TWI830935B

TWI830935B - Manufacturing method of multi-layered long-cycle silicon carbon anode material

Info

Publication number: TWI830935B
Application number: TW109125191A
Authority: TW
Inventors: 賴鴻政; 傅聖育; 張曾隆
Original assignee: 芯量科技股份有限公司
Filing date: 2020-07-24
Publication date: 2024-02-01

Abstract

一種多層狀長循環矽碳負極材料之製造方法，係取一純矽及一第一母膠，該第一母膠的成分為溶劑及分散劑；該分散劑的成分為高分子支撐劑、小分子定錨劑及稠化劑；然後將純矽與第一母膠混合形成第一混合體再進行研磨，而形成第一研磨體；然後取一石墨烯(graphene)及另一第一母膠，將兩者混合後進行研磨，而形成第二研磨體；然後將第一研磨體與第二研磨體混合形成第二混合體，再進行行星式混拌、乳化均質及脫泡行星混拌的程序；然後將奈米碳管(CNT)及一第二母膠混合後置入一葉片攪拌槽中攪拌，再置入乳化機中攪拌而形成第三混合體；該第二母膠的成分為溶劑及包覆劑；再將經過處理的該第二混合體及該第三混合體進行行星式混拌，而形成第四混合體；最後將該第四混合體進行噴霧乾燥作業，而形成本案的矽碳複合結構混體。 A method for manufacturing multi-layered long-circulation silicon-carbon negative electrode material, which is to take a pure silicon and a first masterbatch. The components of the first masterbatch are solvent and dispersant; the components of the dispersant are polymer proppant, Small molecule anchoring agent and thickener; then, pure silicon and the first masterbatch are mixed to form a first mixture and then grinded to form a first grinding body; then, a graphene and another first masterbatch are taken Glue, mix the two and grind them to form a second grinding body; then mix the first grinding body and the second grinding body to form a second mixed body, and then perform planetary mixing, emulsification, homogenization and deaeration planetary mixing. The procedure; then mix the carbon nanotubes (CNT) and a second masterbatch, put them into a blade stirring tank for stirring, and then put them into an emulsifier for stirring to form a third mixture; the components of the second masterbatch as a solvent and a coating agent; then perform planetary mixing on the processed second mixture and the third mixture to form a fourth mixture; and finally spray-dry the fourth mixture to form This case is a silicon-carbon composite structure hybrid.

Description

多層狀長循環矽碳負極材料之製造方法 Manufacturing method of multi-layered long-cycle silicon carbon anode material

本發明係有關於負極材料，尤其是一種多層狀長循環矽碳負極材料之製造方法。 The present invention relates to negative electrode materials, particularly a method for manufacturing a multi-layered long-cycle silicon carbon negative electrode material.

在鋰電池的負極材料中，習知成熟技術上，使用石墨作為負極進行鋰離子插嵌反應；然而因石墨之電容量有限，面對電容量需求日益提升之3C市場與續航力掛帥之車用市場已無法符未來需求，因此改進負極材料的電容量能力已經為一項重要的發展方向。其中矽材料因其優秀之儲鋰能力而備受市場期待。矽在地殼中的含量是除氧外最多的元素，而矽材料為一種非金屬無定形材料，具有純度高、粒徑小、分布均勻、比表面積大、高表面活性、封裝密度低等等的優點，且無毒、無味。因此應用矽材料與石墨材料組成的矽碳複合材料，可用於作為鋰離子電池的負極材料，大幅提高鋰離子電池的容量。所以較佳的方式為應用矽材料(純矽、氧化矽)部分配合石墨使用。因為矽材料的電容量較石墨為高，所以可以使得整個負極具有更大的電容量，以增加電池的儲存能力。 Among the negative electrode materials of lithium batteries, graphite is used as the negative electrode for lithium ion intercalation reaction in the mature technology. However, due to the limited capacity of graphite, it faces the 3C market with increasing demand for capacity and the automotive market where endurance is the key. It is no longer able to meet future needs, so improving the capacitance capacity of negative electrode materials has become an important development direction. Among them, silicon material is highly anticipated by the market because of its excellent lithium storage capacity. The content of silicon in the earth's crust is the largest element besides oxygen, and silicon material is a non-metallic amorphous material with high purity, small particle size, uniform distribution, large specific surface area, high surface activity, low packaging density, etc. Advantages, non-toxic and tasteless. Therefore, silicon-carbon composite materials composed of silicon materials and graphite materials can be used as negative electrode materials for lithium-ion batteries, greatly increasing the capacity of lithium-ion batteries. Therefore, the better way is to use silicon materials (pure silicon, silicon oxide) partially combined with graphite. Because the electric capacity of silicon material is higher than that of graphite, the entire negative electrode can have a larger electric capacity to increase the storage capacity of the battery.

在鋰離子電池中，鋰離子會藉由外部電勢與材料位能差異，以電化學形式嵌插進入矽材料的晶體結構中。當鋰電池以電化學形式進行放電時，俱電化學活性之鋰離子離開矽晶體結構，而形成放電機制進而達到溝通外部電路之電能需求。理論而言開發者與使用者均希望所有之鋰離子在充放電過程中能盡量減少耗損，然而在電池作動中勢必會有一部份的活性鋰會因反應介面增減、電解液或材料中之雜質而與活性鋰發生電化學副反應，進而造成非活性鋰鹽之析出與耗損，始其沉澱在材料周圍，形成一層不可逆薄膜，即SEI膜。此SEI 現象在矽材料中尤其明顯，充電時，矽材料因大量容納鋰離子而使其晶體結構鬆散膨脹(該結構較原矽材料結構大的多)，矽材料容鋰膨脹後，膨脹效應突破材料原結構之表面應力，使得顆粒表面破裂，形成新的反應介面而使材料比表面積BET發生變化，爾後此新反應介面會與殘餘之活性鋰發生不可逆反應，造成鋰離子耗損；另一方面，放電時活性鋰離開矽晶格結構而留下空洞，使得整個材料鬆軟而造成崩塌，崩塌後新的反應介面升成又與活性鋰離子發生反應，造成耗損。在多次充放電後，反覆發生膨脹、破裂、坍塌、耗鋰，使得大量活性鋰耗損造成電容量巨幅衰變，降低電池壽命與使用性。 In lithium-ion batteries, lithium ions are electrochemically inserted into the crystal structure of the silicon material through the difference in external potential and material potential energy. When the lithium battery discharges electrochemically, the electrochemically active lithium ions leave the silicon crystal structure, forming a discharge mechanism to meet the electrical energy needs of the external circuit. Theoretically, developers and users hope that all lithium ions can be lost as little as possible during the charging and discharging process. However, during battery operation, a part of the active lithium will inevitably be lost due to the increase or decrease in the reaction interface, changes in the electrolyte or materials. The impurities undergo electrochemical side reactions with active lithium, causing the precipitation and loss of inactive lithium salts, which then precipitate around the material to form an irreversible thin film, the SEI film. This SEI This phenomenon is especially obvious in silicon materials. When charging, the silicon material accommodates a large amount of lithium ions, causing its crystal structure to loosen and expand (this structure is much larger than the original silicon material structure). After the silicon material expands to accommodate lithium, the expansion effect breaks through the original material. The surface stress of the structure causes the surface of the particles to rupture, forming a new reaction interface and changing the specific surface area BET of the material. This new reaction interface will then irreversibly react with the remaining active lithium, causing the loss of lithium ions; on the other hand, during discharge, The active lithium leaves the silicon lattice structure and leaves a cavity, making the entire material soft and causing collapse. After the collapse, a new reaction interface rises and reacts with the active lithium ions, causing loss. After multiple charges and discharges, repeated expansion, rupture, collapse, and lithium consumption occur, causing a large amount of active lithium to be consumed and causing a huge decay of the capacity, reducing the battery life and usability.

