201212349 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種鐘離子二次電池負極材料及 方法’尤指-種將天然石墨或人工石墨或兩者混合之粉 料’與-種或數種高硬碳含量之樹脂液體授摔混合後，利 用噴霧乾燥與碳化熱處理後，再包㈣殊樹脂材料，製備成 鋰離子二次電池負極材料，以及相關製程方法。 【先前技術】 *鋰離子二次電池的負極材料在最近這幾年被廣泛的研 究，因為傳統上以鋰金屬做為鋰電池負極材料存在著許多缺 點，其中包括鋰金屬表面產生樹枝狀結晶物析出，除了有安 全上的問題外，循環壽命也受影響。這些因素都會使電池失 效。而現今最被廣泛應用的莫過於碳系統，目前商業化鋰離 子二次電池所使用之負極材料為石墨，其中石墨又可分為人 工石墨與天然石墨。而人工石墨中的介穩相球狀碳(MCMB)， 繁雜的製程且需採用石墨化爐處理，造成生產成本過高的問 題。而在天然石墨方面，則由於在電池進行充放電過程中， 其第一次不可逆性較大，目前改善此缺點可用表面改質方 式，在石墨表面披覆上一層含碳層，經碳化熱處理後形成非 晶質碳材，透過這層非晶質碳膜，可以抑制鋰錯化合物嵌入 石墨層間，降低其不可逆電容量。在石墨表面包覆瀝青 (Pitch)，雖然有較小的比表面積，有較低的第一次不可逆 性’且可以改善石墨負極材與電解液的相容性，生產成本較 為低廉，但是隨著充放電次數的增加，其電容量會持續衰 201212349 退’造成循環壽命變差，如日本專利公開第2000-261046號對 石墨做氧化處理，改變石墨表面的狀態，雖可以改善負極材 料與電解液的相容，但是其電容量低於純天然石墨電容量。 中國專利公開第CN1224251A號、第CN1304187A號採用乙醇或 其他溶劑來溶解呋喃樹脂、聚丙烯腈樹脂、酚醛樹脂、尿素 樹脂、環氧樹脂、聚脂樹脂、聚酰胺樹脂、嘧胺樹脂等高硬 石厌含量之樹脂來包覆石墨’但是上述方法有比表面積過大， _ 包覆後石墨顆粒容易黏結成塊，經粉碎處理後會造成包覆層 脫落破損，影響負極材料性能等缺點。 基於先前採用高硬碳含量之樹脂對天然石墨表面型態改 質研究，雖說此方法可以降低第一次不可逆，並在充放電循 環中有較好的電容量保持性，透過這層非晶質碳膜，可以抑 制鐘錯化合物嵌入石墨層間，來降低其不可逆電容量與減緩 充放電遲滯現象’但其研究可發現天然石墨其為片狀結構， 因此鋰離子的嵌入嵌出受石墨晶體邊界限制，所以快速充放 ® 電性能較差，加上包覆非晶質碳之表面時仍有許多縫隙，因 而造成比包覆後的石墨比表面積過大。 【發明内容】 有鑒於習用已採用之多型態碳材料作為鋰離子二次電 池負極材料，除了碳材經石墨化後高成本且繁琐的製程， 而全球對於3C電子產品、電動手工具、電動車的需求大幅 成長’因此’發明人依據多年來從事此課題之相關經驗， 經過長久努力研究與實驗，並配合相關學理，開發設計出 本發明之一種「裡離子二次電池負極材料及其製備方 201212349 法」。 本發明之目的即在提供一種以一人工石墨或一天然石 墨或兩者混合為基礎，並經特殊製程製得之鋰離子二次電 池負極材料。 本發明之次一目的係在提供一種裡離子二次電池負極 材料之製備方法。 可達成上述發明目的之鋰離子二次電池負極材料之技 術手段在於：由一天然石墨、一人工石墨或兩者混合其中 之一者，以形成一石墨粉，並與一高硬碳含量之樹脂混合 經喷霧乾燥處理，經碳化熱處理後，再添加一特殊樹脂材 料，以製配成一链離子電池負極材料之石墨複合材。 在本發明一較佳實施例中，該高硬碳含量之樹脂選自 一呋喃樹脂、一聚丙烯腈樹脂、一酚醛樹脂、一尿素樹脂、 一環氧樹脂、一聚脂樹脂、一聚酰胺樹脂及一嘧胺樹脂其中 之一。 在本發明一較佳實施例中，該石墨粉之獲得係由該 天然石墨及該人工石墨其中之一，以經過篩、研磨、混練 到粒徑至5〜30/zm。 可達成上述發明目的之鋰離子二次電池負極材料之製 備方法之技術手段在於：將一天然石墨、一人工石墨戋兩 者混合其中之—者，以形成—石墨粉；將該石墨粉與一高 硬碳含量_混合絲體，且__賴，混合製作= 粉體’再㈣粉體於—碳化爐中進行熱處理；林處理其 間通入氮氣⑽作為保護氣氛，升溫至所需熱處理溫度 201212349 800〜1400°C，尤以900〜1200°C為佳，升溫時間為 1〜10。C/min，持溫時間為卜5hr，熱處理完後取出；再添 加入一特殊樹脂之溶液中，加以攪拌、混合，經加熱乾燥 後即得到一石墨碳複合材粉體，以作為鋰離子二次電池負 極材料。 在本發明一較佳實施例中，該高硬碳含量樹脂選自一 呋喃樹脂、一聚丙烯腈樹脂、一酚醛樹脂、一尿素樹脂、一 環氧樹脂、一聚脂樹脂、一聚酰胺樹脂及一嘧胺樹脂其中之 〇 在本發明一較佳實施例中，該高硬碳含量之樹脂選自 一呋喃樹脂、一聚丙烯腈樹脂、一酚醛樹脂、一尿素樹脂、 一環氧樹脂、一聚脂樹脂、一聚酰胺樹脂及一嘧胺樹脂其中 之一。 在本發明一較佳實施例中，該高硬碳含量樹脂在該石 墨複合材料中，所佔固含量之比例為3〜25 wt%。 在本發明一較佳實施例中，該特殊樹脂選自一聚苯胺 (Polyaniline )、一聚苯硫醚(Polyphenylene Sulfide)、一 聚吡咯（Polypyrrole)、一聚3,4-乙烯二氧噻吩/聚苯乙烯 %酉欠（PED0T-P0SS)、一聚乙炔系及一聚嘆^坐系、一聚婦N基 胺類其中之一。 在本發明一較佳實施例中，該特殊樹脂之溶液在該石 墨複合材料t，所佔含量之比例為〇.1〜2〇 wt%。 在本發明一較佳實施例中，該添加入該特殊樹脂溶液 之步驟，將其加以攪拌、混合，經加熱乾燥之溫度為 201212349 100〜20(TC，及乾燥時間為30〜120分鐘。 【實施方式】 為便於貴審查委員能對本發明之技術手段及運作過程 有更進一步之認識與瞭解’茲舉實施例配合圖式，詳細說明 如下。 本發明所提供之「製備一種鐘離子二次電池負極材料 及其方法」，係以一天然石墨或人工石墨或兩者混合作為 母材’其粒徑控制於5〜30 ’與3〜25 wt%高硬碳含量 之樹脂混合成漿體，再由喷霧乾燥方式製作成包覆均勻之粉 體後，經破化熱處理溫度800〜1400°C下而後冷卻取出，再 將其加入特殊樹脂材料液體中授拌混合乾燥後，即獲得該 表面改質負極材料’藉以解決習用之多型態碳材料（例 如：天然石墨、煤炭、碳纖維和介穩相球狀碳MCMB)， 具充放電速度慢、電容量低及價格昂貴等缺點。 請參閱第1圖所示’為本發明石墨複合材添加特殊樹 脂後之示意圖，將一石墨材11與一種或數種高硬碳含量之 高分子樹脂12混合成漿料後，先利用噴霧乾燥製作成一樹脂 彼覆石墨之負極材，經熱處理碳化後，再加入一特殊樹脂13 材料，如一聚苯胺(Polyaniline)等，將這些高分子材料披覆 於非晶質碳表面，使表面微孔洞修補填平，而石墨材完全 被非晶質碳與該特殊樹脂材13包覆’其材料結構在石墨複合 材表面成形較為平整無縫之型態，比表面積也明顯降低，且 能提升鋰離子二次電池充放電性能，使鋰離子可以快速的進 出，其對於電解液的反應更穩定、較好的充放電循環性能， 201212349 因此可作為鐘離子電池負極材料。 圖所為本發明石墨複合材之製備流程 圖，该石墨複合材之製備方法’為依下料驟進行執行： 步驟一、將天然或人工或兩者混合之石墨粉末過筛、 研磨’控制其粒徑於5〜30/zm ;201212349 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cathode material and method for a plasma ion secondary battery, particularly a powder of natural graphite or artificial graphite or a mixture of the two. Or a plurality of high-hard carbon content resin liquids are mixed and mixed, and then spray-drying and carbonization heat treatment, and then (four) special resin materials, to prepare lithium ion secondary battery anode materials, and related process methods. [Prior Art] * Anode material for