TWI756982B

TWI756982B - Secondary granulated silicon carbon base battery negative electrode material and preparation method thereof

Info

Publication number: TWI756982B
Application number: TW109144058A
Authority: TW
Inventors: 周憲聰; 吳玉祥; 胡旭添; 陳伯坤; 湯昊; 劉烈凱
Original assignee: 榮炭科技股份有限公司
Priority date: 2020-12-14
Filing date: 2020-12-14
Publication date: 2022-03-01
Also published as: TW202224239A

Abstract

本說明書揭示一種二次造粒之矽碳基材電池負極材料及其製備方法。上述二次造粒之矽碳基材電池負極材料包含碳基材、複數個奈米矽、以及修飾層。上述二次造粒之矽碳基材電池負極材料之製備方法藉由將奈米矽嵌入碳基材的表面孔隙、與修飾層的包覆，可提昇電池調漿時的均勻性與負極材料的滲液性，進而可達到有效提昇電池的循環性能與穩定性之效果。 This specification discloses a secondary granulated silicon carbon base battery negative electrode material and a preparation method thereof. The above-mentioned secondary granulated silicon carbon base battery negative electrode material includes a carbon base material, a plurality of nano-silicon, and a modification layer. The preparation method of the above-mentioned secondary granulated silicon carbon substrate battery negative electrode material can improve the uniformity of the battery and the negative electrode material during sizing by embedding nano-silicon into the surface pores of the carbon substrate and coating the modified layer. The liquid permeability can effectively improve the cycle performance and stability of the battery.

Description

二次造粒之矽碳基材電池負極材料及其製備方法Secondary granulated silicon carbon base battery negative electrode material and preparation method thereof

本發明係關於一種碳基材電池負極材料，特別是關於一種二次造粒之矽碳基材電池負極材料及其製備方法。 The present invention relates to a carbon-based battery negative electrode material, in particular to a secondary granulated silicon carbon-based battery negative electrode material and a preparation method thereof.

新能源電池的發展在很大的程度上取決於高性能正、負極材料的開發與應用。以負極材料為例，習知技藝者已經發現，使用經過造粒製程來形成的電池負極材料可大幅提升電池壽命，增加產品的充放電次數。習知技藝中使用天然或人造石墨來作為電極材料時，為了降低初期的不可逆電容量與提升電池的循環壽命，通常需要先以瀝青類芳烴化合物材料來進行表面改質。 The development of new energy batteries depends to a large extent on the development and application of high-performance positive and negative electrode materials. Taking the negative electrode material as an example, those skilled in the art have found that the use of the battery negative electrode material formed by the granulation process can greatly improve the battery life and increase the charging and discharging times of the product. When natural or artificial graphite is used as the electrode material in the prior art, in order to reduce the initial irreversible capacitance and improve the cycle life of the battery, it is usually necessary to first perform surface modification with a pitch-based aromatic compound material.

習知技藝中常見的負極造粒製程，是先以高溫熔融方式來混合焦碳與瀝青，然後再依序經過碳化、石墨化等程序來完成。 The common negative electrode granulation process in the prior art is to first mix coke and pitch by high temperature melting, and then proceed through carbonization, graphitization and other procedures in sequence.

為了進一步提昇負極材料的性能，習知技藝中常會在上述製程的一開始即添加氧化矽於石墨。第一圖係一習知技藝的碳基材電池負極材料示意圖。在碳基材負極材料100中，所添加的氧化矽140可以是藉由瀝青160來沾附於石墨120的表面上，如第一圖所示。然而，在添加氧化矽140之後，因為氧化矽140與石墨120間的結合力不足，在電池調漿時，氧化矽140自石墨 120脫落，將影響後續應用時電池調漿的均勻性。另一方面，在電池充放電時，氧化矽140的體積變化，也會造成氧化矽140從石墨120的表面脫落，進而影響電池的迴圈穩定性。上述現象都會使得使用習知技藝的負極材料之電池無法發揮其應有的效能。 In order to further improve the performance of the negative electrode material, in the prior art, silicon oxide is often added to the graphite at the beginning of the above process. The first figure is a schematic diagram of a carbon-based battery negative electrode material in the prior art. In the carbon-based negative electrode material 100 , the added silicon oxide 140 may be adhered to the surface of the graphite 120 by the pitch 160 , as shown in the first figure. However, after adding silicon oxide 140, due to insufficient bonding force between silicon oxide 140 and graphite 120, when the battery is slurried, silicon oxide 140 is separated from graphite. 120 will fall off, which will affect the uniformity of battery slurry mixing in subsequent applications. On the other hand, when the battery is charged and discharged, the volume change of the silicon oxide 140 will also cause the silicon oxide 140 to fall off from the surface of the graphite 120, thereby affecting the cycle stability of the battery. The above phenomena will make the battery using the negative electrode material of the prior art unable to exert its due performance.

有鑑於此，開發可在有效地提昇電池負極材料的性能時，同時兼顧負極材料的滲液性、電池調漿的均勻性、與提昇電池迴圈的穩定性之碳基材電池負極材料及其製備方法，是一項相當值得產業重視且可有效提升產業競爭力的課題。 In view of this, the development of carbon-based battery negative electrode materials that can effectively improve the performance of battery negative electrode materials, while taking into account the liquid permeability of negative electrode materials, the uniformity of battery slurry mixing, and the improvement of battery cycle stability. The preparation method is a subject worthy of the industry's attention and can effectively enhance the competitiveness of the industry.

鑒於上述之發明背景中，為了符合產業上之要求，本發明提供一種二次造粒之矽碳基材電池負極材料及其製備方法，上述二次造粒之矽碳基材電池負極材料及其製備方法，不僅製程簡易，更具有可大幅提昇電池調漿時的均勻性與負極材料的滲液性，更好的是，上述二次造粒之矽碳基材電池負極材料及其製備方法可有效提昇電池的迴圈穩定性，進而可有效提昇產業競爭力之效果。 In view of the above background of the invention, in order to meet the requirements of the industry, the present invention provides a secondary granulated silicon carbon base battery negative electrode material and a preparation method thereof, the above secondary granulated silicon carbon base battery negative electrode material and the same The preparation method is not only simple in the process, but also has the advantages of greatly improving the uniformity of the battery during slurry mixing and the liquid permeability of the negative electrode material. What is more, the above-mentioned secondary granulated silicon carbon substrate battery negative electrode material and its preparation method can be used. It can effectively improve the cycle stability of the battery, and then can effectively enhance the effect of industrial competitiveness.

本發明之一目的在於提供一種二次造粒之矽碳基材電池負極材料及其製備方法，藉由將奈米矽嵌入於碳基材表面的孔隙，以降低因為奈米矽脫落而降低電池調漿時的均勻性。 One object of the present invention is to provide a secondary granulated silicon-carbon base battery negative electrode material and a preparation method thereof. By embedding nano-silicon into the pores on the surface of the carbon base material, it can reduce the deterioration of the battery due to the peeling of nano-silicon. Homogeneity when mixing.

本發明之另一目的在於提供一種二次造粒之矽碳基材電池負極材料及其製備方法，藉由使用表面孔隙嵌有奈米矽的碳基材來進行造粒，以提昇電池應用時的滲液性。 Another object of the present invention is to provide a secondary granulated silicon carbon substrate battery negative electrode material and a preparation method thereof. of exudation.

