TWI429130B - Application of graphite powder in anode material of lithium ion battery and its preparation method - Google Patents
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Description
本發明係關於一種石墨微粉應用於鋰離子電池負極材料及其製備方法，尤指一種採負極材料廠生產時所產生尾料的天然石墨微粉，將該天然石墨微粉與高分子樹脂攪拌混合後，再利用噴霧乾燥方式造粒，並經適當熱處理而成為一石墨複合材，製作成一鋰離子電池負極材料。The invention relates to a graphite micropowder applied to a lithium ion battery anode material and a preparation method thereof, in particular to a natural graphite powder produced by the tailing material material factory, and the natural graphite powder and the polymer resin are stirred and mixed. Then, it is granulated by spray drying, and is appropriately heat-treated to form a graphite composite material to prepare a lithium ion battery anode material.
鋰離子二次電池的負極材料在最近幾年被廣泛的研究，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。The anode material of 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 the formation of dendritic crystals on the surface of lithium metal, in addition to safety. In addition to the problem, the cycle life is also affected. These factors will cause the battery to fail.
而現今最被廣泛應用的莫過於碳系統，目前商業化鋰離子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)，繁雜的製程需採用石墨化爐處理，造成生產成本過高的問題。在天然石墨包覆瀝青方面雖然有較小的比表面積，有較低的第一次不可逆性，並可以改善石墨負極材與電解液的相容性，且生產成本較為低廉，但是隨著充放電次數的增加，其電容量會持續衰退，造成循環壽命變差，而且目前商業市售的球形石墨負極材料其粉體平均粒徑為10~25 μm，在10 μm以下的石墨細粉當作為負極材料時其粒徑過小，性能較差難以使用，因而造成許多廢料的產生與生產成本過高等問題。The most widely used today is the carbon system. Currently, the anode material used in commercial lithium-ion batteries is graphite, and graphite can be divided into artificial graphite and natural graphite. However, the metastable phase spheroidal carbon (MCMB) in artificial graphite needs to be treated by a graphitization furnace, which causes the production cost to be too high. Although there is a small specific surface area in the natural graphite coated asphalt, it has a lower first irreversibility, and can improve the compatibility of the graphite negative electrode material with the electrolyte, and the production cost is relatively low, but with the charge and discharge. When the number of times increases, the capacitance will continue to decline, resulting in poor cycle life, and the currently commercially available spherical graphite anode material has an average particle size of 10 to 25 μm, and graphite fine powder of 10 μm or less is used as a negative electrode. When the material is too small in particle size, the performance is poor and difficult to use, which causes problems such as the generation of many waste materials and the high production cost.
基於先前中國申請專利(申請公佈第CN 101800304 A號)採用天然鱗片石墨微粉與黏結劑如聚乙烯醇(PVA)、羧甲基纖維素(CMC)、聚乙烯醇缩丁醛(PVB)混合，經噴霧乾燥後，再經600~1000℃碳化熱處理，其研究發現碳化後可得到20~50 μm的球形石墨粉體，電容量測試後有較高的比容量與好的充放電循環性能，但上述方法發現首次庫倫效率為80~88%，其首次庫倫效率偏低，加上其為低含碳量之黏結劑經碳化處理，其碳化生產過程中低分子量散失造成空氣污染需加以處理，導致生產成本較高等缺點。Based on the previous Chinese patent application (Application No. CN 101800304 A), natural flake graphite fine powder is mixed with a binder such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyvinyl butyral (PVB), After spray drying, it is carbonized and heat treated at 600~1000 °C. It is found that spherical graphite powder of 20~50 μm can be obtained after carbonization. After capacity test, it has higher specific capacity and good charge and discharge cycle performance, but The above method found that the first Coulomb efficiency was 80-88%, and its first coulombic efficiency was low, and its binder with low carbon content was carbonized. The low molecular weight loss in the carbonization production process caused air pollution to be treated, resulting in Shortcomings such as high production costs.
