級’且常溫下不導電，以奈米碳材為載體之 鐘離子電池陰極，可以㈤、粒彳f，_子在陰極中所需 t擴散時間就會縮短’可快速地進人電解液，再擴散至 β端jtb陰極材料可使鐘離子在充放電過程中迅速遷 出及嵌入’加快電池充放電速度，大幅縮短充放電時間 ΰ [0024] 本實施例奈米碳材可採用奈米碳管、 奈米碳球或奈米線 [0025] 該種鋰離子電池之具體實施方式為：請參閱第一圖，該 鐘離子電池UH)包括-陰極11〇、—陽極12〇及連接陰極 110與陽極120並將其分隔開之滲透隔離膜130。該滲透 隔離膜130係多孔結構’其材質為聚乙稀。陽極120之材 質為f墨。本實施例鐘離子電池陰極110包含複數奈米顆 粒’該奈米顆粒係由氧化物包覆奈米碳材而形成。 [0026] 本實施例鐘離子電池100之工作原理為：娜子電池陰極 094119205 表單編St A0101 第7頁/共13頁 0993229577-0 1331817 099年06月29日核正替换頁 110之原子在氧化過程中變成離子，並釋放出電子，離子 通過滲透隔離膜130在另一電極還原，電子則傳輸至外電 路中形成電流。 [0027] 本實施例鋰離子電池陰極110之奈米顆粒係以水熱法製備 。水熱法係一種在密閉容器内完成的濕化學方法，與溶 膠凝膠法等其他濕化學方法之主要區別為溫度和壓力。 其溫度範圍介於水的沸點與臨界點（374°c)之間，通常介 於130〜250°C間，相應之水蒸汽壓為0. 3〜4 MPa。水熱 法所得粉末粒度通常爲0. 1微米至幾微米，甚至幾十納米 · ，且具有結晶好、團聚少、純度高、粒度分佈窄及形貌 _ 可控等優點。 / [0028] 第二圖係鋰離子電池陰極110之製備方法示意圖。其係於 一密閉容器10内進行，該密閉容器10内之水溶液11之溶 質為所需氧化物，將奈米碳材12加入該水溶液11中，加 熱，產生之水蒸氣產生高壓，在該條件下，產生所需之 鋰離子電池陰極材料。 [0029] 在加熱同時可進行攪拌，攪拌方式可採用電磁攪拌，亦 可採用攪拌棒攪拌。 [0030] 還可在加熱同時進行超聲波震盪，使奈米碳材粒子分散 更均勻。 [0031] 本實施例之奈米碳材為奈米碳管、奈米碳球或碳奈米線 [0032] 第三圖係本實施例奈米顆粒20之結構示意圖，其中，氧 化物21包覆於奈米碳材12表面。 094119205 表單編號 A0101 第 8 頁/共 13 頁 0993229577-0 1331817 099年06月29日按正替換頁 [0033] 本實施例鋰離子電池陰極及其製備方法提供了一種結晶 性佳、奈米級粒徑之陰極材料，且奈米碳材之特性提高 了陰極材料本身之導電性及熱穩定性，並縮短了固體陰 極材料中添加助導劑之製程。 [0034] • 本實施例製備之產物在水熱反應下已晶化，無需再經過 常規之熱處理晶化過程，從而可減少或消除熱處理過程 中之顆粒團聚。且不需高溫燒結即可直接得到結晶粉末 ，從而避免研磨及由此帶來的雜質。環境污染少、成本 低、易於商業化。 ' [0035] 綜上所述，本發明符合發明專利要件，爰依法提出專利 申請。惟，以上所述者僅為本發明之較佳實施方式，本 發明之範圍並不以上述實施方式為限，舉凡熟悉本案技 藝之人士，在援依本案發明精神所作之等效修飾或變化 ，皆應包含於以下之申請專利範圍内。 [0036] • [0037] 【圖式簡單說明】 第一圖係本實施例之鋰離子電池結構示意圖。 第二圖係本實施例鋰離子電池陰極之製備方法示意圖。 [0038] 第三圖係本實施例奈米顆粒之結構示意圖。 [0039] 【主要元件符號說明】 密閉容器：10 [0040] 水溶液：11 [0041] 奈米碳材：12 [0042] 奈米顆粒：20 094119205 表單编號A0101 第9頁/共13頁 0993229577-0 1331817 099年06月29日修正替換頁 [0043] 氧化物：21 [0044] 鋰離子電池：100 [0045] 陰極：110 [0046] 陽極：120 [0047] 滲透隔離膜：130 094119205 表單編號A0101 第10頁/共13頁 0993229577-0〇 U carbon atoms are bonded to three adjacent carbon atoms and have three δ bonds and one π bond. The carbon-carbon bond has two lengths, namely 1.38 angstroms and 1.45 angstroms; the carbon-carbon bond shared by two adjacent hexagons is shorter, close to the double bond (C=C) property (by A <5 key and a τι key are combined, and the key shared by the hex ring and the pentagon ring is longer, close to the nature of the single bond (CC). This unique chemical structure makes the chemical properties of nanocarbon spheres quite stable. [0021] It is possible to reduce the particle size of the cathode of the lithium ion battery, further improve the function of the lithium ion battery, increase the charge and discharge capacity, and accelerate the charge and discharge speed by utilizing the above properties of the nanocarbon carbon nanotubes. [0022] The lithium ion battery of this embodiment includes a cathode, an anode, and a permeation separator that connects the cathode and the anode and separates them. The above cathode, anode 0993229577-0 094119205 Form No. Α0101 Page 6 / 13 page of the separator is placed in the metal can, and the electrolyte is injected into the metal can:: the positive electrode, the negative electrode 'to generate an electrochemical reaction, the electrical energy And the conversion to the month "=· mutual conversion. Its t 'infiltration isolating membrane is a porous structure, which can make the electrical insulation of the part, such as polyethylene, polypropylene or polystyrene anode materials, such as various carbon materials including graphite, carbon fiber and metal oxide. Things and so on. [0023] The cathode of the ion battery of the embodiment comprises a plurality of nano particles, wherein the coarse particles are coated with nano-oxides such as oxides such as l (m=c〇, ^2). Made of wood. Since the nano carbon material is not graded and does not conduct electricity at normal temperature, the cathode of the ion battery with nano carbon as the carrier can (f), the particle f, the _ sub-diffusion time required in the cathode Shortening 'can quickly enter the electrolyte, and then diffuse to the β-end jtb cathode material, which can quickly move out and embed the clock ions during charging and discharging process. 