lithium ion secondary batteries has been extensively studied in recent years because conventionally, lithium metal is used as a negative electrode material for lithium batteries, which has many disadvantages, including dendritic crystals on the surface of lithium metal. In addition to the safety problems, the cycle life is also affected. These factors can cause the battery to fail. The most widely used carbon synthesis system today is the graphite material used in commercial lithium ion secondary batteries, which can be divided into artificial graphite and natural graphite. The metastable phase spheroidal carbon (MCMB) in artificial graphite, which is complicated in process and needs to be treated by a graphitization furnace, causes a problem of high production cost. In the case of natural graphite, since the first irreversibility is large during the charging and discharging process of the battery, the surface modification method can be improved by surface modification, and a carbon layer is coated on the surface of the graphite after carbonization heat treatment. The formation of an amorphous carbon material and the passage of the amorphous carbon film prevent the intercalation of the lithium-discriminating compound between the graphite layers and reduce the irreversible capacitance. Pitch coated on the surface of graphite, although it has a small specific surface area, has a low first irreversibility and can improve the compatibility of the graphite negative electrode with the electrolyte, and the production cost is relatively low, but with When the number of times of charge and discharge increases, the capacity of the battery will continue to decline 201212349. The cycle life will be deteriorated. For example, the oxidation treatment of graphite is carried out in Japanese Patent Publication No. 2000-261046, and the state of the graphite surface is changed, although the anode material and the electrolyte can be improved. Compatible, but its capacitance is lower than that of pure natural graphite. Chinese Patent Publication No. CN1224251A, No. CN1304187A uses ethanol or other solvents to dissolve high hardness hardening such as furan resin, polyacrylonitrile resin, phenolic resin, urea resin, epoxy resin, polyester resin, polyamide resin, and pyrimidine resin. Resistant content of resin to coat graphite 'but the above method has a large specific surface area, _ after coating, the graphite particles are easy to stick into a block, which will cause the coating layer to fall off and break, which will affect the performance of the negative electrode material. Based on the previous study of surface modification of natural graphite with high hard carbon content resin, although this method can reduce the first irreversible, and has good capacity retention in the charge and discharge cycle, through this layer of amorphous The carbon film can suppress the incorporation of the clock-error compound into the graphite layer to reduce its irreversible capacitance and slow down the charge-discharge hysteresis. However, its research can find that natural graphite is a sheet-like structure, so the insertion and embedding of lithium ions is restricted by the boundary of the graphite crystal. Therefore, the rapid charge and discharge performance is poor, and there are still many gaps when the surface of the amorphous carbon is coated, resulting in a larger specific surface area than the coated graphite. SUMMARY OF THE INVENTION In view of the conventional use of polymorphic carbon materials as lithium ion secondary battery anode materials, in