日本專利特開第2002-117851號則是採用聚烯丙基胺水溶液與石墨粉混合，加熱到120℃一邊攪拌一邊加熱到水攪乾後，將粉末真空乾燥烘乾，得其粉末可做為鋰離子電池負極材料，然而此固態攪拌乾燥法應用於大量生產時，由於水分乾燥裡外不均，容易造成石墨粉顆粒互相黏貼聚集，不利於粒徑包覆與分散，於電極塗佈過程產生不均的現像。故為提昇放電電容量、降低不可逆容量、改善顆粒成型分散並降低生產成本，是以提出本發明。Japanese Patent Laid-Open No. 2002-117851 is prepared by mixing a polyallylamine aqueous solution with graphite powder, heating to 120 ° C while stirring, heating to water, stirring, and then drying the powder in a vacuum to obtain a powder thereof. Lithium-ion battery anode material, however, when the solid-state stirring and drying method is applied to mass production, the graphite powder particles are easily adhered to each other due to uneven moisture inside and outside, which is not conducive to particle size coating and dispersion, and is produced in the electrode coating process. Uneven appearance. Therefore, the present invention has been proposed in order to increase discharge capacity, reduce irreversible capacity, improve particle molding dispersion, and reduce production cost.
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瑣的製程，與全球對於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「石墨微粉應用於鋰離子電池負極材料及其製備方法」。In view of the conventional use of polymorphic carbon materials as anode materials for lithium ion secondary batteries, in addition to the high cost and cumbersome process of graphitization of carbon materials, there is a great demand for 3C electronic products, electric hand tools, and electric vehicles. As a result, the inventors have developed and designed a "graphite micropowder for lithium ion battery anode material and its preparation method" based on years of experience in research and experimentation with relevant theories. .
本發明之目的即在提供一種以天然石墨為基礎之鋰離子電池負極材料，係先將石墨與高分子樹脂(酚醛樹脂、聚丙烯腈(PAN)、聚苯胺(PA)、聚丙烯醯胺(PAA)、聚乙烯醇(PVA)、聚苯乙烯磺酸鈉(PSS)、聚3,4-乙烯二氧噻吩(PEDOT))攪拌混合，為由粒徑約為1~10 μm的球形石墨細粉，與高分子樹脂混合成漿體，再由噴霧乾燥機製作成15~25 μm顆粒狀粉體後，即獲得表面改質碳材之石墨複合碳材。The object of the present invention is to provide a lithium ion battery anode material based on natural graphite, which is firstly made of graphite and polymer resin (phenolic resin, polyacrylonitrile (PAN), polyaniline (PA), polypropylene decylamine ( PAA), polyvinyl alcohol (PVA), sodium polystyrene sulfonate (PSS), poly 3,4-ethylenedioxythiophene (PEDOT) are stirred and mixed to form spherical graphite with a particle size of about 1 to 10 μm. The powder is mixed with a polymer resin to form a slurry, and then a particle-shaped powder of 15 to 25 μm is produced by a spray dryer to obtain a graphite composite carbon material having a surface-modified carbon material.
本發明之次一目的為提供該鋰離子電池負極材料之製備方法。A second object of the present invention is to provide a method for preparing the negative electrode material of the lithium ion battery.
為達成上述本發明目的之技術手段在於：以成份為球形1~10 μm天然石墨作為鋰離子電池負極材料之碳材，該負極材配製方法包括：利用1~10 μm的球形石墨微粉與高分子樹脂混合，攪拌1~10小時均勻混合成泥漿狀；在經由噴霧乾燥機造粒與乾燥過程中製造出粉體，其噴霧乾燥進口溫度為200~380℃，出口溫度為70~150℃，乾燥後即得到粒徑為15~25 μm的球形複合石墨粉，其複合石墨粉為石墨表面披覆樹脂之球形粉體，以作為鋰離子電池負極材料。The technical means for achieving the above object of the present invention is as follows: a natural graphite having a spherical shape of 1 to 10 μm is used as a carbon material for a negative electrode material of a lithium ion battery, and the method for preparing the negative electrode material comprises: using spherical graphite powder and polymer of 1 to 10 μm. The resin is mixed and stirred for 1 to 10 hours to be uniformly mixed into a slurry. The powder is produced during the granulation and drying process by a spray dryer. The spray drying inlet temperature is 200-380 ° C, the outlet temperature is 70-150 ° C, and the drying is performed. Then, a spherical composite graphite powder having a particle diameter of 15 to 25 μm is obtained, and the composite graphite powder is a spherical powder coated with a graphite surface as a negative electrode material for a lithium ion battery.