此外矽材料本身不具備相對應之導電能力，須以導電材料輔助方能進行電子傳導與離子傳導，此導電碳往往以附加形式形附於其上，因此在膨脹破裂之充放電過程中容易失區連結而造成導電度喪失，導電度喪失後相對應之容量亦產生巨幅衰變。 In addition, the silicon material itself does not have corresponding electrical conductivity, and must be assisted by conductive materials for electronic conduction and ion conduction. This conductive carbon is often attached to it in an additional form, so it is easily lost during the charge and discharge process due to expansion and rupture. The area connection causes a loss of conductivity, and the corresponding capacity also undergoes a huge decay after the conductivity is lost.

故本案提出一種嶄新的具高導電度、高容量、膨脹緩衝性及循環壽命強化之長效矽碳負極材料的製造方法，以解決上述先前技術上的缺陷。 Therefore, this project proposes a new manufacturing method of long-lasting silicon carbon anode material with high conductivity, high capacity, expansion buffering properties and enhanced cycle life to solve the above-mentioned shortcomings of the previous technology.

所以本發明的目的係為解決上述習知技術上的問題，本發明中提出一種具有高導電度、高容量、膨脹緩衝性&循環壽命強化的製造方法，係將原始之矽材料中加入分散劑(其組成成分為高分子支撐劑、小分子定錨劑、以及稠化劑)，此複合分散劑用於分散並支撐奈微化之矽材料，避免矽材料在分散過程中反團失區分散效益；並且在材料中加入特定層數之高純度精煉化石墨烯，利用石墨烯、特殊碳材料與奈微化矽材結合形成特殊3D結構以增加矽材料間的導電溝通橋樑。在分散工藝中以研磨機應用研磨片及鋯珠，以及應用特殊行星式混拌機，在各階段工藝中協作使複合材料可以藉由特殊binder配方充分互溶，均勻混合，並輔以造粒噴霧設備賦予其結構形貌；總和產生具較佳的導電性與膨脹緩能力之高循環性矽碳結構。 Therefore, the purpose of the present invention is to solve the above-mentioned problems in the conventional technology. The present invention proposes a manufacturing method with high conductivity, high capacity, expansion buffering properties & enhanced cycle life, by adding a dispersant to the original silicon material. (Its composition is a polymer proppant, a small molecule anchoring agent, and a thickener). This composite dispersant is used to disperse and support micronized silicon materials to prevent the silicon materials from being deagglomerated and dispersed during the dispersion process. benefits; and a specific number of layers of high-purity refined graphene are added to the material, and graphene, special carbon materials and nano-micron silicon materials are combined to form a special 3D structure to increase the conductive communication bridge between silicon materials. In the dispersion process, a grinding machine is used to apply grinding discs and zirconium beads, and a special planetary mixer is used to cooperate in each stage of the process so that the composite materials can be fully miscible with each other through a special binder formula. Evenly mixed, and supplemented by granulation spray equipment to give it a structural shape; the sum total produces a highly cyclic silicon-carbon structure with better conductivity and expansion retardation capabilities.

為達到上述目的本發明中提出一種多層狀長循環矽碳負極材料之製造方法，包含下列步驟：步驟A：取一純矽；步驟B：另外取一第一母膠A，該第一母膠A的成分為溶劑及分散劑；其中該溶劑的組成成分為乙醇、丙酮及水；該分散劑的組成成分為高分子支撐劑、小分子定錨劑、以及稠化劑；步驟C：將10%wt的純矽與90%wt的第一母膠A混合形成第一混合體，再進行研磨，其研磨的方式為將該第一混合體進入一研磨機中研磨，因此形成第一研磨體；步驟D：取一石墨烯(graphene)；步驟E：另外取第一母膠B，其成分同於上述第一母膠A；將10%wt的石墨烯與90%wt的第一母膠B混合後再進入該研磨機中研磨，因此形成第二研磨體；步驟F：將等重量的第一研磨體與第二研磨體混合形成第二混合體，再進行行星式混拌、乳化均質及脫泡行星混拌的程序；步驟G：將奈米碳管(CNT)及一第二母膠混合，該奈米碳管為陣列式奈米碳管，且該第二母膠的成分為溶劑及包覆劑，其中該溶劑為水；步驟H：將該奈米碳管及該第二母膠的混合體置入一葉片攪拌槽中，該葉片攪拌槽包含葉片，經由該葉片攪拌一預定時間，再置入上述的乳化機中攪拌一預定時間而形成第三混合體；步驟I：將上述經過處理的該第二混合體及該第三混合體進行行星式混拌，而形成第四混合體；步驟J：然後將該第四混合體進行噴霧乾燥作業，而形成矽碳複合結構混體；其中以上各成分的數值均可以做±20%的變動。 In order to achieve the above object, the present invention proposes a manufacturing method of multi-layered long-cycle silicon carbon negative electrode material, which includes the following steps: Step A: Get a pure silicon; Step B: In addition, get a first masterbatch A, the first masterbatch A The components of glue A are solvent and dispersant; the solvent is composed of ethanol, acetone and water; the dispersant is composed of polymer proppant, small molecule anchoring agent and thickener; step C: 10%wt of pure silicon and 90%wt of the first masterbatch A are mixed to form a first mixture, and then ground. The grinding method is to grind the first mixture into a grinder, thus forming a first grinding body. Body; Step D: Take a graphene (graphene); Step E: In addition, take the first masterbatch B, whose composition is the same as the above-mentioned first masterbatch A; mix 10%wt of graphene and 90%wt of the first masterbatch Glue B is mixed and then grinded in the grinder to form a second grinding body; Step F: Mix the first grinding body and the second grinding body of equal weight to form a second mixture, and then perform planetary mixing and emulsification. Homogenization and defoaming planetary mixing process; Step G: Mix carbon nanotubes (CNT) and a second masterbatch. The carbon nanotubes are array carbon nanotubes, and the composition of the second masterbatch is a solvent and a coating agent, wherein the solvent is water; Step H: Place the mixture of the carbon nanotubes and the second masterbatch into a blade stirring tank, the blade stirring tank includes blades, and the blades are stirred A predetermined time, and then placed in the above-mentioned emulsifier and stirred for a predetermined time to form a third mixture; Step I: Perform planetary mixing of the above-mentioned processed second mixture and the third mixture to form The fourth mixture; Step J: The fourth mixture is then spray-dried to form a silicon-carbon composite structure mixture; the values of each of the above components can be varied by ±20%.