addition to the high cost and cumbersome process of carbon material after graphitization, and global 3C electronic products, electric hand tools, electric The demand for the car has grown significantly. Therefore, the inventor has developed and designed a "Li-ion secondary battery anode material and its preparation based on long-term efforts and research, and with relevant theories, based on years of experience in this subject. Party 201212349 Law. SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithium ion secondary battery anode material which is based on an artificial graphite or a natural graphite or a mixture of the two and which has been specially prepared. A second object of the present invention is to provide a method for preparing a negative electrode material for a ionic secondary battery. The technical means for achieving the lithium ion secondary battery anode material of the above object is to form a graphite powder from a natural graphite, an artificial graphite or a mixture of the two, and a resin having a high hard carbon content. The mixture is spray-dried, and after carbonization heat treatment, a special resin material is further added to prepare a graphite composite material which is a negative electrode material of a chain ion battery. In a preferred embodiment of the present invention, the high hard carbon content resin is selected from the group consisting of a furan resin, a polyacrylonitrile resin, a phenolic resin, a urea resin, an epoxy resin, a polyester resin, and a polyamide. One of resin and monopyramine resin. In a preferred embodiment of the present invention, the graphite powder is obtained by sieving, grinding and kneading one of the natural graphite and the artificial graphite to a particle size of 5 to 30/zm. The technical means for preparing the lithium ion secondary battery anode material which can achieve the above object of the invention is that: a natural graphite, an artificial graphite crucible is mixed therein to form - graphite powder; the graphite powder and the graphite powder High hard carbon content _ mixed silk body, and __ Lai, mixed production = powder 're (four) powder in the carbonization furnace for heat treatment; during the forest treatment, nitrogen (10) is passed as a protective atmosphere, and the temperature is raised to the required heat treatment temperature 201212349 800 to 1400 ° C, especially 900 to 1200 ° C is preferred, and the heating time is 1 to 10. C/min, holding temperature for 5hr, taken out after heat treatment; added to a special resin solution, stirred, mixed, heated and dried to obtain a graphite carbon composite powder, as lithium ion two Secondary battery anode material. In a preferred embodiment of the present invention, the high hard carbon content resin is selected from the group consisting of a furan resin, a polyacrylonitrile resin, a phenolic resin, a urea resin, an epoxy resin, a polyester resin, and a polyamide resin. And a pyrimidine resin, wherein in the preferred embodiment of the present invention, the high hard carbon content resin is selected from the group consisting of a furan resin, a polyacrylonitrile resin, a phenolic resin, a urea resin, an epoxy resin, One of a polyester resin, a polyamide resin and a monopyramine resin. In a preferred embodiment of the invention, the high hard carbon content resin has a solid content ratio of from 3 to 25 wt% in the graphite composite. In a preferred embodiment of the present invention, the special resin is selected from the group consisting of polyaniline, polyphenylene Sulfide, polypyrrole, and