本發明之再一目的在於提供一種二次造粒之矽碳基材電池負極材料及其製備方法，藉由使用修飾層來包覆表面孔隙嵌有奈米矽的碳基材，使得在上述二次造粒之矽碳基材電池負極材料可進一步預防奈米矽從碳基材脫落，進而降低因為奈米矽脫落而降低電池調漿時的均勻性與提昇電池應用時的滲液性。 Another object of the present invention is to provide a secondary granulated silicon carbon base A material battery negative electrode material and a preparation method thereof, by using a modified layer to coat a carbon substrate with nano-silicon embedded in the surface pores, so that the above-mentioned secondary granulated silicon-carbon substrate battery negative material can further prevent nano-silicon It is peeled off from the carbon substrate, thereby reducing the uniformity of the battery during sizing and improving the liquid permeability during battery application due to the peeling of the nano-silicon.

本發明之又一目的在於提供一種二次造粒之矽碳基材電池負極材料及其製備方法，藉由使用修飾層來包覆表面孔隙嵌有奈米矽的碳基材，使得上述二次造粒之矽碳基材電池負極材料可在電池應用時提供充分緩衝能力來因應奈米矽因充放電而產生的體積變化，進而達到提昇電池的迴圈穩定性之效果。 Another object of the present invention is to provide a secondary granulated silicon carbon substrate battery negative electrode material and a preparation method thereof. By using a modified layer to coat the carbon substrate with nano-silicon embedded in the surface pores, the above secondary granulation can be achieved. The granulated silicon carbon-based battery negative electrode material can provide sufficient buffering capacity during battery application to cope with the volume change of nano-silicon due to charge and discharge, thereby improving the cycle stability of the battery.

本發明之又一目的在於提供一種二次造粒之矽碳基材電池負極材料之製備方法，藉由使用可改變溫度之迴轉爐，使得上述二次造粒之矽碳基材電池負極材料之製備方法可在迴轉爐中完成二次造粒，進而達到簡化製程之效果。 Another object of the present invention is to provide a method for preparing a secondary granulated silicon carbon base battery negative electrode material, by using a temperature-changeable rotary kiln to make the above secondary granulated silicon carbon base battery negative electrode material The preparation method can complete the secondary granulation in the rotary kiln, thereby achieving the effect of simplifying the process.

根據以上所述之目的，本發明揭示了一種二次造粒之矽碳基材電池負極材料及其製備方法。上述二次造粒之矽碳基材電池負極材料包含碳基材、複數個奈米矽、以及修飾層。上述的複數個奈米矽可以是分別嵌入於上述碳基材的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。在根據本說明書之一較佳範例中，上述的複數個奈米矽可以是分別擠壓嵌入於上述碳基材的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。上述的修飾層可以是包覆於上述表面孔隙嵌有奈米矽的碳基材之上。 According to the above purpose, the present invention discloses a secondary granulated silicon carbon base battery negative electrode material and a preparation method thereof. The above-mentioned secondary granulated silicon carbon base battery negative electrode material includes a carbon base material, a plurality of nano-silicon, and a modification layer. The plurality of nano-silicons can be respectively embedded in the surface pores of the carbon substrate to form a carbon substrate with nano-silicon embedded in the surface pores. In a preferred example according to the present specification, the plurality of nano-silicons can be respectively extruded and embedded in the surface pores of the carbon substrate to form a carbon substrate with nano-silicon embedded in the surface pores. The above-mentioned modification layer may be coated on the above-mentioned carbon substrate with surface pores embedded with nano-silicon.

上述二次造粒之矽碳基材電池負極材料之製備方法包含混合奈米矽與碳基材、添加黏合劑、造粒與碳化、解碎、以及過篩等步驟。在根據本說明書之一較佳範例中，上述混合奈米矽與碳基材的步驟可以更包含將奈米矽擠壓嵌入碳基材的步驟。在根據本說明書之一較佳範例中，上述的造粒與碳化步驟可以是在一迴轉爐中完成。根據本說明書之技術方案，藉由奈米矽與修飾層的使用，不僅可大幅提昇電池調漿時的均勻性與負極材料的滲液性，更好的是，上述二次造粒之矽碳基材電池負極材料及其製備方法可有效提昇電池的迴圈穩定性，進而可有效提昇產業競爭力之效果。 The preparation method of the secondary granulated silicon carbon base battery negative electrode material includes the steps of mixing nano-silicon and carbon base material, adding a binder, granulating and carbonizing, disintegrating, and sieving. In a preferred example according to the present specification, the above-mentioned hybrid nanometer The step of silicon and carbon substrate may further include the step of extruding nano-silicon into the carbon substrate. In a preferred example according to the present specification, the above-mentioned granulation and carbonization steps may be performed in a rotary kiln. According to the technical solution in this specification, the use of nano-silicon and the modified layer can not only greatly improve the uniformity of the battery and the liquid permeability of the negative electrode material during slurry mixing, but also better, the above-mentioned secondary granulation silicon carbon base The material battery anode material and the preparation method thereof can effectively improve the cycle stability of the battery, thereby effectively enhancing the effect of industrial competitiveness.

100:習知技藝的碳基材電池負極材料 100: Carbon-based battery negative electrode materials of the prior art

120:焦碳 120: Coke

140:氧化矽 140: Silicon oxide

160:瀝青 160: Asphalt

200:二次造粒之矽碳基材電池負極材料 200: Secondary granulated silicon carbon substrate battery anode material

220:碳基材 220: carbon substrate

240:奈米矽 240: Nano Silicon

260:修飾層 260: Retouch layer

200’:二次造粒之矽碳基材電池負極材料 200': Secondary granulated silicon carbon substrate battery anode material

220’:碳基材 220': carbon substrate

240’:奈米矽 240’: Nano Silicon

260’:修飾層 260': Retouch layer

300:二次造粒之矽碳基材電池負極材料之製備方法 300: Preparation method of secondary granulated silicon carbon substrate battery negative electrode material

310:混合奈米矽與碳基材的步驟 310: Steps to Mix Nanosilicon with Carbon Substrate

320:添加黏合劑的步驟 320: Steps for adding binders

330:造粒與碳化步驟 330: Granulation and Carbonization Steps

340:解碎步驟 340: Shredding Step

350:過篩步驟 350: Sieve Step

第一圖係習知技藝的矽碳基材電池負極材料之示意圖；第二A圖係根據本說明書之一範例的二次造粒之矽碳基材電池負極材料之示意圖；第二B圖係根據本說明書之另一範例的二次造粒之矽碳基材電池負極材料之示意圖；第三圖係根據本說明書的二次造粒之矽碳基材電池負極材料之製備方法的流程圖；第四圖係不同負極材料製成的扣式電池進行50次電池循環測試之比較圖；以及第五圖係不同負極材料製成的軟包電池進行的1000次電池循環測試之比較圖。 The first diagram is a schematic diagram of the negative electrode material of a silicon carbon base battery in the prior art; the second diagram A is a schematic diagram of the negative electrode material of a secondary granulated silicon carbon substrate battery according to an example of this specification; the second diagram B is a diagram A schematic diagram of a secondary granulation silicon carbon base battery negative electrode material according to another example of this specification; the third figure is a flow chart of a preparation method of a secondary granulated silicon carbon base battery negative electrode material according to this specification; The fourth graph is a comparison graph of 50 battery cycle tests of button batteries made of different negative electrode materials; and the fifth graph is a comparison graph of 1000 battery cycle tests of pouch batteries made of different negative electrode materials.