由下文的說明可更進一步瞭解本發明的特徵及其優點，閱讀時並請參考附圖。 The features and advantages of the present invention can be further understood from the following description. Please refer to the accompanying drawings when reading.

1:第一母膠 1: First masterbatch

2:第一母膠 2: First masterbatch

3:第二母膠 3: Second masterbatch

4:純矽 4:Pure silicon

5:石墨烯 5: Graphene

6:奈米碳管 6: Carbon nanotubes

9:矽碳複合結構混體 9: Silicon-carbon composite structure hybrid

10:第一混合體 10:First mixture

15:第一研磨體 15: First grinding body

16:第二研磨體 16: Second grinding body

20:第二混合體 20:Second mixture

30:第三混合體 30:The third mixture

40:第四混合體 40:The fourth hybrid

50:研磨機 50:Grinder

51:研磨片 51: Grinding disc

52:鋯珠 52:Zirconium beads

60:四流體噴頭 60:Four-fluid nozzle

70:葉片攪拌槽 70: Blade mixing tank

71:葉片 71: blade

80:第一母膠 80:The first masterbatch

81:內桶 81:Inner barrel

82:外桶 82:Outer barrel

83:公轉式攪拌器 83:Revolving mixer

84:自轉式攪拌器 84: Rotating mixer

85:驅動機構 85:Driving mechanism

86:驅動機構 86:Driving mechanism

90:乳化機 90: Emulsifying machine

91:乳化桶 91: Emulsification barrel

92:攪拌桶 92: Mixing bucket

93:攪拌器 93: Blender

100:冷卻水 100: cooling water

831:框架 831:Frame

832:刀片 832:Blade

841:轉球 841: Turn the ball

842:懸鐵柱 842:Suspended iron column

921:輸入孔 921:Input hole

922:第一輸出孔 922: First output hole

923:第二輸出孔 923: Second output hole

圖1顯示本案之第一研磨體及第二研磨體之製造流程示意圖。 Figure 1 shows a schematic diagram of the manufacturing process of the first grinding body and the second grinding body in this case.

圖2顯示本案之第二混合體進行行星式混拌、乳化均質及脫泡行星混拌的流程示意圖。 Figure 2 shows a schematic flow chart of the planetary mixing, emulsification, homogenization and defoaming planetary mixing of the second mixture in this case.

圖3顯示本案之第三混合體之製造流程示意圖。 Figure 3 shows a schematic diagram of the manufacturing process of the third hybrid in this case.

圖4顯示本案之行星式混拌機之示意圖。 Figure 4 shows a schematic diagram of the planetary mixer in this case.

圖5顯示本案之乳化機之示意圖。 Figure 5 shows the schematic diagram of the emulsifier in this case.

圖6顯示本案中應用第二混合體及第三混合體製造矽碳複合結構混體之流程示意圖。 Figure 6 shows a schematic flow chart of using the second mixture and the third mixture to manufacture the silicon-carbon composite structure mixture in this case.

茲謹就本案的結構組成，及所能產生的功效與優點，配合圖式，舉本案之一較佳實施例詳細說明如下。 Hereby, we would like to give a detailed description of the structural composition of this case, as well as the functions and advantages it can produce, together with the drawings, and give a detailed description of one of the preferred embodiments of this case as follows.

請參考圖1至圖6所示，顯示本發明之多層狀長循環矽碳負極材料之製造方法，包含下列步驟：取一純矽4(金屬還原矽)，其純度為99.999%，原始粒徑為10~15mm。 Please refer to Figures 1 to 6, which show the manufacturing method of the multi-layered long-cycle silicon carbon negative electrode material of the present invention, which includes the following steps: take a pure silicon 4 (metal reduced silicon), its purity is 99.999%, and the original particles The diameter is 10~15mm.

另外取一第一母膠1，該第一母膠1的成分為98.8%wt(重量百分比)的溶劑加上1.2%wt的分散劑。其中該溶劑的組成成分為40%wt的乙醇、2%wt的丙酮及58%wt的水。該分散劑的組成成分為0.6~1.2%wt的高分子支撐劑(如PVP或PVA，其分子量約20000~30000g/mole(克/莫耳)，較佳者其分子量為25000g/mole)、0.1~0.3%wt的小分子定錨劑(如不飽和醚酮類或苯磺酸鹽類)、以及0.1~0.4%wt的稠化劑(如羧乙基或羧丙基纖維素鈉、或聚醣類高分子)。 In addition, a first masterbatch 1 is taken. The composition of the first masterbatch 1 is 98.8%wt (weight percent) solvent plus 1.2%wt dispersant. The solvent consists of 40%wt ethanol, 2%wt acetone and 58%wt water. The dispersant consists of 0.6~1.2%wt polymer proppant (such as PVP or PVA, with a molecular weight of about 20000~30000g/mole (gram/mole), preferably a molecular weight of 25000g/mole), 0.1 ~0.3%wt of small molecule anchoring agents (such as unsaturated ether ketones or benzene sulfonates), and 0.1~0.4%wt of thickening agents (such as carboxyethyl or carboxypropyl cellulose sodium, or poly carbohydrate polymer).

如圖1所示，將10%wt的純矽4與90%wt的第一母膠1混合形成第一混合體10，再進行研磨，其研磨的方式為將該第一混合體10進入一研磨機50中研磨，其中該研磨機50包含研磨片51及鋯珠52，該研磨片51係以3000~3400rpm的轉速轉動，鋯珠52的粒徑為0.2~0.4mm(較佳者為0.3mm)，在16~23℃的環境下進行12~16小時的研磨，其中該鋯珠52與該第一混合體10的比例為該鋯珠52佔70~78%wt。因此形成第一研磨體15。 As shown in Figure 1, 10%wt pure silicon 4 and 90%wt first masterbatch 1 are mixed to form a first mixture 10, and then grinded. The grinding method is to put the first mixture 10 into a Grinding in a grinder 50, wherein the grinder 50 includes a grinding disc 51 and zirconium beads 52. The grinding disc 51 rotates at a rotation speed of 3000~3400 rpm. The particle size of the zirconium beads 52 is 0.2~0.4mm (preferably 0.3 mm), in an environment of 16~23℃ Grinding is performed for 12 to 16 hours, in which the ratio of the zirconium beads 52 to the first mixture 10 is 70 to 78%wt of the zirconium beads 52 . The first grinding body 15 is thus formed.