poly(3,4-ethylenedioxythiophene). Polystyrene% 酉 ( (PED0T-P0SS), a polyacetylene system and a polysulphide system, one of the N-amines. In a preferred embodiment of the present invention, the ratio of the content of the special resin to the graphite composite t is 〇1 to 2 〇 wt%. In a preferred embodiment of the present invention, the step of adding the special resin solution is carried out by stirring and mixing, and the temperature by heating and drying is 201212349 100~20 (TC, and the drying time is 30 to 120 minutes. The present invention provides a more detailed understanding and understanding of the technical means and operation process of the present invention. The following is a detailed description of the following: "Preparation of a clock ion secondary battery" The anode material and the method thereof are prepared by mixing a natural graphite or artificial graphite or a mixture of the two as a base material, wherein the particle size is controlled at 5 to 30' and the resin having a high hard carbon content of 3 to 25 wt% is mixed into a slurry. After being spray-dried to form a uniformly coated powder, it is cooled and cooled at a temperature of 800 to 1400 ° C, and then cooled and taken out, and then added to a special resin material liquid to be mixed and dried, thereby obtaining the surface modification. The material of the negative electrode material is used to solve the multi-type carbon materials (for example, natural graphite, coal, carbon fiber and metastable phase spherical carbon MCMB), which has a slow charge and discharge rate and a low capacitance. Disadvantages such as high price. Please refer to Fig. 1 for a schematic diagram of adding a special resin to the graphite composite of the present invention, and mixing a graphite material 11 with one or several high-hard carbon content polymer resins 12 into a slurry. First, spray-drying a negative electrode material of graphite and graphite, after carbonization by heat treatment, and then adding a special resin 13 material, such as polyaniline, etc., the polymer material is coated on the surface of the amorphous carbon. The surface micro-holes are repaired and filled, and the graphite material is completely covered by the amorphous carbon and the special resin material 13. The material structure is formed into a flat and seamless shape on the surface of the graphite composite material, and the specific surface area is also significantly reduced. Moreover, it can improve the charge and discharge performance of the lithium ion secondary battery, so that the lithium ion can enter and exit quickly, the reaction to the electrolyte is more stable, and the charge and discharge cycle performance is better, 201212349 can be used as the anode material of the clock ion battery. The flow chart for preparing the graphite composite material, the preparation method of the graphite composite material is performed according to the following steps: Step 1: Natural or artificial or The graphite powder mixed with the two is sieved and ground to control the particle size of 5~30/zm;