本發明在此所探討的方向為一種二次造粒之矽碳基材電池負極材料及其製備方法。為了能徹底地瞭解本發明，將在下列的描述中提出詳盡的製程步驟或組成結構。顯然地，本發明的施行並未限定於該領域之技藝者所熟習的特殊細節。另一方面，眾所周知的組成或製程步驟並未描述於細節中，以避免造成本發明不必要之限制。本發明的較佳體系會詳細描述如下，然而除了這些詳細描述之外，本發明還可以廣泛地施行在其他的體系中，且本發明的範圍不受限定，以其之後的專利範圍為準。 The direction of the present invention discussed here is a secondary granulated silicon carbon-based Material battery negative electrode material and preparation method thereof. In order to provide a thorough understanding of the present invention, detailed process steps or compositional structures will be set forth in the following description. Obviously, the practice of the present invention is not limited to the specific details familiar to those skilled in the art. In other instances, well-known compositions or process steps have not been described in detail to avoid unnecessarily limiting the invention. The preferred system of the present invention will be described in detail below, however, in addition to these detailed descriptions, the present invention can also be widely implemented in other systems, and the scope of the present invention is not limited, and the following patent scope shall prevail.

本發明之一實施例揭露一種二次造粒之矽碳基材電池負極材料。上述二次造粒之矽碳基材電池負極材料包含碳基材、複數個奈米矽、以及修飾層。上述的複數個奈米矽可以是分別嵌入於上述碳基材的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。在根據本實施例之一較佳範例中，可藉由一外力擠壓，使得上述的複數個奈米矽分別擠壓嵌入於每一碳基材的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。上述的修飾層可以是包覆於上述表面孔隙嵌有奈米矽的碳基材之上，以形成包覆有修飾層之表面孔隙嵌有奈米矽的碳基材。 An embodiment of the present invention discloses a secondary granulated silicon carbon base battery negative electrode material. The above-mentioned secondary granulated silicon carbon base battery negative electrode material includes a carbon base material, a plurality of nano-silicon, and a modification layer. The plurality of nano-silicons can be respectively embedded in the surface pores of the carbon substrate to form a carbon substrate with nano-silicon embedded in the surface pores. In a preferred example according to this embodiment, the above-mentioned plurality of nano-silicons can be squeezed and embedded in the surface pores of each carbon substrate by extruding by an external force, so as to form the surface pores embedded with nano-silicon. Silicon carbon substrate. The modification layer can be coated on the carbon substrate with the nano-silicon embedded in the surface pores, so as to form the carbon substrate with the nano-silicon embedded in the surface pores coated with the modification layer.

在根據本實施例之一較佳範例中，複數個上述包覆有修飾層之表面孔隙嵌有奈米矽的碳基材可堆疊成一碳基材集合。 In a preferred example according to the present embodiment, a plurality of carbon substrates with nano-silicon embedded in the surface pores coated with the modification layer can be stacked to form a set of carbon substrates.

第二A圖係一根據本實施例的一較佳範例之二次造粒之矽碳基材電池負極材料的示意圖。如第二A圖所示，上述二次造粒之矽碳基材電池負極材料200包含碳基材220、複數個奈米矽240、以及修飾層260。在根據本範例之一較佳實施方式中，上述碳基材220可以是選自下列群組之一者或其組合：天然石墨、人造石墨、石墨烯、奈米碳管(CNT)、以及氣相成長碳纖維(VGCF)、中間相碳微球材料(MCMB)。在根據本範例之一較佳實施方式中，上述碳基材220的粒徑約5-20μm。在根據本範例之另一較佳實施方式中，上述碳基材220的粒徑約15μm。 The second figure A is a schematic diagram of the negative electrode material of the secondary granulated silicon carbon base battery according to a preferred example of the present embodiment. As shown in FIG. 2 A, the above-mentioned secondary granulated silicon carbon base battery negative electrode material 200 includes a carbon base material 220 , a plurality of nano-silicon 240 , and a modification layer 260 . In a preferred embodiment according to this example, the above-mentioned carbon substrate 220 may be selected from one of the following groups or a combination thereof: natural graphite, Artificial graphite, graphene, carbon nanotubes (CNTs), as well as vapor grown carbon fibers (VGCF), mesophase carbon microsphere materials (MCMB). In a preferred embodiment according to the present example, the particle size of the carbon substrate 220 is about 5-20 μm. In another preferred embodiment according to this example, the particle size of the carbon substrate 220 is about 15 μm.

參見第二A圖，複數個奈米矽240可以是分別嵌入於碳基材220的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。在根據本實施例之一較佳範例中，可藉由一外力擠壓，使得上述的複數個奈米矽240分別擠壓嵌入於每一碳基材220的表面孔隙，如此一來，奈米矽240可擠壓嵌入至碳基材220表面之更深處，以形成表面孔隙嵌有奈米矽的碳基材。在根據本範例之一較佳實施方式中，上述奈米矽240的粒徑約100-900nm。在根據本範例之另一較佳實施方式中，上述奈米矽240的粒徑約200nm。修飾層260包覆於上述表面孔隙嵌有奈米矽的碳基材之上，以形成包覆有修飾層之表面孔隙嵌有奈米矽的碳基材。在根據本範例之一較佳實施方式中，上述修飾層260的厚度約15-1000nm。在根據本範例之另一較佳實施方式中，上述修飾層260的厚度約100nm。上述修飾層260的組成可以是包含黏合劑。在根據本範例之一較佳實施方式中，上述黏合劑可以是選自下列群組之一者或其組合：瀝青、酚醛樹酯、羧甲基纖維素(Carboxymethyl Cellulose，簡稱CMC)、麥芽糊精、丁苯橡膠(Styrene-Butadiene Rubber，簡稱SBR)。 Referring to the second figure A, a plurality of nano-silicon 240 can be respectively embedded in the surface pores of the carbon substrate 220 to form a carbon substrate with nano-silicon embedded in the surface pores. In a preferred example according to this embodiment, the above-mentioned plurality of nano-silicon 240 can be squeezed and embedded in the surface pores of each carbon substrate 220 by an external force. The silicon 240 can be extruded and embedded deeper into the surface of the carbon substrate 220 to form a carbon substrate with surface pores embedded with nano-silicon. In a preferred embodiment according to the present example, the particle size of the above-mentioned nano-silicon 240 is about 100-900 nm. In another preferred embodiment according to the present example, the particle size of the above-mentioned nano-silicon 240 is about 200 nm. The modification layer 260 is coated on the carbon substrate with the nano-silicon embedded in the surface pores, so as to form the carbon substrate with the nano-silicon embedded in the surface pores coated with the modification layer. In a preferred embodiment according to this example, the thickness of the modification layer 260 is about 15-1000 nm. In another preferred embodiment according to this example, the thickness of the modification layer 260 is about 100 nm. The composition of the above-mentioned modification layer 260 may include an adhesive. In a preferred embodiment according to this example, the above-mentioned binder can be selected from one of the following groups or a combination thereof: pitch, phenolic resin, carboxymethyl cellulose (CMC for short), malt Dextrin, styrene-butadiene rubber (Styrene-Butadiene Rubber, referred to as SBR).