取一石墨烯(graphene)5。 Take a graphene 5.

另外取第一母膠2，其成分同於上述第一母膠1。將10%wt的石墨烯5與90%wt的第一母膠2混合後再進入該研磨機50中研磨，但研磨條件為使用粒徑為0.6~1.0mm(較佳者為0.8mm)的鋯珠52，研磨片51以2200~2600rpm的轉速轉動，在18~25℃的環境下進行20~24小時的研磨，其中該鋯珠52與該第一混合體10的比例為該鋯珠52佔70~78%wt。因此形成第二研磨體16。 In addition, take the first masterbatch 2, the composition of which is the same as the above-mentioned first masterbatch 1. 10%wt graphene 5 and 90%wt first masterbatch 2 are mixed and then grinded in the grinder 50, but the grinding conditions are to use a particle size of 0.6~1.0mm (preferably 0.8mm) The zirconium beads 52 and the grinding disc 51 rotate at a speed of 2200 to 2600 rpm, and grind for 20 to 24 hours in an environment of 18 to 25°C, where the ratio of the zirconium beads 52 to the first mixture 10 is the zirconium beads 52 Accounting for 70~78%wt. The second grinding body 16 is thus formed.

如圖2所示，將等重量的第一研磨體15與第二研磨體16混合形成第二混合體20，再進行行星式混拌、乳化均質及脫泡行星混拌的程序。圖2中的A點係對應到圖1中流程的A點位置，圖2中的A’點係對應到圖1中流程的A’點位置。其方式為：先將該第二混合體20置入一行星式混拌機80中，其中該行星式混拌機80的公轉速率為10~30rpm(較佳者為20rpm)，自轉的速率為3500~5000rpm，操作時間為1小時。 As shown in FIG. 2 , equal weights of the first grinding body 15 and the second grinding body 16 are mixed to form the second mixture 20 , and then the processes of planetary mixing, emulsification and homogenization, and deaeration planetary mixing are performed. Point A in Figure 2 corresponds to the position of point A in the process in Figure 1, and point A’ in Figure 2 corresponds to the position of point A’ in the process in Figure 1. The method is: first put the second mixture 20 into a planetary mixer 80, wherein the revolution speed of the planetary mixer 80 is 10~30rpm (preferably 20rpm), and the rotation speed is 3500~5000rpm, operating time is 1 hour.

如圖4所示，其中該行星式混拌機80主要包含：一內桶81，用於放置該第二混合體20，並攪拌該第二混合體20。 As shown in FIG. 4 , the planetary mixer 80 mainly includes: an inner barrel 81 for placing the second mixture 20 and stirring the second mixture 20 .

一外桶82，係容納該內桶81，該外桶82及該內桶81之間配置有冷卻水100，以冷卻該內桶81內部的該第二混合體20，該冷卻水100可外接循環冷卻系統(為熟知之習知技術，不贅述其細部結構)，以達到該冷卻水100循環及熱交換的效果。 An outer barrel 82 accommodates the inner barrel 81. Cooling water 100 is disposed between the outer barrel 82 and the inner barrel 81 to cool the second mixture 20 inside the inner barrel 81. The cooling water 100 can be externally connected. A circulating cooling system (a well-known conventional technology, and its detailed structure will not be described in detail) is used to achieve the effects of 100 circulation and heat exchange of the cooling water.

一公轉式攪拌器83，配置於該內桶81內，並外接驅動機構85，該公轉式攪拌器83係用於將該第二混合體20作大路徑的攪拌，以使得該第二混合體20在該內桶81內部形成較大區域的位移。其中該公轉式攪拌器83為一近似U形或V形的框架831，並在該框架831的側邊配置多數個刀片832的結構。攪拌時該公轉式攪拌器83沿著該框架831的軸線轉動，而使得該第二混合體20形成較大路徑的位移。較佳者該公轉式攪拌器83轉動時所掃出的體積超過該內桶81容積之一半。 A revolving stirrer 83 is disposed in the inner barrel 81 and is connected to an external driving mechanism 85. The revolving stirrer 83 is used to stir the second mixed body 20 in a large path, so that the second mixed body 20 forms a larger area of displacement inside the inner barrel 81 . The revolving agitator 83 is approximately U-shaped. Or a V-shaped frame 831, and a structure in which a plurality of blades 832 are arranged on the sides of the frame 831. During stirring, the revolving stirrer 83 rotates along the axis of the frame 831 , causing the second mixing body 20 to form a larger displacement path. Preferably, the volume swept out by the revolution-type agitator 83 when rotating exceeds half of the volume of the inner barrel 81 .

一自轉式攪拌器84，係用於將該第二混合體20做局部的充分攪拌，主要是由塊狀體沿著自身的軸線作自轉，而使得在該自轉式攪拌器84周圍的該第二混合體20形成渦流。本案中該自轉式攪拌器84為至少一轉球841，並由一懸鐵柱842懸吊，再經由驅動機構86加以驅動。轉動時該轉球841繞著通過其球心的軸線轉動，而對該第二混合體20形成渦流。 A rotating stirrer 84 is used to fully stir the second mixed body 20 locally, mainly because the block rotates along its own axis, so that the third mixture around the rotating stirrer 84 The two mixtures 20 form a vortex. In this case, the self-rotating stirrer 84 is at least one rotating ball 841, which is suspended by a hanging iron column 842 and is driven by a driving mechanism 86. When rotating, the rotating ball 841 rotates around an axis passing through its center, thereby forming a vortex flow on the second mixed body 20 .

本案中該至少一轉球841可為多個轉球841，各該轉球841分別經由一懸鐵柱842懸吊，各該轉球841的旋轉方向可相同或不同。在圖中以兩個轉球841作為說明。 In this case, the at least one rotating ball 841 can be a plurality of rotating balls 841. Each rotating ball 841 is suspended by a hanging iron column 842, and the rotation direction of each rotating ball 841 can be the same or different. In the figure, two rotating balls 841 are used as illustrations.

本案中自轉的目的在於使得該第二混合體20形成局部性的渦流，主要是將該第二混合體20打散。公轉的目的在於使得該內桶81的該第二混合體20形成大位移的對流，而使得整體該第二混合體20可以均勻分布。所以利用公轉及自轉充分的將該第二混合體20完全融合。 The purpose of rotation in this case is to cause the second mixed body 20 to form a local vortex, mainly to break up the second mixed body 20 . The purpose of the revolution is to cause the second mixed body 20 in the inner barrel 81 to form large-displacement convection, so that the entire second mixed body 20 can be evenly distributed. Therefore, the second mixed body 20 is fully integrated using revolution and rotation.