步驟二、將該步驟-所獲得之石墨粉與含有適當比例 溶劑之㈣碳含量之卿液體混合，均勻㈣絲狀液 體。如是採溶劑型樹酬須先·_加熱的方式溶劑去 除，才可投入喷霧乾燥機内進行噴霧乾燥製程； 步驟三、將該步驟二所獲得之聚料投人噴霧乾燥機 内’製作絲棚〜心m之石墨健後，再進行碳化熱處 理； * 步驟四、其熱處理升溫速度為1〜1〇〇c/min至所需 熱處理溫度800〜1400°C，尤以在900〜ll〇〇°c最佳，在 §玄溫度維持1〜15小時後，冷卻至室溫； 步驟五、將該步驟四所獲得之粉料添加入固含量〇. j 〜20%之特殊樹脂液體中加以攪拌、混合，經1〇〇〜2〇(Γ(： 加熱乾燥，時間為30〜120分鐘’即得到本發明之石墨複合 材’並將其作為鋰離子二次電池負極材料。 前述該高硬碳含量之高分子樹脂12係選自指一呋喃樹 月曰、一聚丙稀腈樹脂、一酌搭樹脂、一尿素樹脂、一環氧樹 脂、一聚脂樹脂、一聚酰胺樹脂、一嘧胺樹脂…等之樹脂。 前述該特殊樹脂13係指選自一聚笨胺 (Polyaniline )、 一聚苯硫鍵（Polyphenylene 201212349Step 2. Mix the graphite powder obtained in this step with a liquid of (4) carbon content in an appropriate proportion of the solvent to uniformly (four) the filamentous liquid. If it is a solvent-based tree, it must be heated before the solvent is removed, and then it can be put into the spray dryer to carry out the spray drying process. Step 3: The material obtained in the second step is injected into the spray dryer to make a silk shed~ After the graphite of the heart m is cured, the carbonization heat treatment is further performed; * Step 4, the heat treatment temperature is 1~1〇〇c/min to the required heat treatment temperature of 800~1400°C, especially at 900~ll〇〇°c Preferably, after maintaining for 1 to 15 hours, the temperature is cooled to room temperature; Step 5, adding the powder obtained in the step 4 to a special resin liquid having a solid content of 〇. j to 20%, stirring and mixing The graphite composite of the present invention is obtained by using 1 〇〇 2 〇 (: (heat drying, time is 30 to 120 minutes) and is used as a negative electrode material for a lithium ion secondary battery. The high hard carbon content is as described above. The polymer resin 12 is selected from the group consisting of a furan tree, a polyacrylonitrile resin, a resin, a urea resin, an epoxy resin, a polyester resin, a polyamide resin, a pyrimidine resin, etc. The foregoing resin 13 is selected from the group consisting of Stupid amine poly (Polyaniline), a polyphenylene sulfide linkage (Polyphenylene 201212349
Sulfide)、一聚吡咯（Polypyrrole)、一聚噻吩磺酸鹽 類（PED0T)、一聚乙炔系、一聚噻唑系、一聚烯N基胺 類等。 表1-1樣本A1與A2製程條件輿比袅面猜比較 樣本 過篩 研磨 處理 尚硬碳含量 樹脂彼覆 (D夫喃樹脂） 噴霧 乾燥 碳化 熱處理 聚〇比洛 液體 比表面積 (mV) A1 有 8wt% 有 有 無添加 20.41 A2 有 8wt% 有 有 5wt% 2.85 表1-2樣本B1與B2製程條件與比表面積比較 ---- 樣本 過師 研磨 高硬碳含量 樹脂披覆 噴霧 碳化 聚苯胺 比表面積 處理 (聚酰胺樹脂） 乾燥 熱處理 液體 (mV) B1 有 8wt% 有 有 無添加 28.50 B2 有 8wt% 有 有 5wt% 3. 15 參看表1-1與表卜2所示，經由喷霧乾燥與碳化熱處 理後’加入5wt%該特殊樹脂！3 (聚各液體、聚苯胺液體) 材料的石墨複合材A2、B2比表面積分別為2 85 y疒、 3. 15 m2g 1，遠小於經過噴霧乾燥但無添加該特殊樹脂13 1料之石墨複合材A卜B1的比表面積2G 41 my丨、28 5〇 m g 1。未添加該特殊樹脂13的“、M，其石墨材丨丨經研 201212349 磨處理後與8w%料樹丨旨、8w%聚跌胺樹丨旨混合，再經 喷霧乾燥後’石墨表面披覆了—層細旨，碳化減理後為 所需之石墨複合材’但是經由比表面積儀檢測後，發現比 表面積偏大，該表面積為20.41〜28.50 n^g1，這是因為 ；5墨外層雖然披覆了—層樹脂，但碳化熱處理後，樹脂受 加熱溫度與持溫時間的影響下，會造成樹脂與石墨材^内 部有些物質析出’使得石墨麟複合材表面產生孔洞與細 縫，而造成其比表面積偏大。而A2、於為石墨樹脂混合 後經喷霧麟無倾處理後，縣加該特殊樹脂13之石 墨複合材，其比表面積經由比表面積儀檢測後為2 85〜 3. 15 m2g 1，其原因為經噴霧乾燥處理，該特殊樹脂以可 以完整的披覆於石墨表面上，熱處理後其表面會有微孔 /同，造成比表面積增加，因此添加適當比例的特殊樹脂材 後，可將細縫修補填平，使粉末表面坑洞與細縫減少結 構更為元整’因此可以將比表面積有效的降低。 以下是將該石墨複合材Al、A2、Bl、B2粉體，作為 鋰離子動力電池負極材料塗佈與電池組裝之實施例： 電池負極材料塗佈： 1. 先將0.1 wt%微量草酸與1〇 wt%之聚偏氟乙烯 (Polyvinylidene fluoride (PVDF))黏結劑 (Binder)，混入N —曱基呲咯烷酮（ prrolidone (NMP))溶劑中，均勻攪拌2〇分鐘，使得該 聚偏氟乙稀（PVDF)能均勻分散於該溶劑之混合液中. 2. 將該石墨複合材Al、A2、Bl、B2粉末置入擾拌均 201212349 勻之混合液，持續攪拌20分鐘； 3.該混合液形成泥漿狀物，以i3〇；Wm刮刀均勻塗佈 在銅箔上’以100 c烘乾去除殘留溶劑，以25%之碾壓 率進行碾壓，再以150°C烘乾。 電池組裝： 1. 將塗佈完整之負極極片裁成直徑13 mm的圓板，正 極則採用鐘金屬箔片； 2. 將硬t形電池所需之組件，於乾燥氣氛控制室中依 序組裝，並添加一電解質液（1M裡六氟鱗酸鹽（^ρρ6) (溶質）一碳酸乙烯酯（EC) /碳酸曱乙酯（EMC)(溶劑） (Volume 1:2))’即完成一硬幣形電池； 3. 將組裝完成之硬幣型電池進行連續充放電性能測 试，其充放電速率為0. 2C，定電流密度進行連續充放電 50次，充電截止電壓為2V (vs. Li / U+ )，放電截止 電壓為0. 005V (vs. Li / Li+ )。 請同時參閱第3圖及第4圖所示，由圖中可以看到 Al、A2的第一次充電電容量分別為344 “h/g和365 mAh/g ’第一次放電電容量分別為3U mAh/g、338 mAh/g。而B1、B2的第一次充電電容量分別為mi mAh/g 和350 mAh/g，第一次放電電容量分別為3〇〇 mAh/g、 320 mAh/g。因此可以發現在第一次充放電之不可逆電容 中，石墨複合材A1與B1的不可逆電容量較大為33 mAh/g 與41 mAh/g，而有添加該特殊樹脂13處理的石墨複合材 A2與B2，其第一次不可逆電容量可降低為28 mAh/g和30 201212349 mAh/g，如下表2-1、2-2所示： 表2-1樣本A1與A2的電化學性質比較 樣本 第一次 充電容量 (mAh/g) 第一次 放電容量 (mAh/g) 第一次充放電 不可逆電容量 (mAh/g) 第一次充放 電不可逆性 (%) 第50^ 庫倫效率 (%) -- 88 A1 344 311 33 11 A2 366 338 28 8 98 表2-2 樣本B1與B2的電化學性皙此 --—-_ 4交 第一次 第一次 第一次充放電 第一次充放 、---- 第50次 樣本 充電容量 放電容量 不可逆電容量 電不可逆性 庫倫效率 (mAh/g) (mAh/g) (mAh/g) (%) (%) B1 341 300 41 13 85 B2 350 320 30 9 95 • 此外’石墨複合材M、B1為該石墨材11與該高分子樹脂 12先均勻混合後’經由喷霧乾燥與碳化熱處理後，其表面有 許多微孔洞，而造成其比表面積過大，而導致第一次不可逆 性較大的因素’由石墨複合材A2、B2更能驗證。 