第二B圖係一根據本實施例的另一較佳範例之二次造粒之矽碳基材電池負極材料的示意圖。如第二B圖所示，上述二次造粒之矽碳基材電池負極材料200’包含複數個碳基材 220’、複數個奈米矽240’、以及修飾層260’。 The second figure B is a schematic diagram of the negative electrode material of the secondary granulated silicon carbon base battery according to another preferred example of the present embodiment. As shown in Figure 2 B, the above-mentioned secondary granulated silicon carbon base battery negative electrode material 200' includes a plurality of carbon base materials 220', a plurality of nano-silicon 240', and a modification layer 260'.

根據本範例，上述的複數個奈米矽240’分別嵌入於每一碳基材220’的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。在根據本實施例之一較佳範例中，可藉由一外力擠壓，使得上述的複數個奈米矽240’分別擠壓嵌入於每一碳基材220’的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。 According to this example, the above-mentioned plurality of nano-silicon 240' are respectively embedded in the surface pores of each carbon substrate 220' to form a carbon substrate with nano-silicon embedded in the surface pores. In a preferred example according to the present embodiment, the above-mentioned plurality of nano-silicon 240 ′ can be squeezed into the surface pores of each carbon substrate 220 ′ by extruding by an external force, so as to form surface pores A carbon substrate embedded with nanosilicon.

在根據本範例之一較佳實施方式中，上述碳基材220’可以是選自下列群組之一者或其組合：天然石墨、人造石墨、石墨烯、奈米碳管(CNT)、以及氣相成長碳纖維(VGCF)、中間相碳微球材料(MCMB)。在根據本範例之一較佳實施方式中，上述碳基材220’的粒徑約5-20μm。在根據本範例之另一較佳實施方式中，上述碳基材220’的粒徑約15μm。在根據本範例之一較佳實施方式中，上述奈米矽240’的粒徑約100-900nm。在根據本範例之另一較佳實施方式中，上述奈米矽240’的粒徑約200nm。 In a preferred embodiment according to the present example, the carbon substrate 220 ′ can be selected from one or a combination of the following groups: natural graphite, artificial graphite, graphene, carbon nanotube (CNT), and Vapor grown carbon fiber (VGCF), mesocarbon microsphere material (MCMB). In a preferred embodiment according to this example, the particle size of the carbon substrate 220' is about 5-20 μm. In another preferred embodiment according to this example, the particle size of the carbon substrate 220' is about 15 μm. In a preferred embodiment according to this example, the particle size of the above-mentioned nano-silicon 240' is about 100-900 nm. In another preferred embodiment according to this example, the particle size of the above-mentioned nano-silicon 240' is about 200 nm.

上述修飾層260’可以是包覆於上述表面孔隙嵌有奈米矽的碳基材之上，如第二B圖所示。在根據本範例之一較佳實施方式中，複數個包覆有修飾層之表面孔隙嵌有奈米矽的碳基材可堆疊成一碳基材集合，如第二B圖所示。在根據本範例之一較佳實施方式中，上述修飾層260’的厚度約15-30nm。在根據本範例之另一較佳實施方式中，上述修飾層260’的厚度約20nm。上述修飾層260’包含黏合劑。在根據本範例之一較佳實施方式中，上述黏合劑可以是選自下列群組之一者或其組合：瀝青、酚醛樹酯、羧甲基纖維素(Carboxymethyl Cellulose，簡稱CMC)、麥芽糊精、丁苯橡膠(Styrene-Butadiene Rubber，簡稱SBR)。 The above-mentioned modification layer 260' may be coated on the above-mentioned carbon substrate with surface pores embedded with nano-silicon, as shown in the second Figure B. In a preferred embodiment according to the present example, a plurality of carbon substrates coated with modified layers with surface pores embedded with nano-silicon can be stacked to form a carbon substrate set, as shown in the second Figure B. In a preferred embodiment according to this example, the thickness of the modification layer 260' is about 15-30 nm. In another preferred embodiment according to this example, the thickness of the modification layer 260' is about 20 nm. The above-mentioned modification layer 260' contains an adhesive. In a preferred embodiment according to this example, the above-mentioned binder can be selected from one of the following groups or a combination thereof: pitch, phenolic resin, carboxymethyl cellulose (CMC for short), malt Dextrin, styrene-butadiene rubber (Styrene-Butadiene Rubber, referred to as SBR).

本發明之另一實施例揭露一種二次造粒之矽碳基材電池負極材料之製備方法。第三圖係一根據本實施例之二次造粒之矽碳基材電池負極材料之製備方法的示意圖。如第三圖所示，上述二次造粒之矽碳基材電池負極材料之製備方法包含混合奈米矽與碳基材、添加黏合劑、造粒與碳化、解碎、以及過篩等步驟。 Another embodiment of the present invention discloses a preparation method of a secondary granulated silicon carbon base battery negative electrode material. Figure 3 is a schematic diagram of a method for preparing a negative electrode material for a secondary granulated silicon carbon base battery according to the present embodiment. As shown in Figure 3, the above-mentioned preparation method of the secondary granulated silicon carbon substrate battery negative electrode material includes the steps of mixing nano-silicon and carbon substrate, adding a binder, granulating and carbonizing, disintegrating, and sieving. .

根據本實施例之二次造粒之矽碳基材電池負極材料之製備方法，先將碳基材與奈米矽予以混合，使奈米矽分別嵌入於碳基材之表面空隙，以形成表面孔隙嵌有奈米矽的碳基材，如步驟310所示。在根據本實施例之一較佳範例中，上述步驟310可更包含將奈米矽擠壓嵌入碳基材的步驟。根據本範例，藉由一外力擠壓，使得上述的複數個奈米矽分別擠壓嵌入至碳基材表面之更深處，以形成表面孔隙嵌有奈米矽的碳基材。在根據本實施例之一較佳範例中，上述碳基材可以是選自下列之一者或其組合：天然石墨、人造石墨、石墨烯、奈米碳管(CNT)、以及氣相成長碳纖維(VGCF)、中間相碳微球材料(MCMB)。在根據本實施例之一較佳範例中，上述奈米矽之佔比約為0.1-20wt%之碳基材。在根據本實施例之一較佳範例中，上述奈米矽之佔比約為3-15wt%之碳基材。在根據本實施例之一較佳範例中，上述混合碳基材與奈米矽之步驟可以在室溫(約10-40℃)完成。在根據本範例之一較佳實施方式中，上述碳基材的粒徑約5-20μm。在根據本範例之另一較佳實施方式中，上述碳基材的粒徑約15μm。在根據本範例之一較佳實施方式中，上述奈米矽的粒徑約100-900nm。在根據本範例之另一較佳實施方式中，上述奈米矽的粒徑約200nm。 According to the preparation method of the secondary granulated silicon-carbon base battery negative electrode material of this embodiment, the carbon base material and nano-silicon are first mixed, so that the nano-silicon is respectively embedded in the surface voids of the carbon base material to form a surface The pores are embedded with nanosilicon carbon substrate, as shown in step 310 . In a preferred example according to the present embodiment, the above-mentioned step 310 may further include the step of extruding the nano-silicon into the carbon substrate. According to this example, the above-mentioned plurality of nano-silicons are respectively extruded and embedded into the surface of the carbon substrate by extruding by an external force, so as to form a carbon substrate with surface pores embedded with nano-silicon. In a preferred example according to the present embodiment, the carbon substrate may be selected from one of the following or a combination thereof: natural graphite, artificial graphite, graphene, carbon nanotube (CNT), and vapor grown carbon fiber (VGCF), mesophase carbon microsphere material (MCMB). In a preferred example according to the present embodiment, the proportion of the above-mentioned nano-silicon is about 0.1-20 wt % of the carbon substrate. In a preferred example according to the present embodiment, the proportion of the above-mentioned nano-silicon is about 3-15 wt % of the carbon substrate. In a preferred example according to the present embodiment, the above-mentioned step of mixing the carbon substrate and the nano-silicon can be performed at room temperature (about 10-40° C.). In a preferred embodiment according to this example, the particle size of the carbon substrate is about 5-20 μm. In another preferred embodiment according to this example, the particle size of the carbon substrate is about 15 μm. In a preferred embodiment according to the present example, the particle size of the above-mentioned nano-silicon is about 100-900 nm. In another preferred embodiment according to the present example, the particle size of the above-mentioned nano-silicon is about 200 nm.