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。In order to facilitate the review committee to have a further understanding and understanding of the technical means and operation process of the present invention, the embodiments are combined with the drawings, and the details are as follows.
請參閱第1圖所示，為本發明所提供之石墨樹脂複合材添加樹脂經噴霧乾燥後之示意圖，係以一天然石墨作為碳材，先將石墨與高分子樹脂攪拌混合，為粒徑約為1~10 μm的球形石墨細粉，與高分子樹脂混合成漿體，再由噴霧乾燥機製作成15~25 μm顆粒狀粉體後，即獲得表面改質碳材之石墨複合碳材。Referring to FIG. 1 , a schematic diagram of a graphite resin composite material added with a resin after spray drying is a natural graphite as a carbon material, and the graphite and the polymer resin are first stirred and mixed to have a particle size of about A spherical graphite fine powder of 1 to 10 μm is mixed with a polymer resin to form a slurry, and then a particle-shaped powder of 15 to 25 μm is produced by a spray dryer to obtain a graphite composite carbon material having a surface-modified carbon material.
請參閱第2圖所示，係為本發明前述石墨碳材之製備流程圖，該石墨碳材之製備方法包括下列步驟：首先執行步驟S10，將粒徑1~10 μm天然石墨微粉與0.1~20 wt%比例之高分子樹脂(如：高分子導電樹脂或高分子化合物)混合並加入適當比例的溶劑，例如：水(添加水溶性樹脂)或甲醇、乙醇(添加醇溶性樹脂)之後均勻攪拌，攪拌1~10小時形成漿狀液體，如是採醇溶性樹脂則須先將醇類溶劑去除，利用攪拌加熱的方式；加熱溫度70~90℃下將醇類溶劑去除後，再投入噴霧乾燥機內，接著進至步驟S11。Please refer to FIG. 2 , which is a flow chart for preparing the graphite carbon material according to the present invention. The method for preparing the graphite carbon material comprises the following steps: firstly, performing step S10 to prepare a natural graphite powder having a particle diameter of 1 to 10 μm and 0.1~ 20 wt% of polymer resin (such as polymer conductive resin or polymer compound) is mixed and added with a suitable proportion of solvent, such as water (adding water-soluble resin) or methanol, ethanol (adding alcohol-soluble resin), and then uniformly stirred. Stir for 1~10 hours to form a slurry liquid. If the alcohol-soluble resin is used, the alcohol solvent must be removed first, and the alcohol solvent is removed by heating; the alcohol solvent is removed at a heating temperature of 70-90 ° C, and then the spray dryer is put into the spray dryer. Then, the process proceeds to step S11.
於步驟S11中，將漿料投入噴霧乾燥機內，利用噴霧乾燥機乾燥造粒之效能製作成15~25 μm顆粒狀粉體，噴霧乾燥機其原理為將石墨漿料霧化後瞬間乾燥，使霧滴收縮形成類球狀乾燥粉體，接著進至步驟S12。In step S11, the slurry is put into a spray dryer, and the particle size of 15~25 μm is prepared by the effect of drying and granulating by a spray dryer. The principle of the spray dryer is to instantaneously dry the graphite slurry after atomization. The mist is contracted to form a spherical dry powder, and then proceeds to step S12.
於步驟S12中，其噴霧乾燥機溫度參數設定：進口溫度為200~380℃，出口溫度為70~150℃，經噴霧乾燥後即得到本發明之石墨複合碳材，並將其作為鋰離子電池負極材料。In step S12, the spray dryer temperature parameter is set: the inlet temperature is 200-380 ° C, the outlet temperature is 70-150 ° C, and the graphite composite carbon material of the invention is obtained by spray drying, and is used as a lithium ion battery. Anode material.
請參閱第3圖所示，係為石墨複合碳材50次放電循環次數電容量圖。Please refer to the figure 3, which is the capacitance diagram of the number of discharge cycles of graphite composite carbon material.
下列為比較例與實施例的描述，以說明本發明之特點與優勢，首先針對比較例1敘述，然後再對實施例1至實施例4加以比較，來證明本發明之效果。The following are descriptions of comparative examples and examples to illustrate the features and advantages of the present invention. First, the description will be made with respect to Comparative Example 1, and then Examples 1 to 4 will be compared to demonstrate the effects of the present invention.