然後將經過行星式混拌的該第二混合體20置入一乳化機90中。如圖5所示，其中該乳化機90包含一乳化桶91，該乳化桶91內部包含經過該行星式混拌的第二混合體20。 Then, the second mixture 20 that has undergone planetary mixing is placed in an emulsifier 90 . As shown in FIG. 5 , the emulsifier 90 includes an emulsification barrel 91 , and the interior of the emulsification barrel 91 contains the second mixed body 20 that has been mixed by the planetary type.

其中該乳化桶91內部尚包含一攪拌桶92，該攪拌桶92的底部包含多個輸入孔921，可以將該第二混合體20置入該攪拌桶92。該攪拌桶92內部有攪拌器93用於將該攪拌桶92內的該第二混合體20攪拌使其均勻並且將其顆粒打散成為較小粒徑的顆粒。該攪拌桶92的下側邊包含多個第一輸出孔922，經攪拌的該第二混合體20且粒徑較小者可以由該第一輸出孔922輸出至該乳化桶91。該攪拌桶92的上側邊包含多個第二輸出孔923，經攪拌的該第二混合體20且未由該第一輸出孔922輸出者，在該攪拌桶92內經過進一步的攪拌，再由該第二輸出孔923輸出至該乳化桶91。其中從該第一輸出孔922及該第二輸出孔923輸出到該乳化桶91的第二混合體20再從該輸入孔921輸入到該攪拌桶92內，因此使得該第二混合體20在該乳化桶91內反覆循環攪拌而去團聚形成乳化狀態。在該乳化桶91的內側位在第二輸出孔923的上方處可以進行抽氣，以導引該第二混合體20由下往上流動。 The emulsification barrel 91 also includes a stirring barrel 92 inside. The bottom of the mixing barrel 92 includes a plurality of input holes 921 , and the second mixture 20 can be placed into the stirring barrel 92 . There is a stirrer 93 inside the mixing barrel 92 for stirring the second mixed body 20 in the mixing barrel 92 to make it uniform and breaking the particles into smaller particles. The lower side of the stirring barrel 92 includes a plurality of first output holes 922 , and the stirred second mixture 20 with smaller particle sizes can be output to the emulsification barrel 91 through the first output holes 922 . Should stir up The upper side of the mixing barrel 92 includes a plurality of second output holes 923. The stirred second mixture 20 that is not output through the first output holes 922 is further stirred in the mixing barrel 92, and then passed through the mixing barrel 92. The second output hole 923 outputs to the emulsification barrel 91 . The second mixture 20 output from the first output hole 922 and the second output hole 923 to the emulsification barrel 91 is then input into the mixing barrel 92 from the input hole 921, so that the second mixture 20 is The emulsification barrel 91 is repeatedly stirred and circulated to remove agglomeration and form an emulsified state. Air can be pumped inside the emulsification barrel 91 above the second output hole 923 to guide the second mixture 20 to flow from bottom to top.

本案中該乳化機90進行乳化的轉速為9000~11000rpm(較佳者為10000rpm)，乳化時間為1小時。 In this case, the rotation speed of the emulsifier 90 for emulsification is 9000~11000rpm (preferably 10000rpm), and the emulsification time is 1 hour.

然後將經過乳化均質後的該第二混合體20再置入該行星式混拌機80內進行脫泡行星混拌作業。其中係在該內桶81內進行抽氣，而且自轉速度為0rpm，公轉速度為30rpm，共進行30分鐘，因此完成該第二混合體20的處理。 Then, the emulsified and homogenized second mixture 20 is placed into the planetary mixer 80 to perform deaeration planetary mixing operation. The air is pumped in the inner barrel 81 at a rotation speed of 0 rpm and a revolution speed of 30 rpm for a total of 30 minutes. Therefore, the processing of the second mixture 20 is completed.

如圖3所示，將奈米碳管(CNT)6及一第二母膠3混合，該奈米碳管6為陣列式奈米碳管，且該第二母膠3的成分為溶劑及包覆劑，該包覆劑的重量百分比為2~6.8%wt，其餘為溶劑。該溶劑為水。該包覆劑的材料為寡糖類高分子加上少量的寡糖酮類，寡糖類高分子及寡糖酮類的重量比為3~6：1。而該奈米碳管6與該第二母膠3混合的重量比為，該奈米碳管6占0.1~0.18%wt，其餘為該第二母膠3。 As shown in Figure 3, carbon nanotubes (CNT) 6 and a second masterbatch 3 are mixed. The carbon nanotubes 6 are array carbon nanotubes, and the components of the second masterbatch 3 are solvent and Coating agent, the weight percentage of the coating agent is 2~6.8%wt, and the rest is solvent. The solvent is water. The coating agent is made of oligosaccharide polymers plus a small amount of oligosaccharide ketones, and the weight ratio of oligosaccharide polymers and oligosaccharide ketones is 3 to 6:1. The weight ratio of the carbon nanotubes 6 and the second masterbatch 3 is: the carbon nanotubes 6 account for 0.1~0.18%wt, and the rest is the second masterbatch 3.

將該奈米碳管6及該第二母膠3的混合體置入一葉片攪拌槽70中，該葉片攪拌槽70包含葉片71，經由該葉片71攪拌30分鐘，再置入上述的乳化機90中攪拌30分鐘而形成第三混合體30。 The mixture of the carbon nanotubes 6 and the second masterbatch 3 is placed into a blade stirring tank 70. The blade stirring tank 70 includes blades 71. It is stirred for 30 minutes through the blades 71, and then placed into the above-mentioned emulsifier. Stir at 90° C. for 30 minutes to form a third mixture 30 .

如圖6所示，將上述經過處理的該第二混合體20及該第三混合體30應用該行星式混拌機80進行行星式混拌，其中公轉速度為25rpm，自轉速度為 2500rpm，共混合3小時，而形成第四混合體40。圖6中的B點係對應到圖2中流程的B點位置，圖6中的C點係對應到圖3中流程的C點位置。 As shown in FIG. 6 , the processed second mixture 20 and the third mixture 30 are planetary mixed using the planetary mixer 80 , where the revolution speed is 25 rpm and the rotation speed is 2500 rpm, and mixed for a total of 3 hours to form a fourth mixture 40. Point B in Figure 6 corresponds to the position of point B in the process in Figure 2, and point C in Figure 6 corresponds to the position of point C in the process in Figure 3.