在根據本實施例之一較佳範例中，上述混合碳基材與奈米矽之步驟可以在一帶有擠壓力的混合機中完成。 In a preferred example according to the present embodiment, the above-mentioned step of mixing the carbon substrate and the nano-silicon can be performed in a mixer with extrusion force.

接下來，將黏合劑添加至上述表面孔隙嵌有奈米矽的碳基材，如步驟320所示。在黏合劑與上述表面孔隙嵌有奈米矽的碳基材充分混合後，即可開始升溫，進入造粒與碳化步驟，如步驟330所示。 Next, a binder is added to the carbon substrate with nanosilicon embedded in the surface pores, as shown in step 320 . After the binder is fully mixed with the carbon substrate with the nano-silicon embedded in the surface pores, the temperature can be started to enter into the granulation and carbonization steps, as shown in step 330 .

在根據本實施例之一較佳範例中，上述黏合劑可以是選自下列群組之一者或其組合：瀝青、酚醛樹酯、羧甲基纖維素(Carboxymethyl Cellulose，簡稱CMC)、麥芽糊精、丁苯橡膠(Styrene-Butadiene Rubber，簡稱SBR)。在根據本實施例之一較佳範例中，步驟320可以是在室溫(約為10-40℃)完成。在根據本實施例之一較佳範例中，上述黏合劑之重量比約為表面孔隙嵌有奈米矽的碳基材之5-15wt%。在根據本實施例之一較佳範例中，上述黏合劑之重量比約為表面孔隙嵌有奈米矽的碳基材之5-10wt%。 In a preferred example according to this embodiment, the above-mentioned binder may be selected from one of the following groups or a combination thereof: pitch, phenolic resin, carboxymethyl cellulose (CMC for short), malt Dextrin, styrene-butadiene rubber (Styrene-Butadiene Rubber, referred to as SBR). In a preferred example according to this embodiment, step 320 may be performed at room temperature (about 10-40° C.). In a preferred example according to the present embodiment, the weight ratio of the above-mentioned binder is about 5-15 wt% of the carbon substrate whose surface pores are embedded with nanosilicon. In a preferred example according to the present embodiment, the weight ratio of the above-mentioned binder is about 5-10 wt % of the carbon substrate whose surface pores are embedded with nano-silicon.

在根據本實施例之一較佳範例中，上述步驟320可以更包含添加一溶劑至上述表面孔隙嵌有奈米矽的碳基材，其中，上述溶液中的溶劑可在後續的造粒與碳化步驟中揮發。上述溶劑可以是選自下列一者或其組合：水、酒精。 In a preferred example according to this embodiment, the step 320 may further include adding a solvent to the carbon substrate with the nano-silicon embedded in the surface pores, wherein the solvent in the solution can be used for subsequent granulation and carbonization. volatilized during the step. The above-mentioned solvent may be selected from one or a combination of the following: water, alcohol.

在造粒與碳化步驟330的升溫過程中，黏合劑將發生熔融，並包覆於上述表面孔隙嵌有奈米矽的碳基材上，以形成包覆有修飾層之表面孔隙嵌有奈米矽的碳基材。在根據本實施例之一較佳範例中，隨著所使用的黏合劑不同，上述包覆有修飾層之表面孔隙嵌有奈米矽的碳基材的形成溫度可以是在升溫至約為20-350℃時完成。在根據本範例之一較佳實施方式中，複數個上述包覆有修飾層之表面孔隙嵌有奈米矽的碳基材可堆疊成一碳基材集合。在根據本範例之一較佳實施方式中，上述修飾層的厚度約15-1000nm。在根據本範例之另一較佳實施方式中，上述修飾層的厚度約100nm。 During the heating process of the granulation and carbonization step 330, the adhesive will be melted and coated on the carbon substrate with the nano-silicon embedded in the surface pores to form the surface pores embedded with nano-silicon coated with the modification layer. Silicon carbon substrate. In a preferred example according to this embodiment, with the different adhesives used, the above-mentioned coating is covered with a modification layer The formation temperature of the carbon substrate with the nano-silicon embedded in the surface pores can be completed when the temperature is raised to about 20-350°C. In a preferred embodiment according to the present example, a plurality of carbon substrates with nano-silicon embedded in the surface pores coated with the modification layer can be stacked to form a set of carbon substrates. In a preferred embodiment according to this example, the thickness of the modification layer is about 15-1000 nm. In another preferred embodiment according to this example, the thickness of the modification layer is about 100 nm.

在根據本實施例之一較佳範例中，上述碳化的溫度約為900-1100℃。在根據本實施例之一較佳範例中，步驟330的造粒與碳化過程可以在迴轉爐、管式爐、推板爐、滾道爐、或靜態加熱爐中完成。 In a preferred example according to this embodiment, the carbonization temperature is about 900-1100°C. In a preferred example according to the present embodiment, the granulation and carbonization process of step 330 can be completed in a rotary furnace, a tube furnace, a push-plate furnace, a rolling furnace, or a static heating furnace.

經過造粒與碳化步驟後，可將上述碳化後之包覆有修飾層之表面孔隙嵌有奈米矽的碳基材進行解碎，如步驟340所示。在根據本實施例之一較佳範例中，步驟340可將上述包覆有修飾層之表面孔隙嵌有奈米矽的碳基材解碎成複數個小顆粒。根據本實施例，在解碎步驟340之後，可對解碎後的小顆粒進行一過濾的步驟350。在根據本實施例之一較佳範例中，上述步驟350之可篩選出D50約為10-30μm的顆粒。在根據本實施例之一較佳範例中，上述步驟350之可篩選出D50約為17-23μm的顆粒。 After the granulation and carbonization steps, the carbon substrate with nano-silicon embedded in the surface pores coated with the modification layer after carbonization can be disintegrated, as shown in step 340 . In a preferred example according to the present embodiment, step 340 can disintegrate the above-mentioned carbon substrate covered with the modification layer and embedded with nano-silicon in the surface pores into a plurality of small particles. According to this embodiment, after the disintegration step 340, a filtering step 350 may be performed on the disintegrated small particles. In a preferred example according to the present embodiment, the above step 350 can screen out particles with a D50 of about 10-30 μm. In a preferred example according to the present embodiment, the above step 350 can screen out particles with a D50 of about 17-23 μm.