比較例1：將平均粒徑3 μm天然石墨微粉與酒精混合加入反絮凝劑，調節固含量至30~50 wt%，再加入石墨微粉質量5%的聚乙烯醇缩丁醛(PVB)作為黏結劑，再攪拌槽中攪拌2~5小時後，再採噴霧乾燥機進行乾燥、造粒，並經由碳化爐做熱處理，其中熱處理溫度600~1000℃，所得粉體作為鋰離子負極材，而塗佈與電池組裝之方法如下：將0.1 wt%微量草酸與10 wt%之聚偏氟乙烯(PVDF)黏結劑(Binder)混入N-甲基吡咯烷酮(NMP)溶劑中，均勻攪拌20分鐘，使得該聚偏氟乙烯能均勻分散於該溶劑之混合液中；將該石墨碳粉末置入攪拌均勻之該混合液，持續攪拌20分鐘後該混合液形成泥漿狀物，以130 μm刮刀均勻塗佈在一銅箔上，以100℃烘乾去除殘留溶劑，以25%之碾壓率進行碾壓，再以110℃烘乾。電池組裝部份先把塗佈完整之負極極片裁成直徑1.3 cm的圓板，正極則採用鋰金屬箔片；硬幣形電池所需之組件，於乾燥氣氛控制室中依序組裝，並添加電解質液(1M鋰六氟磷酸鹽(LiPF6 )(溶質)-碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)(溶劑)(Volume 1:2))，即完成一硬幣形電池；組裝完成之硬幣型電池進行連續充放電性能測試，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/Li+ )，放電截止電壓為0.005V(vs. Li/Li+ )。其首次充電電容量為400.8 mAh/g，放電電容量為341.8 mAh/g，庫倫效率為85.2%。第50次充電電容量為340.6 mAh/g，放電電容量為322.8 mAh/g。Comparative Example 1: Mixing an average graphite particle size of 3 μm of natural graphite powder with alcohol to a deflocculant, adjusting the solid content to 30-50% by weight, and adding 5% of polyvinyl butyral (PVB) as a binder of graphite fine powder. After stirring for 2 to 5 hours in a stirred tank, the spray dryer is used for drying, granulation, and heat treatment through a carbonization furnace, wherein the heat treatment temperature is 600 to 1000 ° C, and the obtained powder is used as a lithium ion anode material. The cloth and battery assembly method is as follows: 0.1 wt% trace oxalic acid and 10 wt% polyvinylidene fluoride (PVDF) binder (Binder) are mixed into N-methylpyrrolidone (NMP) solvent, and uniformly stirred for 20 minutes. The polyvinylidene fluoride can be uniformly dispersed in the mixed solution of the solvent; the graphite carbon powder is placed in the uniformly stirred mixture, and the mixture is continuously stirred for 20 minutes to form a slurry, which is uniformly coated with a 130 μm doctor blade. On a copper foil, the residual solvent was dried at 100 ° C, rolled at a rolling ratio of 25%, and dried at 110 ° C. In the battery assembly part, the coated negative electrode piece is first cut into a circular plate with a diameter of 1.3 cm, and the positive electrode is made of a lithium metal foil; the components required for the coin-shaped battery are sequentially assembled in a dry atmosphere control room, and added. Electrolyte solution (1M lithium hexafluorophosphate (LiPF 6 ) (solute) - ethylene carbonate (EC) / ethyl methyl carbonate (EMC) (solvent) (Volume 1: 2)), that is, complete a coin-shaped battery; assembly The completed coin-type battery was tested for continuous charge and discharge performance. The charge and discharge rate was 0.2C constant current density for continuous charge and discharge 50 times, the charge cut-off voltage was 2V (vs. Li/Li + ), and the discharge cut-off voltage was 0.005V ( Vs. Li/Li + ). Its first charge capacity is 400.8 mAh/g, discharge capacity is 341.8 mAh/g, and Coulomb efficiency is 85.2%. The 50th charge capacity was 340.6 mAh/g, and the discharge capacity was 322.8 mAh/g.