請參閱第5圖所示’由圖中可以看到石墨複合材M、 A2、B卜B2的循環次數與放電容量關係圖，由於链離子 在充放電過程中，會與鐘離子電池中的電解液發生反應， 而在該石墨材11的表面形成一種薄獏狀的SEi(s〇Hd electrolyte interface)膜，使鋰離子二次電池不可逆 201212349 電谷量增加，石墨複合材A1、81雖然表面有樹脂包覆的 結構，可以減緩SEI膜的形成，但是由於表面上有許多微 孔洞與細縫，所以一但充放電循環次數增加後，其石墨層 也會開始崩落脫離，造成循環穩定度變差，加上比表面積 偏尚，第一次不可逆性也會較大。…與犯複合材分別都 添加了该特殊樹脂13，該特殊樹脂13除了可填補原本石 墨表面包覆經碳化熱處理所造成非晶質碳的微孔洞外，可 以減緩SEI膜的形成，加上該特殊樹脂13為一種具有低電 ，值與彈性之材料，除了可以改善該石墨材u與該高分子 樹脂12的導電特性外，也讓鋰離子進出自由更有效率，因 此A2、B2複合材會有較高的電容量與較佳的循環穩定 性。 請參閱第6圖所示，可以比較石墨複合材A1、A2、 B1、B2的50次循環的庫倫效率，由圖可知石墨複合材“ 和B1第一次循環的庫倫效率小於Α2、β2，且在5〇次循環之 後其電容量保持率（Capacity reterrti〇ns)為八2、β2大於 Α1和Β1，所以可知是由於石墨複合材…與於在熱處理後 添加該特殊樹脂12的效果，其原因為添加該特殊樹脂12 後，除了可以填補石墨複合材的表面縫隙，以降低其比表 面積，且此低電阻之特殊樹脂，進而使鐘離子的進出更為 順暢，加上該特殊樹脂13可以減緩SEI膜的發生，所以能 造成如此高的循環穩定度及電容量保持率，其庫倫效率5〇次 均可達到98%〜95%。 上列洋細說明係針對本發明之一可行實施例之具體說 201212349 明，惟該實施例並非用以限制本發明之專利範圍，凡未脫 離本發明技藝精神所為之等效實施或變更，均應包含於本 案之專利範圍中。 【圖式簡單說明】 第1圖為本發明石墨複合材添加特殊樹脂後之示意 圖； 第2圖為本發明石墨複合材之製備流程圖； ¥ 第3圖為本發明第一次石墨複合材Al、A2的充放電電 容量圖； 第4圖為本發明第一次石墨複合材Bl、B2的充放電電 容量圖； 第5圖為本發明石墨複合材Al、A2、Bl、B2的50次循 環次數對放電容量圖；以及 第6圖為本發明石墨複合材Al、A2、Bl、B2的50次循 環次數之庫倫效率圖。 • 【主要元件符號說明】 11 石墨材 12 高分子樹脂 13 特殊樹脂 15Sulfide), polypyrrole, polythiophene sulfonate (PEDOT), polyacetylene, polythiazole, monoolefin N-amine, and the like. Table 1-1 Sample A1 and A2 process conditions 舆Compared with the surface comparison sample sieving and grinding treatment still hard carbon content resin (Duffan resin) Spray drying carbonization heat treatment polypyridyl liquid specific surface area (mV) A1 8wt% with or without addition 20.41 A2 with 8wt% with 5wt% 2.85 Table 1-2 Sample B1 and B2 process conditions and specific surface area comparison---- Samples have been milled with high hard carbon content resin coated spray carbonized polyaniline specific surface area Treatment (polyamide resin) Dry heat treatment liquid (mV) B1 has 8wt% with or without addition 28.50 B2 with 8wt% with 5wt% 3. 15 See Table 1-1 and Table 2, through spray drying and carbonization heat treatment After 'add 5wt% of this special resin! 3 (Poly liquid, polyaniline liquid) The graphite composite materials A2 and B2 have a specific surface area of 2 85 y 疒, 3. 15 m2g 1, which is much smaller than the graphite composite which has been spray-dried but has no special resin added. The specific surface area of the material Ab B1 is 2G 41 my丨, 28 5〇mg 1. ", M, which is not added with the special resin 13, is a graphite material, and is subjected to grinding treatment with 201212349, and is mixed with 8w% of the tree, 8w% polyamine, and then spray-dried. Covered - the layer is designed to be the desired graphite composite after carbonization reduction. However, after detecting by the specific surface area meter, it is found that the specific surface area is too large, and the surface area is 20.41~28.50 n^g1, which is because; Although the layer of resin is coated, after the carbonization heat treatment, the resin is affected by the heating temperature and the holding time, which causes some substances in the resin and the graphite material to precipitate out, which causes pores and slits on the surface of the graphite lining composite. The specific surface area is too large. After A2, the graphite resin is mixed and sprayed without tilting, the graphite composite material of the special resin 13 is added to the county, and the specific surface area is 2 85~3 after being detected by the specific surface area meter. 