以下將敘明根據本說明書之二次造粒之矽碳基材電池負極材料及其製備方法的較佳範例。然而，本說明書之範圍應以其後的申請專利範圍為準，而不應以下列實施範例為限。 A preferred example of the secondary granulated silicon carbon base battery negative electrode material and its preparation method according to the present specification will be described below. However, the scope of this specification should be based on the scope of the subsequent patent applications, and should not be limited by the following examples.

比較例1：Comparative Example 1:

將奈米矽粉(D50約300nm)、人造石墨(D50約14-17 μm)、以及瀝青(D50約2-5μm)在V型混合機內一次混合均勻後，轉移到管式爐中。上述奈米矽粉的添加量約為人造石墨與奈米矽粉總重量的3wt%。上述瀝青的添加量約為人造石墨與奈米矽粉總重量的7wt%。 Nano silicon powder (D50 about 300nm), artificial graphite (D50 about 14-17 μm), and pitch (D50 about 2-5 μm) were uniformly mixed once in a V-type mixer, and then transferred to a tube furnace. The added amount of the above-mentioned nano-silicon powder is about 3wt% of the total weight of the artificial graphite and the nano-silicon powder. The addition amount of the above-mentioned pitch is about 7 wt % of the total weight of artificial graphite and nano-silica.

以管式爐加熱至1000℃進行碳化。在惰性氣氛下，將管式爐從室溫以5℃/min的升溫速率升溫到1000℃，並保溫3小時。之後將管式爐內降溫回室溫，以得到矽碳複合材料。 Carbonization was performed by heating to 1000°C in a tube furnace. Under an inert atmosphere, the tube furnace was heated from room temperature to 1000°C at a heating rate of 5°C/min, and held for 3 hours. Then, the temperature in the tube furnace is returned to room temperature to obtain the silicon-carbon composite material.

比較例2：Comparative Example 2:

首先將奈米矽粉(D50約300nm)、與人造石墨(D50約14-17μm)在V型混合機內混合均勻。上述奈米矽粉的添加量約為人造石墨與奈米矽粉總重量的3wt%。 Firstly, nano silicon powder (D50 about 300nm) and artificial graphite (D50 about 14-17μm) are mixed uniformly in a V-type mixer. The added amount of the above-mentioned nano-silicon powder is about 3wt% of the total weight of the artificial graphite and the nano-silicon powder.

隨後將瀝青(D50約2-5μm)添加至上述V型混合機中，使瀝青與上述奈米矽粉與人造石墨混合均勻後，轉移到管式爐中。上述瀝青的添加量約為人造石墨與奈米矽粉總重量的7wt%。 Subsequently, the pitch (D50 about 2-5 μm) was added to the above V-type mixer, and the pitch, the above-mentioned nano-silica powder and artificial graphite were uniformly mixed, and then transferred to a tube furnace. The addition amount of the above-mentioned pitch is about 7 wt % of the total weight of artificial graphite and nano-silica.

在惰性氣氛下，將管式爐從室溫以5℃/min的升溫速率升溫到1000℃，並保溫3小時。之後將管式爐內降溫回室溫，以得到矽碳複合材料。 Under an inert atmosphere, the tube furnace was heated from room temperature to 1000°C at a heating rate of 5°C/min, and held for 3 hours. Then, the temperature in the tube furnace is returned to room temperature to obtain the silicon-carbon composite material.

比較例3：Comparative Example 3:

隨後將瀝青(D50約2-5μm)添加至上述V型混合機中，使瀝青與上述奈米矽粉與人造石墨混合均勻後，轉移到迴轉爐中。上述瀝青的添加量約為人造石墨與奈米矽粉總重量的7wt%。 Subsequently, the pitch (D50 about 2-5 μm) was added to the above V-type mixer to make the pitch, the above-mentioned nano-silica powder and artificial graphite evenly mixed, and then transferred to the rotary kiln. The addition amount of the above-mentioned pitch is about 7 wt % of the total weight of artificial graphite and nano-silica.

在惰性氣氛下，將迴轉爐從室溫以5℃/min的升溫速率升溫到1000℃，並保溫3小時。之後將迴轉爐內降溫回室溫，以得到矽碳複合材料。 Under an inert atmosphere, the rotary furnace was heated from room temperature to 1000°C at a heating rate of 5°C/min, and kept for 3 hours. Then, the temperature in the rotary furnace is returned to room temperature to obtain the silicon-carbon composite material.

範例1：Example 1:

首先將奈米矽粉(D50約300nm)、與人造石墨(D50約14-17μm)在帶有擠壓力的混合機內混合均勻，使上述奈米矽粉嵌入上述人造石墨。上述奈米矽粉的添加量約為人造石墨與奈米矽粉總重量的3wt%。 Firstly, nano silicon powder (D50 about 300nm) and artificial graphite (D50 about 14-17μm) are mixed uniformly in a mixer with extrusion force, so that the nano silicon powder is embedded in the artificial graphite. The added amount of the above-mentioned nano-silicon powder is about 3wt% of the total weight of the artificial graphite and the nano-silicon powder.

範例1所得到之矽碳複合材料，由於奈米矽粉擠壓嵌入於人造石墨的表面，加上有修飾層(瀝青)包覆於表面孔隙嵌有奈米矽粉的人造石墨上。所以，在範例1所得到的矽碳複合材料將不會發現從人造石墨脫落下來的奈米矽粉。另一方面，由於有了修飾層的包覆，上述矽碳複合材料應用於電池之後，在充放電的過程中，也將不易因為膨脹而出現破裂或奈米矽粉逸出的現象。 The silicon-carbon composite material obtained in Example 1, because the nano-silica powder is extruded and embedded on the surface of the artificial graphite, and a modified layer (pitch) is added to coat the artificial graphite with the nano-silica powder embedded in the surface pores. Therefore, the silicon-carbon composite material obtained in Example 1 will not find nano-silica powder falling off the artificial graphite. On the other hand, since there are In order to cover the modification layer, after the above-mentioned silicon-carbon composite material is applied to the battery, during the charging and discharging process, the phenomenon of cracking or nano-silicon powder escaping due to expansion will not occur easily.

上述比較例1-3與範例1所製得之矽碳複合材料之性質可整理如下表一。 The properties of the silicon-carbon composites prepared in Comparative Examples 1-3 and Example 1 can be summarized in Table 1 below.