然後將該第四混合體40進行噴霧乾燥作業。其方式為：首先將該第四混合體40置入該行星式混拌機80之內桶81進行混拌，其中自轉速度為0rpm，公轉速度為10rpm。經過2~4小時後，再應用幫浦將該第四混合體40抽送到一四流體噴頭60噴出而形成噴霧。其中該四流體噴頭60的氣壓為3kg/cm2。其中該第四混合體40在該四流體噴頭60內部進行熱烘。其熱烘溫度為170~185℃。而在熱烘出口的溫度為150~160℃。因此形成本案所需要的矽碳複合結構混體9，其中該矽碳複合結構混體9的粒徑D50落在3~10微米之間，即指其中有50%的矽碳複合結構混體9之粒徑落在3~10微米之間。 The fourth mixture 40 is then spray-dried. The method is as follows: first put the fourth mixture 40 into the barrel 81 of the planetary mixer 80 for mixing, where the rotation speed is 0 rpm and the revolution speed is 10 rpm. After 2 to 4 hours, a pump is used to pump the fourth mixture 40 to a four-fluid nozzle 60 for spraying to form a spray. The air pressure of the four-fluid nozzle 60 is 3kg/cm2. The fourth mixture 40 is heated inside the four-fluid nozzle 60 . The baking temperature is 170~185℃. The temperature at the hot drying outlet is 150~160℃. Therefore, the silicon carbon composite structure mixture 9 required in this case is formed, in which the particle size D50 of the silicon carbon composite structure mixture 9 falls between 3 and 10 microns, which means that 50% of the silicon carbon composite structure mixture 9 is contained in it. The particle size falls between 3 and 10 microns.

在本案中以上各成分的數值均可以做±20%的變動，並不影響本案的結果。 In this case, the values of each of the above components can be changed by ±20%, which will not affect the result of this case.

本案中在原始之矽材料中加入複合分散劑(其組成成分為高分子支撐劑、小分子定錨劑、以及稠化劑)，此複合分散劑用於分散並支撐奈微化之矽材料，避免矽材料在分散過程中反團失區分散效益；並且在材料中加入特定層數之高純度精煉化石墨烯，利用石墨烯、特殊碳材料與奈微化矽材結合形成特殊3D結構以增加矽材料間的導電溝通橋樑。而且在分散工藝中以研磨機應用研磨片及鋯珠，以及應用特殊行星式混拌機，在各階段工藝中協作使複合材料可以藉由特殊binder配方充分互溶，均勻混合，並輔以造粒噴霧設備賦予其結構形貌；總和產生具有較佳的導電性與膨脹緩能力之高循環性矽碳結構。 In this case, a composite dispersant (composed of polymer proppant, small molecule anchoring agent, and thickening agent) was added to the original silicon material. This composite dispersant is used to disperse and support the micronized silicon material. To prevent the silicon material from being deagglomerated during the dispersion process and losing the dispersion efficiency; and adding a specific number of layers of high-purity refined graphene to the material, using graphene, special carbon materials and nano-micronized silicon materials to combine to form a special 3D structure to increase the Conductive communication bridge between silicon materials. Moreover, in the dispersion process, a grinding machine is used to apply grinding discs and zirconium beads, and a special planetary mixer is used to cooperate in each stage of the process so that the composite materials can be fully miscible and uniformly mixed through a special binder formula, supplemented by granulation. The spray equipment gives it a structural morphology; the sum total produces a highly cyclic silicon-carbon structure with better conductivity and expansion retardation capabilities.

綜上所述，本案人性化之體貼設計，相當符合實際需求。其具體改進現有缺失，相較於習知技術明顯具有突破性之進步優點，確實具有功效之增進，且非易於達成。本案未曾公開或揭露於國內與國外之文獻與市場上，已符合專利法規定。 To sum up, the humanized and considerate design of this case is quite in line with actual needs. Its specific improvement has the existing deficiencies, and it has obvious breakthrough advantages compared to the conventional technology, and it does have an improvement in efficacy, and it is not easy to achieve. This case has not been published or disclosed in domestic or foreign documents or markets, and it complies with the provisions of the patent law.

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 above detailed description is a specific description of one possible embodiment of the present invention. However, this embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not depart from the technical spirit of the present invention shall be included in within the scope of the patent in this case.

1:第一母膠 1: First masterbatch

2:第一母膠 2: First masterbatch

4:純矽 4:Pure silicon

5:石墨烯 5: Graphene

15:第一研磨體 15: First grinding body

16:第二研磨體 16: Second grinding body

50:研磨機 50:Grinder

51:研磨片 51: Grinding disc

10:第一混合體 10:First mixture

52:鋯珠 52:Zirconium beads

Claims

一種多層狀長循環矽碳負極材料之製造方法，包含下列步驟：步驟A：取一純矽；步驟B：另外取一第一母膠A，該第一母膠A的成分為溶劑及分散劑；其中該溶劑的組成成分為乙醇、丙酮及水；該分散劑的組成成分為高分子支撐劑、小分子定錨劑、以及稠化劑；步驟C：將10%wt的純矽與90%wt的第一母膠A混合形成第一混合體，再進行研磨，其研磨的方式為將該第一混合體進入一研磨機中研磨，因此形成第一研磨體；步驟D：取一石墨烯(graphene)；步驟E：另外取第一母膠B，其成分同於上述第一母膠A；將10%wt的石墨烯與90%wt的第一母膠B混合後再進入該研磨機中研磨，因此形成第二研磨體；步驟F：將等重量的第一研磨體與第二研磨體混合形成第二混合體，再進行行星式混拌、乳化均質及脫泡行星混拌的程序；步驟G：將奈米碳管(CNT)及一第二母膠混合，該奈米碳管為陣列式奈米碳管，且該第二母膠的成分為溶劑及包覆劑，其中該溶劑為水；步驟H：將該奈米碳管及該第二母膠的混合體置入一葉片攪拌槽中，該葉片攪拌槽包含葉片，經由該葉片攪拌一預定時間，再置入乳化機中攪拌一預定時間而形成第三混合體；步驟I：將上述經過處理的該第二混合體及該第三混合體進行行星式混拌，而形成第四混合體；步驟J：然後將該第四混合體進行噴霧乾燥作業，而形成矽碳複合結構混體；其中以上各成分的數值均可以做±20%的變動。 A method for manufacturing multi-layered long-circulation silicon-carbon negative electrode materials, including the following steps: Step A: Get a piece of pure silicon; Step B: Get a first masterbatch A, the components of the first masterbatch A are solvent and dispersion agent; wherein the solvent is composed of ethanol, acetone and water; the dispersant is composed of polymer proppant, small molecule anchoring agent, and thickener; step C: mix 10%wt pure silicon with 90 %wt of the first masterbatch A is mixed to form a first mixture, and then ground. The grinding method is to grind the first mixture into a grinder, thereby forming a first grinding body; Step D: Take a graphite graphene; Step E: In addition, take the first masterbatch B, whose composition is the same as the above-mentioned first masterbatch A; mix 10%wt graphene and 90%wt first masterbatch B before entering the grinding Grinding in the machine, thus forming a second grinding body; Step F: Mix the first grinding body and the second grinding body of equal weight to form a second mixture, and then perform planetary mixing, emulsification, homogenization and deaeration planetary mixing. Procedure; Step G: Mix carbon nanotubes (CNT) and a second masterbatch, the carbon nanotubes are arrayed carbon nanotubes, and the components of the second masterbatch are solvents and coating agents, wherein The solvent is water; Step H: Place the mixture of carbon nanotubes and the second masterbatch into a blade stirring tank. The blade stirring tank contains blades, stir for a predetermined time through the blades, and then put into the emulsifying tank. Stir in the machine for a predetermined time to form a third mixture; Step I: Perform planetary mixing of the above-mentioned processed second mixture and the third mixture to form a fourth mixture; Step J: Then The fourth mixture is spray-dried to form a silicon-carbon composite structure mixture; the values of each of the above components can vary by ±20%.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟A中，該純矽為金屬還原矽，原始粒徑為10~15mm。 The manufacturing method of multi-layered long-cycle silicon-carbon negative electrode material as described in claim 1, wherein in step A, the pure silicon is metal-reduced silicon, and the original particle size is 10~15mm.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟A中，該第一母膠的溶劑其比例為98.8%wt(重量百分比)；該第一母膠的分散劑其比例為1.2%wt；其中該溶劑的組成成分為40%wt的乙醇、2%wt的丙酮及58%wt的水；以該第一母膠的重量計，該分散劑的組成成分為0.6~1.2%wt的高分子支撐劑、0.1~0.3%wt的小分子定錨劑、以及0.1~0.4%wt的稠化劑；其中以上各成分的數值均可以做±20%的變動。 The manufacturing method of multi-layered long-cycle silicon carbon negative electrode material as described in claim 1, wherein in step A, the proportion of the solvent of the first masterbatch is 98.8%wt (weight percentage); The proportion of the dispersant is 1.2%wt; the solvent is composed of 40%wt ethanol, 2%wt acetone and 58%wt water; based on the weight of the first masterbatch, the composition of the dispersant It consists of 0.6~1.2%wt polymer proppant, 0.1~0.3%wt small molecule anchoring agent, and 0.1~0.4%wt thickening agent; the values of each of the above components can be changed by ±20%.