15 m2g 1, the reason is that after spray drying, the special resin can be completely coated on the surface of the graphite, and the surface of the graphite will have micropores/same after heat treatment, resulting in an increase in specific surface area, so adding an appropriate proportion of the special After the resin material, the repair of the slit can be filled flat, so that the surface pit and the slit reduction structure of the powder are more uniform. Therefore, the specific surface area can be effectively reduced. The following is the graphite composite material Al, A2, Bl, B2. Powder, as an example of coating and battery assembly of lithium ion power battery anode material: Battery anode material coating: 1. First 0.1 wt% trace oxalic acid and 1 wt% polyvinylidene fluoride (PVDF) Binder, mixed with N-mercaptopyrrolidone (prrolidone (NMP)) solvent, stirred evenly for 2 minutes, so that the polyvinylidene fluoride (PVDF) can be uniformly dispersed in the solvent mixture 2. The graphite composite Al, A2, Bl, B2 powder is placed in a mixture of 0.212349 and stirred for 20 minutes; 3. The mixture forms a slurry, i3〇; Wm scraper evenly Coated on copper foil 'drying at 100 c to remove residual solvent, rolling at 25% rolling ratio, and drying at 150 ° C. Battery assembly: 1. Cut the coated negative electrode piece into a circular plate with a diameter of 13 mm and a metal foil for the positive electrode; 2. a hard t-shaped The components required for the pool are assembled in the dry atmosphere control room in sequence, and an electrolyte solution (1M hexafluorophosphate (^ρρ6) (solute) ethylene carbonate (EC) / cesium carbonate (EMC) is added. 2C, continuous current density for continuous operation. The charge-discharge rate is 0. 2C, continuous current density is continuous. (Colour 1:2)) Charge and discharge 50 times, the charge cut-off voltage is 2V (vs. Li / U+), and the discharge cut-off voltage is 0. 005V (vs. Li / Li+ ). Please also refer to Figure 3 and Figure 4. It can be seen from the figure that the first charge capacity of Al and A2 is 344 "h/g and 365 mAh/g respectively". The first discharge capacity is 3U mAh/g, 338 mAh/g, while the first charge capacities of B1 and B2 are mi mAh/g and 350 mAh/g, respectively, and the first discharge capacity is 3〇〇mAh/g and 320 mAh, respectively. /g. Therefore, it can be found that in the irreversible capacitance of the first charge and discharge, the irreversible electric capacity of the graphite composite materials A1 and B1 is 33 mAh/g and 41 mAh/g, and the graphite treated with the special resin 13 is added. For composites A2 and B2, the first irreversible capacity can be reduced to 28 mAh/g and 30 201212349 mAh/g, as shown in Tables 2-1 and 2-2 below: Table 2-1 Electrochemistry of samples A1 and A2 Property comparison sample first charge capacity (mAh/g) First discharge capacity (mAh/g) First charge and discharge irreversible capacity (mAh/g) First charge and discharge irreversibility (%) 50^ Coulomb Efficiency (%) -- 88 A1 344 311 33 11 A2 366 338 28 8 98 Table 2-2 Electrochemical properties of samples B1 and B2 ----_ 4 first time first first charge and discharge First charge ,---- 50th sample charge capacity discharge capacity irreversible capacity electrical irreversibility Coulomb efficiency (mAh/g) (mAh/g) (mAh/g) (%) (%) B1 341 300 41 13 85 B2 350 320 30 9 95 • In addition, 'Graphite composites M and B1 are the above-mentioned graphite material 11 and the polymer resin 12 are uniformly mixed first. After passing through spray drying and carbonization heat treatment, there are many micropores on the