由表一可看出，雖然比較例1-3與範例1所得到的矽碳複合材料經解碎過篩後，所得到材料粒徑相似，但範例1所得到矽碳複合材料具有最低的比表面積。說明根據範例1的作法，瀝青又對矽碳複合材料發揮最佳的包覆效果，從而減少了表面孔隙。再者，由表一也可發現，範例1所得到之矽碳複合材料中，由矽材料氧化殘留即灰分值較高。上述灰分值說明擠壓入石墨後，矽粉可以更穩固存在於石墨表面。 It can be seen from Table 1 that although the silicon-carbon composite materials obtained in Comparative Examples 1-3 and Example 1 have similar particle sizes after being crushed and sieved, the silicon-carbon composite material obtained in Example 1 has the lowest ratio. surface area. It is explained that according to the practice of Example 1, the asphalt has the best coating effect on the silicon-carbon composite, thereby reducing the surface porosity. Furthermore, it can also be found from Table 1 that in the silicon-carbon composite material obtained in Example 1, the ash content is higher due to the oxidation residue of the silicon material. The above ash content indicates that after extruding graphite, silicon powder can more firmly exist on the surface of graphite.

範例2：扣式電池測試Example 2: Button Cell Test

將上述比較例1-3與範例1所得之矽碳複合材料用作負極材料，並分別組裝成扣式電池，以進行CR2032扣式半電測試。上述扣式電池的組裝方式與CR2032扣式半電測試過程簡述如下。 The silicon-carbon composite materials obtained in the above Comparative Examples 1-3 and Example 1 were used as negative electrode materials, and were assembled into coin-type batteries respectively to conduct CR2032 coin-type semi-electric tests. The assembly method of the above button battery and the CR2032 button half battery test process are briefly described as follows Down.

將比較例1-3和範例1中所得之矽碳複合材料、導電劑、基底粘結劑、分散劑和溶劑在行星攪拌機中攪拌3小時，以得到混合均勻的漿料。以自動塗膜機將上述漿料均勻塗佈到銅箔集流體上，塗佈厚度約為200μm。在60℃下鼓風乾燥30分鐘後，放置於真空乾燥箱中，使其在120℃真空乾燥12小時，以得到負極極片。上述基底粘結劑為丁苯橡膠(SBR)，分散劑為羧甲基纖維素鈉(CMC)，導電劑超級碳黑(SP)。上述負極材料、SP、CMC、與SBR的重量比約為負極材料：SP：CMC：SBR=94.5：2：1.5：2。扣式電池採用的電解液為1M的LiPF₆[in EC：DMC：EMC(1：1：1 vol.%)with 3wt.% FEC]，金屬鋰片為對電極，隔膜採用聚丙烯(PP)微孔膜。 The silicon-carbon composite material, conductive agent, base binder, dispersant and solvent obtained in Comparative Examples 1-3 and Example 1 were stirred in a planetary mixer for 3 hours to obtain a uniformly mixed slurry. The above slurry was uniformly coated on the copper foil current collector with an automatic film coating machine, and the coating thickness was about 200 μm. After drying by blowing at 60° C. for 30 minutes, it was placed in a vacuum drying oven and vacuum-dried at 120° C. for 12 hours to obtain a negative electrode piece. The above-mentioned base binder is styrene-butadiene rubber (SBR), the dispersant is sodium carboxymethyl cellulose (CMC), and the conductive agent is super carbon black (SP). The weight ratio of the negative electrode material, SP, CMC, and SBR is about negative electrode material: SP:CMC:SBR=94.5:2:1.5:2. The electrolyte used in the button battery is 1M LiPF ₆ [in EC:DMC:EMC(1:1:1 vol.%)with 3wt.% FEC], the metal lithium sheet is the counter electrode, and the separator is polypropylene (PP) Microporous membrane.

將最終得到的負極片用沖孔機進行裁片，以得到直徑為12mm的電極片。然後將電極片轉移到充滿氬氣的超級淨化手套箱中，進行CR2032扣式半電池的組裝。 The finally obtained negative electrode sheet was cut with a punching machine to obtain an electrode sheet with a diameter of 12 mm. The electrode sheets were then transferred into an argon-filled super-purified glove box for the assembly of CR2032 coin-type half-cells.

CR2032扣式半電池的組裝之大致操作流程如后。將電極片放置於正極殼的中央，在上面滴加電解液，使電極片完全浸潤。將隔膜平整地放置在極片上，再滴加電解液，使隔膜完全浸潤。將鋰片作為對電極放置在隔膜上。將上述墊片、彈片依序放置在鋰片上，使其處於電池的中心位置，再將負極殼扣上。再使用封裝機進行加壓封裝，以得到CR2032扣式半電池。 The general operation process of CR2032 coin-type half-cell assembly is as follows. The electrode sheet is placed in the center of the positive electrode case, and the electrolyte is dropped on it to completely soak the electrode sheet. Place the diaphragm flat on the pole piece, and then add the electrolyte dropwise to make the diaphragm completely infiltrated. A lithium sheet was placed on the separator as a counter electrode. Place the above-mentioned gaskets and shrapnel on the lithium sheet in order so that they are in the center of the battery, and then buckle the negative electrode shell. Then use a packaging machine to carry out pressure packaging to obtain a CR2032 coin-type half-cell.

將上述封裝完成的CR2032扣式半電池擱置12小時後即可開始進行測試。上述CR2032扣式半電池可使用藍電電池測試系統在0.005-2.0V的電壓範圍下以0.1C的電流密度對電池進行恒電流充放電迴圈測試。50次的充放電迴圈測試結果如第四圖所示。第四圖是將上述比較例1-3與範例1所得之矽碳複合材料用作負極材料依據本範例進行50次的充放電迴圈測試的電池循環測試之比較圖。其中，X軸為循環測試圈數；Y軸為比容量，單位為mAh/g。 The CR2032 coin-type half-cell that has been encapsulated above can be put on hold for 12 hours before the test can be started. The above CR2032 coin-type half-cell can be tested with a blue battery test system at a current density of 0.1C under a voltage range of 0.005-2.0V. Constant current charge and discharge loop test. The results of the 50-time charge-discharge cycle test are shown in the fourth figure. The fourth figure is a comparison chart of the battery cycle test performed 50 times of charge-discharge cycle test according to this example using the silicon-carbon composite materials obtained in the above Comparative Examples 1-3 and Example 1 as the negative electrode material. Among them, the X-axis is the number of cycles of the cycle test; the Y-axis is the specific capacity, in mAh/g.