如請求項3所述之多層狀長循環矽碳負極材料之製造方法，其中該高分子支撐劑選自PVP或PVA，且其分子量約為20000~30000g/mole(克/莫耳)；該小分子定錨劑選自不飽和醚酮類或苯磺酸鹽類；該稠化劑選自羧乙基或羧丙基纖維素鈉、或聚醣類高分子。 The manufacturing method of multi-layered long-cycle silicon carbon negative electrode material as described in claim 3, wherein the polymer proppant is selected from PVP or PVA, and its molecular weight is about 20000~30000g/mole (gram/mol); The small molecule anchoring agent is selected from unsaturated ether ketones or benzene sulfonates; the thickening agent is selected from carboxyethyl or carboxypropyl cellulose sodium, or polysaccharide polymers.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟C中，該研磨機包含研磨片及鋯珠，該研磨片係以3000~3400rpm的轉速轉動，鋯珠的粒徑為0.2~0.4mm，在16~23℃的環境下進行12~16小時的研磨，其中該鋯珠與該第一混合體的比例為該鋯珠佔70~78%wt。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 1, wherein in step C, the grinder includes a grinding disc and zirconium beads, the grinding disc rotates at a speed of 3000~3400 rpm, and the zirconium beads The particle size is 0.2~0.4mm, and the grinding is carried out in an environment of 16~23°C for 12~16 hours, in which the ratio of the zirconium beads to the first mixture is 70~78%wt of the zirconium beads.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟E中，該研磨機包含研磨片及鋯珠，進行研磨的條件為使用粒徑為0.6~1.0mm的鋯珠，研磨片以2200~2600rpm的轉速轉動，在18~25℃的環境下進行20~24小時的研磨，其中該鋯珠與該第一混合體的比例為該鋯珠佔70~78%wt。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 1, wherein in step E, the grinder includes grinding discs and zirconium beads, and the conditions for grinding are to use particles with a particle size of 0.6~1.0mm. The zirconium beads and the grinding disc rotate at a speed of 2200 to 2600 rpm, and are ground for 20 to 24 hours in an environment of 18 to 25°C. The ratio of the zirconium beads to the first mixture is 70 to 78% of the zirconium beads. wt.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟F中進行行星式混拌的方式為將該第二混合體置入一行星式混拌機中進行混拌，其中該行星式混拌機包含：一內桶，用於放置該第二混合體，並攪拌該第二混合體；一外桶，係容納該內桶，該外桶及該內桶之間配置有冷卻水，以冷卻該內桶內部的該第二混合體，該冷卻水外接循環冷卻系統，以達到該冷卻水循環及熱交換的效果；一公轉式攪拌器，配置於該內桶內，並外接驅動機構，該公轉式攪拌器係用於將該第二混合體作大路徑的攪拌，以使得該第二混合體在該內桶內部形成較大區域的位移；一自轉式攪拌器，係用於將該第二混合體做局部的充分攪拌，主要是由塊狀體沿著自身的軸線作自轉，而使得在該自轉式攪拌器周圍的該第二混合體形成渦流；其中該自轉式攪拌器為至少一轉球，並由一懸鐵柱懸吊，再經由驅動機構加以驅動。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 1, wherein the planetary mixing method in step F is to put the second mixture into a planetary mixer for mixing. Mixing, wherein the planetary mixer includes: an inner barrel for placing the second mixture and stirring the second mixture; An outer barrel accommodates the inner barrel. Cooling water is disposed between the outer barrel and the inner barrel to cool the second mixture inside the inner barrel. The cooling water is externally connected to a circulating cooling system to achieve the cooling water circulation. And the effect of heat exchange; a revolution-type stirrer is arranged in the inner barrel and is connected to an external driving mechanism. The revolution-type stirrer is used to stir the second mixture in a large path, so that the second mixture The body forms a large area of displacement inside the inner barrel; a rotating stirrer is used to fully stir the second mixed body locally, mainly because the block body rotates along its own axis, so that The second mixture forms a vortex around the self-rotating stirrer; wherein the self-rotating stirrer is at least one rotating ball, suspended by a suspension iron column, and driven by a driving mechanism.