surface, resulting in a ratio of The surface area is too large, and the factor that causes the first irreversibility is more validated by the graphite composites A2 and B2. Please refer to Figure 5, where the graphite composites M, A2, B, and B2 can be seen. The relationship between the number of cycles and the discharge capacity, since the chain ions react with the electrolyte in the ion battery during charge and discharge, a thin braided SEi (s〇Hd electrolyte) is formed on the surface of the graphite material 11. Interface) membrane, lithium ion secondary battery irreversible 201212349 electric valley increase, graphite composite A1, 81 surface with a resin-coated structure, can slow the formation of SEI film, but because there are many micro-pores and fine on the surface Sew, so charge and discharge After the increase in the number of rings, it also began to crumble from the graphite layer, resulting in poor circulation stability, coupled with the specific surface area is still partial, for the first time irreversibility will be larger. The special resin 13 is added to the composite material, and the special resin 13 can not only fill the micropores of the amorphous carbon surface caused by the carbonization heat treatment, but also slow down the formation of the SEI film. The special resin 13 is a material having low electric power, value and elasticity. In addition to improving the conductive properties of the graphite material u and the polymer resin 12, the lithium ion is more and more free to enter and exit, so the A2 and B2 composite materials are used. There will be higher capacitance and better cycle stability. Referring to Figure 6, the coulombic efficiency of the 50 cycles of the graphite composites A1, A2, B1, and B2 can be compared. It can be seen from the figure that the coulombic efficiency of the graphite composite "and the first cycle of B1 is less than Α2, β2, and After 5 cycles, the capacity retention ratio (Capacity reterrti〇ns) is 8.2, and β2 is larger than Α1 and Β1, so it is known that the graphite composite material and the effect of adding the special resin 12 after heat treatment are the reasons. In order to add the special resin 12, in addition to filling the surface gap of the graphite composite to reduce the specific surface area thereof, and the low-resistance special resin, the clock ions can be smoothly moved in and out, and the special resin 13 can be slowed down. The occurrence of the SEI film can result in such high cycle stability and capacity retention, and the Coulomb efficiency can reach 98% to 95% at 5 times. The above description is directed to a possible embodiment of the present invention. In particular, the present invention is not intended to limit the scope of the invention, and equivalents to the embodiments of the invention should be included in the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the addition of a special resin to the graphite composite material of the present invention; Fig. 2 is a flow chart for preparing the graphite composite material of the present invention; Fig. 4 is a charge and discharge capacity diagram of the first graphite composite materials B1 and B2 of the present invention; Fig. 5 is a graph showing the graphite composite materials Al, A2, B1 and B2 of the present invention. 50 cycles of discharge capacity map; and Fig. 6 is a Coulomb efficiency diagram of the number of cycles of the graphite composites Al, A2, Bl, and B2 of the present invention. • [Main component symbol description] 11 Graphite material 12 Polymer resin 13 special resin 15