實施例1：將平均粒徑3 μm的天然石墨30g與0.9g的樹脂聚丙烯醯胺(PAA)加入去離子水中混合攪拌，攪拌時間為1~5小時，混合成漿體後再採噴霧乾燥機進行乾燥、造粒，其噴霧乾燥進口溫度為280℃，出口溫度為150℃，乾燥後可得到粒徑約為15~25 μm的複合石墨粉，可作為負極材料使用。其電池之備製方式與電容量測試同比較例1。此材料首次充電電容量為399.6 mAh/g，放電電容量為360 mAh/g，庫倫效率為90%。第50次充電電容量為364.6 mAh/g，放電電容量為358.5 mAh/g。比較上述實驗，可知實施例1之放電電容量及庫倫效率以及循環穩定性明顯較比較例1來得佳。Example 1: 30 g of natural graphite with an average particle diameter of 3 μm and 0.9 g of resin polyacrylamide (PAA) were mixed and mixed in deionized water for a period of 1 to 5 hours, mixed into a slurry and then spray dried. The machine is dried and granulated, and the spray drying inlet temperature is 280 ° C, the outlet temperature is 150 ° C, and after drying, a composite graphite powder having a particle diameter of about 15 to 25 μm can be obtained, which can be used as a negative electrode material. The preparation method and capacitance test of the battery were the same as in Comparative Example 1. This material has a first charge capacity of 399.6 mAh/g, a discharge capacity of 360 mAh/g, and a Coulomb efficiency of 90%. The 50th charge capacity was 364.6 mAh/g, and the discharge capacity was 358.5 mAh/g. Comparing the above experiments, it was found that the discharge capacity, coulombic efficiency, and cycle stability of Example 1 were significantly better than those of Comparative Example 1.
實施例2：將粒徑1 μm的天然石墨微粉30g與0.6g之聚3,4-乙烯二氧噻吩(PEDOT)樹脂加入足量的去離子水中混合攪拌，攪拌時間為1~5小時，混合成漿體後再採噴霧乾燥機進行乾燥、造粒，其噴霧乾燥進口溫度為280℃，出口溫度為150℃，乾燥後可得到粒徑約為15~25 μm的複合石墨粉，可作為負極材料使用，其電池之備製方式與電容量測試同比較例1。此材料首次充電電容量為379.1 mAh/g，放電電容量為348.8 mAh/g，庫倫效率為92%。第50次充電電容量為350.6 mAh/g，放電電容量為346.8 mAh/g，循環性與放電電容量亦較比較例1有明顯提升且穩定。Example 2: 30 g of natural graphite fine powder having a particle size of 1 μm and 0.6 g of poly 3,4-ethylenedioxythiophene (PEDOT) resin were mixed and mixed in a sufficient amount of deionized water for a period of 1 to 5 hours, and mixed. After the slurry is formed, the spray dryer is used for drying and granulation. The spray drying inlet temperature is 280 ° C, the outlet temperature is 150 ° C, and after drying, the composite graphite powder with a particle size of about 15-25 μm can be obtained, which can be used as a negative electrode. The material was used, and the preparation method and capacity test of the battery were the same as in Comparative Example 1. This material has a first charge capacity of 379.1 mAh/g, a discharge capacity of 348.8 mAh/g, and a Coulomb efficiency of 92%. The 50th charge capacity was 350.6 mAh/g, and the discharge capacity was 346.8 mAh/g. The cycle and discharge capacity were also significantly improved and stable compared with Comparative Example 1.
實施例3：將粒徑2 μm的天然石墨30g與3g水性酚醛樹脂，加入去離子水混合攪拌，攪拌時間為1~5小時，混合成漿體後再採噴霧乾燥機進行乾燥、造粒，其噴霧乾燥進口溫度為280℃，出口溫度為150℃，乾燥後可得到粒徑約為15~25 μm的複合石墨粉，然後再經1250℃碳化熱處理後，可作為負極材料使用，其電池之備製方式與電容量測試同比較例1。此材料首次充電電容量為388.4mAh/g，放電電容量為348.7mAh/g，庫倫效率為89.8%。第50次充電電容量為355.8mAh/g，放電電容量為346.2mAh/g，亦較比較例1之電容量大且穩定。Example 3: 30 g of natural graphite having a particle size of 2 μm and 3 g of an aqueous phenolic resin were mixed and mixed with deionized water for a period of 1 to 5 hours, mixed into a slurry, and then dried and granulated by a spray dryer. The spray drying inlet temperature is 280 ° C, the outlet temperature is 150 ° C, and after drying, the composite graphite powder having a particle diameter of about 15 to 25 μm can be obtained, and then after being subjected to carbonization heat treatment at 1250 ° C, it can be used as a negative electrode material, and the battery thereof The preparation method and the capacitance test are the same as in Comparative Example 1. The material has a first charge capacity of 388.4 mAh/g, a discharge capacity of 348.7 mAh/g, and a Coulomb efficiency of 89.8%. The 50th charge capacity was 355.8 mAh/g, and the discharge capacity was 346.2 mAh/g, which was also larger and stable than the capacitance of Comparative Example 1.