如請求項7所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟F中進行行星式混拌時，該行星式混拌機的公轉速率為10~30rpm，自轉的速率為3500~5000rpm。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 7, wherein when planetary mixing is performed in step F, the revolution speed of the planetary mixer is 10~30rpm, and the rotation speed is 3500~5000rpm.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟F中進行乳化均質的方式為將經過行星式混拌的該第二混合體置入一乳化機中；其中該乳化機包含一乳化桶，該乳化桶內部包含經過該行星式混拌的第二混合體；其中該乳化桶內部尚包含一攪拌桶，該攪拌桶的底部包含多個輸入孔，可以將該第二混合體置入該攪拌桶；該攪拌桶內部有攪拌器用於將該攪拌桶內的該第二混合體攪拌使其均勻並且將其顆粒打散成為較小粒徑的顆粒；該攪拌桶的下側邊包含多個第一輸出孔，經攪拌的該第二混合體且粒徑較小者可以由該第一輸出孔輸出至該乳化桶；該攪拌桶的上側邊包含多個第二輸出孔，經攪拌的該第二混合體且未由該第一輸出孔輸出者，在該攪拌桶內經過進一步的攪拌，再由該第二輸出孔輸出至該乳化桶；其中從該第一輸出孔及該第二輸出孔輸出到該乳化桶的第二混合體再從該輸入孔輸入到該攪拌桶內，因此使得該第二混合體在該乳化桶內反覆循環攪拌而去團聚形成乳化狀態；在該乳化桶的內側位在第二輸出孔的上方處可以進行抽氣，以導引該第二混合體由下往上流動。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 1, wherein the emulsification and homogenization method in step F is to place the second mixture that has undergone planetary mixing into an emulsifier; The emulsifying machine includes an emulsifying barrel, the inside of the emulsifying barrel contains the second mixture that has been mixed by the planetary type; the inside of the emulsifying barrel also includes a stirring barrel, and the bottom of the stirring barrel includes a plurality of input holes, which can The second mixture is placed in the mixing barrel; there is a stirrer inside the mixing barrel for stirring the second mixture in the mixing barrel to make it uniform and breaking its particles into smaller particles; the stirring The lower side of the barrel includes a plurality of first output holes, and the stirred second mixture with smaller particle size can be output from the first output hole to the emulsification barrel; the upper side of the mixing barrel includes a plurality of The second output hole, the stirred second mixture that is not output from the first output hole, is further stirred in the mixing barrel, and then output from the second output hole to the emulsification barrel; where from the The first output hole and the second output hole The second mixture output to the emulsification barrel is then input into the mixing barrel from the input hole, so that the second mixture is repeatedly circulated and stirred in the emulsification barrel to deagglomerate and form an emulsified state; inside the emulsification barrel Air can be evacuated above the second output hole to guide the second mixture to flow from bottom to top.

如請求項9所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟F中進行乳化均質時，該乳化機進行乳化時的轉速為9000~11000rpm。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 9, wherein when the emulsification and homogenization are carried out in step F, the rotation speed of the emulsifier during emulsification is 9000~11000 rpm.

如請求項7所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟F中進行脫泡行星混拌的方式為將經過乳化均質後的該第二混合體置入該行星式混拌機內進行脫泡行星混拌作業；其中係在該內桶內進行抽氣，因此完成該第二混合體的處理。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 7, wherein the degassing planetary mixing method in step F is to place the emulsified and homogenized second mixture into the planetary mixer. The degassing planetary mixing operation is carried out in the mixer; the air is pumped in the inner barrel, thereby completing the processing of the second mixture.

如請求項11所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟F中進行脫泡行星混拌時，該行星式混拌機的自轉速度為0rpm，公轉速度為30rpm，共進行30分鐘。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 11, wherein when performing degassing planetary mixing in step F, the rotation speed of the planetary mixer is 0 rpm and the revolution speed is 30 rpm, Take 30 minutes in total.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟G中，在該第二母膠中該包覆劑的比例為2~6.8%wt，其餘則為該溶劑；該包覆劑的材料為寡糖類高分子及少量的寡糖酮類，其中該寡糖類高分子及該寡糖酮類的重量比為3~6：1；其中該奈米碳管與該第二母膠混合的重量比為，該奈米碳管占0.1~0.18%wt，其餘則為該第二母膠；其中以上各成分的數值均可以做±20%的變動。 The manufacturing method of multi-layered long-cycle silicon carbon negative electrode material as described in claim 1, wherein in step G, the proportion of the coating agent in the second masterbatch is 2~6.8%wt, and the rest is Solvent; the material of the coating agent is oligosaccharide polymer and a small amount of oligosaccharide ketone, wherein the weight ratio of the oligosaccharide polymer and the oligosaccharide ketone is 3~6:1; wherein the carbon nanotube and The weight ratio of the second masterbatch is: the carbon nanotubes account for 0.1~0.18%wt, and the rest is the second masterbatch; the values of each of the above components can be changed by ±20%.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟J中進行噴霧乾燥作業的方式為先將該第四混合體置入行星式混拌機之內桶進行混拌，經過一預定時間後，再應用幫浦將該第四混合體抽送到一四流體噴頭噴出而形成噴霧；其中該第四混合體在該四流體噴頭內部進行熱烘；因此形成該矽碳複合結構混體。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 1, wherein the spray drying operation in step J is to first place the fourth mixture into the inner barrel of a planetary mixer. Mix, and after a predetermined time, use a pump to pump the fourth mixture to a four-fluid nozzle and spray it to form a spray; wherein the fourth mixture is heated and baked inside the four-fluid nozzle; thus forming the silicon Carbon composite structure hybrid.

如請求項14所述之多層狀長循環矽碳負極材料之製造方法，其中在步驟J中進行噴霧乾燥作業時，該行星式混拌機的自轉速度為0rpm，公轉速度為10rpm；然後經過2~4小時後，再將該第四混合體抽送到該四流體噴頭；其中該四流體噴頭的氣壓為3kg/cm2；其中該四流體噴頭內部進行熱烘的溫度為170~185℃，而在熱烘出口的溫度為150~160℃。 The manufacturing method of multi-layered long-circulation silicon carbon negative electrode material as described in claim 14, wherein during the spray drying operation in step J, the rotation speed of the planetary mixer is 0 rpm and the revolution speed is 10 rpm; and then through After 2 to 4 hours, the fourth mixture is pumped to the four-fluid nozzle; the air pressure of the four-fluid nozzle is 3kg/cm2; the baking temperature inside the four-fluid nozzle is 170~185°C, and The temperature at the hot drying outlet is 150~160℃.

如請求項1所述之多層狀長循環矽碳負極材料之製造方法，其中該矽碳複合結構混體的粒徑D50落在3~10微米之間，即其中有50%的矽碳複合結構混體之粒徑落在3~10微米之間。 The manufacturing method of multi-layered long-cycle silicon-carbon negative electrode material as described in claim 1, wherein the particle size D50 of the silicon-carbon composite structure mixture falls between 3 and 10 microns, that is, 50% of the silicon-carbon composite structure mixture is The particle size of the structural mixture falls between 3 and 10 microns.