'Accelerate the battery charging and discharging speed, greatly shorten the charging and discharging time ΰ [0024] The nano carbon material can be a carbon nanotube, a nano carbon sphere or a nanowire [0025] The specific embodiment of the lithium ion battery is as follows: Please refer to the first figure, the clock ion battery UH) includes a cathode 11 The anode, the anode 12, and the permeation separator 130 that connects the cathode 110 to the anode 120 and separates it. The permeable separator 130 is a porous structure, which is made of polyethylene. The material of the anode 120 is f ink. The cathode ion battery cathode 110 of the present embodiment comprises a plurality of nanoparticles. The nanoparticles are formed by coating a nanocarbon material with an oxide. [0026] The working principle of the clock ion battery 100 of the present embodiment is: Nazi battery cathode 094119205 Form editing St A0101 Page 7 / Total 13 page 0993229577-0 1331817 099 June 29 nuclear replacement page 110 atom is oxidized During the process, it becomes ions and emits electrons. The ions are reduced by the permeable separator 130 at the other electrode, and the electrons are transferred to an external circuit to form a current. [0027] The nanoparticle of the cathode 110 of the lithium ion battery of the present embodiment is prepared by a hydrothermal method. The hydrothermal method is a wet chemical method performed in a closed vessel, and the main difference from other wet chemical methods such as the sol gel method is temperature and pressure. 5〜4 MPa。 The temperature range is between the boiling point of the water and the critical point (374 ° C), usually between 130~250 ° C, the corresponding water vapor pressure is 0. 3~4 MPa. The particle size of the powder obtained by the hydrothermal method is usually from 0.1 μm to several micrometers, even several tens of nanometers, and has the advantages of good crystallization, less agglomeration, high purity, narrow particle size distribution and controllability. [0028] The second figure is a schematic diagram of a method of preparing a cathode of a lithium ion battery 110. It is carried out in a closed container 10, the solute of the aqueous solution 11 in the sealed container 10 is a desired oxide, and the nano carbon material 12 is added to the aqueous solution 11, and heated to generate high pressure in the water vapor. The cathode material of the desired lithium ion battery is produced. [0029] Stirring may be carried out while heating, and the stirring may be carried out by electromagnetic stirring or by stirring with a stirring bar. [0030] Ultrasonic vibration can also be performed while heating to make the nano carbon material particles more uniformly dispersed. [0031] The nano carbon material of the embodiment is a carbon nanotube, a carbon balloon or a carbon nanowire [0032] The third diagram is a schematic diagram of the structure of the nanoparticle 20 of the present embodiment, wherein the oxide 21 package Covered with the surface of nano carbon material 12. 094119205 Form No. A0101 Page 8 of 13 0993229577-0 1331817 June 29, 1999, according to the replacement page [0033] The lithium ion battery cathode of the present embodiment and the preparation method thereof provide a crystallized, nano-sized grain The cathode material of the diameter, and the characteristics of the nano carbon material improve the conductivity and thermal stability of the cathode material itself, and shorten the process of adding a promoter in the solid cathode material. [0034] The product prepared in this example has been crystallized under hydrothermal reaction, and no conventional heat treatment crystallization process is required, thereby reducing or eliminating particle agglomeration during heat treatment. The crystal powder can be directly obtained without high-temperature sintering, thereby avoiding grinding and impurities caused thereby. Less environmental pollution, low cost, and easy commercialization. [0035] In summary, the present invention complies with the requirements of the invention patent and submits a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described embodiments, and those skilled in the art will be equivalently modified or changed in accordance with the spirit of the invention. All should be included in the scope of the following patent application. [0037] [Simple Description of the Drawings] The first figure is a schematic structural view of a lithium ion battery of the present embodiment. The second figure is a schematic diagram of the preparation method of the cathode of the lithium ion battery of the present embodiment. [0038] The third figure is a schematic structural view of the nanoparticle of the present embodiment. [Description of main component symbols] Closed container: 10 [0040] Aqueous solution: 11 [0041] Nano carbon material: 12 [0042] Nanoparticle: 20 094119205 Form No. A0101 Page 9/Total 13 Page 0993229577- 0 1331817 Correction replacement page on June 29, 099 [0043] Oxide: 21 [0044] Lithium-ion battery: 100 [0045] Cathode: 110 [0046] Anode: 120 [0047] Permeable separator: 130 094119205 Form No. A0101 Page 10 of 13 Page 0993229577-0