實施例4：將15 μm的天然石墨30g與0.6g聚3,4-乙烯二氧噻吩(PEDOT)樹脂加入去離子水中混合攪拌，攪拌時間為1~5小時，混合成漿體後再採噴霧乾燥機進行乾燥，其噴霧乾燥進口溫度為280℃，出口溫度為150℃乾燥後可得到粒徑約為18~20 μm的複合石墨粉，可作為負極材料使用，其電池之備製方式與電容量測試同比較例1。此材料首次充電電容量為377.2 mAh/g，放電電容量為341.5 mAh/g，庫倫效率為90.5%。第50次充電電容量為360.5 mAh/g，放電電容量為339.1 mAh/g。Example 4: Mixing 30 g of 15 μm natural graphite with 0.6 g of poly 3,4-ethylenedioxythiophene (PEDOT) resin in deionized water, stirring for 1 to 5 hours, mixing into a slurry and then spraying The dryer is dried. The spray drying inlet temperature is 280 ° C, and the outlet temperature is 150 ° C. After drying, a composite graphite powder with a particle size of about 18-20 μm can be obtained, which can be used as a negative electrode material, and the preparation method and electricity of the battery. The capacity test was the same as in Comparative Example 1. The material has a first charge capacity of 377.2 mAh/g, a discharge capacity of 341.5 mAh/g, and a Coulomb efficiency of 90.5%. The 50th charge capacity was 360.5 mAh/g, and the discharge capacity was 339.1 mAh/g.
綜合上述實驗可以了解在包覆相同且等量的高分子樹脂下，當採用粒徑15~18 μm的天然石墨包覆高分子樹脂之電容量與庫倫效率等性質，與採用細粒徑1~10 μm天然石墨微粉包覆高分子樹脂性質是相當接近，因此可以進一步確定，細小粒徑的天然石墨粉也可做為鋰離子電池的負極材料。Based on the above experiments, it can be understood that the capacitance and coulombic efficiency of the natural graphite-coated polymer resin with a particle size of 15 to 18 μm are used under the same and equal amount of polymer resin, and the fine particle size is used. The properties of the 10 μm natural graphite micropowder coated polymer resin are quite close, so it can be further confirmed that the fine graphite natural graphite powder can also be used as the negative electrode material of the lithium ion battery.
本發明是將微小的球形天然石墨粉1~10 μm，與高分子樹脂混合後，利用噴霧乾燥的造粒與乾燥特性，製作成粒徑約15~25 μm且表面包覆一層高分子聚合物薄膜，或經碳化之碳膜的石墨複合材，其石墨表面多了這層薄膜後，可以抑制與降低鈍化膜與電解液所造成的不可逆電容量損失，其循環壽命與電容量也明顯較天然石墨佳，加上本發明採用負極材料廠生產時所產生的石墨細粉廢料，其目前商業上尚無採用粒徑約為1~10 μm的微粉做為鋰離子電池負極材料，因此本發明除了能夠提升負極材料的性能外，並且有廢物再利用的成效，對於降低生產成本有很大的助益。The invention adopts a micro spherical natural graphite powder of 1~10 μm, which is mixed with a polymer resin, and then has a particle size of about 15-25 μm and a surface coated with a high molecular polymer by spray granulation and drying characteristics. The film, or the carbonized carbon film of the graphite composite, has a larger amount of graphite on the surface of the graphite, which can suppress and reduce the irreversible capacity loss caused by the passivation film and the electrolyte, and its cycle life and capacitance are also significantly higher than natural stones. Ink, together with the graphite fine powder waste produced by the negative electrode material factory of the present invention, it is currently not commercially used as a negative electrode material of lithium ion battery with a particle size of about 1~10 μm, so the present invention is In addition to improving the performance of the anode material, and the effectiveness of waste recycling, it is of great help to reduce production costs.
表1：為對於不同實施例與比較例1中石墨負極材之電性比較之總整理，由表可知實施例1有較佳的充放電性與庫倫效率，可視為一種鋰離子電池負極材。Table 1 is a summary of the electrical properties of the graphite negative electrode materials of the different examples and Comparative Example 1. As can be seen from the table, Example 1 has better charge and discharge properties and coulombic efficiency, and can be regarded as a lithium ion battery negative electrode material.
表2：為對於不同實施例與比較例1中石墨負極材之比表面積與平均粒徑比較，由表可知原本為1～3 μm的石墨粉體，經高分子樹脂混合後，經噴霧乾燥的造粒與乾燥特性，製作成粒徑約18~20 μm且比表面積為1.8~2 m2 g-1 的石墨複合材。Table 2: For comparison of the specific surface area and the average particle diameter of the graphite negative electrode material in the different examples and Comparative Example 1, it is known from the table that the graphite powder originally of 1 to 3 μm is spray-dried after being mixed with the polymer resin. The granulation and drying characteristics were prepared into a graphite composite having a particle size of about 18 to 20 μm and a specific surface area of 1.8 to 2 m 2 g -1 .
本發明之優勢為使石墨與高分子樹脂的結合更為密合，高分子樹脂均勻的包覆於石墨表面，將石墨表面缺陷補平，又可將細小的石墨粉顆粒相互連結，形成較大的類球型顆粒粉體，其可以防止SEI膜脫落，改善電解液不相容問題，因而使不可逆電容量降低，庫倫效率增加，穩定的循環壽命與較高的充放電電容量。The invention has the advantages that the bonding of the graphite and the polymer resin is more closely combined, the polymer resin is uniformly coated on the surface of the graphite, the surface defects of the graphite are filled up, and the fine graphite powder particles are connected to each other to form a larger one. The ball-like particle powder can prevent the SEI film from falling off and improve the electrolyte incompatibility problem, thereby reducing the irreversible capacity, increasing the coulombic efficiency, stable cycle life and high charge and discharge capacity.
藉此可知，本發明石墨微粉應用於鋰離子電池負極材料及其製備方法，係先將天然石墨與高分子樹脂攪拌混合，由其粒徑約為1~10μm的球形石墨細粉，與高分子樹脂混合成漿體，再由噴霧乾燥機製作成15~25μm顆粒狀粉體後，製作獲得表面改質碳材之石墨複合碳材，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)之具充放電速度慢、電容量低、環境汙染及價格昂貴等缺點。It can be seen that the graphite fine powder of the present invention is applied to a lithium ion battery anode material and a preparation method thereof, and the natural graphite and the polymer resin are first stirred and mixed, and the spherical graphite fine powder having a particle diameter of about 1 to 10 μm and the polymer are mixed. The resin is mixed into a slurry, and then a 15~25 μm granular powder is prepared by a spray dryer, and then a graphite composite carbon material obtained by obtaining a surface modified carbon material is prepared, thereby solving the problem. Polymorphic carbon materials (eg, natural graphite, coal, carbon fiber, and metastable phase spheroidal carbon MCMB) have shortcomings such as slow charge and discharge rates, low capacitance, environmental pollution, and high cost.
上列詳細說明係針對本發明之一可行實施例之具體說明，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。The detailed description of the preferred embodiments of the present invention is intended to be limited to the scope of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.
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第1圖為本發明石墨與高分子樹脂混合後經噴霧乾燥後之示意圖；第2圖為本發明石墨複合材之製備流程圖；以及第3圖為本發明石墨複合碳材50次放電循環次數電容量圖。1 is a schematic view of the graphite composite of the present invention after being spray-dried; FIG. 2 is a flow chart of preparing the graphite composite of the present invention; and FIG. 3 is a 50-times discharge cycle of the graphite composite carbon of the present invention. Capacitance map.
S10~S12‧‧‧步驟S10~S12‧‧‧Steps
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