由第四圖可看出，比較例2的測試結果相較於比較例1更好。上述比較說明了，先將奈米矽粉與人造石墨混合的操作方式，可讓奈米矽粉均勻沾附於人造石墨表面。先混合奈米矽粉與人造石墨之後再添加瀝青，再經過加熱碳化所得到的矽碳複合材料可發揮出較佳性能。同時由第四圖也可發現，雖然比較例3前十次迴圈測試結果較差，但整體迴圈保持率優於比較例2。這是因為僅以普通混合方式，矽粉不能穩固存在於石墨表面。在動態的迴轉爐進行碳化過程雖然可得到較佳的瀝青包覆与造粒效果，但是因為部分矽粉已經由石墨上脫落並團聚，而脫落並團聚的矽粉造成測試中的迴圈性能衰減迅速。另一方面，由第四圖也可發現，範例1的測試結果又遠比使用比較例1-3更優越。亦即，在混合奈米矽粉與人造石墨時，如加上外力擠壓，使奈米矽粉擠壓嵌入至人造石墨的表面，所得到的矽碳複合材料應用於電池負極時，更可進一步提昇電池的循環性能。 It can be seen from the fourth figure that the test result of Comparative Example 2 is better than that of Comparative Example 1. The above comparison shows that the operation method of mixing nano-silicon powder and artificial graphite first can make the nano-silicon powder evenly adhere to the surface of artificial graphite. The silicon-carbon composite material obtained by mixing nano-silicon powder and artificial graphite first, then adding pitch, and then heating and carbonizing can exert better performance. At the same time, it can also be found from the fourth figure that although the first ten lap test results of Comparative Example 3 are poor, the overall lap retention rate is better than that of Comparative Example 2. This is because the silica powder cannot exist firmly on the graphite surface only by the ordinary mixing method. Although the carbonization process in a dynamic rotary kiln can obtain better asphalt coating and granulation effects, because part of the silicon powder has fallen off and agglomerated from the graphite, and the falling off and agglomerated silicon powder will cause the cycle performance to decline in the test. fast. On the other hand, it can also be found from the fourth figure that the test results of Example 1 are far superior to those of Comparative Examples 1-3. That is, when mixing nano-silicon powder and artificial graphite, if an external force is applied to extrude, the nano-silicon powder is extruded and embedded on the surface of artificial graphite, and the obtained silicon-carbon composite material can be used in the negative electrode of battery. Further improve the cycle performance of the battery.

上述比較例1-3與範例1所製得之矽碳複合材料依據本範例進行電池循環測試的結果可整理如下表二。 The results of the battery cycle test of the silicon-carbon composite materials prepared in the above Comparative Examples 1-3 and Example 1 according to this example can be summarized in Table 2 below.

由表二可看出，由於添加了奈米矽粉，比較例1-3與範例1的克容量均比石墨大幅提升(石墨的克容量理論值是372mAh/g)。更好的是，範例1的庫倫效率又優於比較例1-3。 It can be seen from Table 2 that due to the addition of nano-silicon powder, the gram capacity of Comparative Examples 1-3 and Example 1 is significantly higher than that of graphite (the theoretical value of gram capacity of graphite is 372mAh/g). Even better, the Coulombic efficiency of Example 1 is better than that of Comparative Examples 1-3.

範例3：全電池測試之電池性能比較Example 3: Battery performance comparison of full battery test

將上述比較例與範例所得之矽碳複合材料用作負極材料，並分別和523型正極三元材料組裝成軟包電池，以進行全電池測試。上述軟包電池的組裝方式與全電池測試過程簡述如下。 The silicon-carbon composite materials obtained in the above comparative examples and examples were used as negative electrode materials, and were assembled with 523-type positive ternary materials to form soft-pack batteries for full battery testing. The assembly method and full battery testing process of the above-mentioned soft pack battery are briefly described as follows.

將聚偏氟乙烯(PVDF)與N-甲基-2-吡咯烷酮(NMP)在行星攪拌機中混合均勻以製成膠液。然後，在上述膠液中加入超級碳黑(SP)並混合均勻以製成導電膠液。在上述導電膠液裡加入正極活性物質523型三元材料，並在行星攪拌機中攪拌4小時，使其混合均勻以製得正極漿料。再以NMP將上述正極漿料的粘度調節至8000±2000cp，以得到流動性良好的正極漿料。之後，將上述流動性良好的正極漿液均勻塗布在鋁箔的兩面再經過乾燥、輥壓、分切、模切等工藝後，可得到正極片。最後，將上述正極片放入烘箱，進行真空乾燥後待用。其中，上述523型三元材料、導電劑、以及粘結劑的重量比約為，523型三元材料：導電劑：粘結劑=95：2：3。 Polyvinylidene fluoride (PVDF) and N-methyl-2-pyrrolidone (NMP) were mixed well in a planetary mixer to make a glue solution. Then, super carbon black (SP) was added to the above glue solution and mixed well to make conductive glue solution. The positive electrode active material 523 type ternary material was added to the above conductive glue solution, and stirred in a planetary mixer for 4 hours to make it evenly mixed to prepare a positive electrode slurry. Then, the viscosity of the positive electrode slurry was adjusted to 8000±2000 cp with NMP to obtain a positive electrode slurry with good fluidity. After that, the positive electrode slurry with good fluidity is uniformly coated on both sides of the aluminum foil, and the positive electrode sheet can be obtained after drying, rolling, slitting, die-cutting and other processes. Finally, will The above-mentioned positive electrode sheet is put into an oven, and vacuum-dried for later use. Among them, the weight ratio of the above-mentioned 523-type ternary material, conductive agent, and binder is about, 523-type ternary material: conductive agent: binder=95:2:3.

將CMC與蒸餾水在行星攪拌機上混合均勻製成膠液。然後，在上述膠液中加入SP，並均勻混合，以製成導電膠液。將比較例1-3和範例1中所得負極材料(矽碳複合材料)分別加入到上述的導電膠液中，並予以均勻混合，以製得負極漿料。最後，使用蒸餾水將上述負極漿料的粘度調節至2000±500cp，以得到流動性良好的負極漿料。將上述流動性良好的負極漿液均勻塗佈在銅箔的兩面，並經過乾燥、輥壓、分切、模切等工藝後，即可得到負極片。最後，將上述負極片放入烘箱，並進行真空乾燥後待用。其中，上述負極材料、SP、CMC、與SBR之重量比約為，負極材料：SP：CMC：SBR=94.5：2：1.5：2。 Mix CMC and distilled water on a planetary mixer to make a glue solution. Then, SP is added to the above glue solution and mixed uniformly to make a conductive glue solution. The negative electrode materials (silicon-carbon composite materials) obtained in Comparative Examples 1-3 and Example 1 were respectively added to the above-mentioned conductive glue solution and mixed uniformly to prepare negative electrode slurry. Finally, the viscosity of the negative electrode slurry was adjusted to 2000±500 cp using distilled water to obtain a negative electrode slurry with good fluidity. The negative electrode slurry with good fluidity is uniformly coated on both sides of the copper foil, and the negative electrode sheet can be obtained after drying, rolling, slitting, die-cutting and other processes. Finally, the above-mentioned negative electrode sheet is put into an oven, and vacuum-dried for later use. Wherein, the weight ratio of the negative electrode material, SP, CMC, and SBR is about, negative electrode material: SP:CMC:SBR=94.5:2:1.5:2.

將前述的負極片、隔膜(聚丙烯微孔膜)、正極片裝入疊片機中進行疊片，以得到裸電芯。上述裸電芯經鋁塑膜封裝，再經過真空烘烤、注液[1M LiPF₆ in EC：DMC：EMC(1：1：1 vol.%)with 3wt.% FEC]、封裝、靜置等步驟後，即可得到鋰離子二次電池。上述二次電池可在0.5C充電/1C放電，電壓範圍3.0V-4.2V，室溫條件下進行能量密度測試，以及在室溫或45℃條件下進行迴圈穩定性測試。全電池1000次循環充放電迴圈測試的結果如第五圖所示。第五圖是將上述比較例1-3與範例1所得之矽碳複合材料用作負極材料依據本範例進行1000次循環充放電迴圈測試的電池循環測試之比較圖。其中，X軸為循環測試圈數；Y軸為保持率。 The aforementioned negative electrode sheet, separator (polypropylene microporous membrane), and positive electrode sheet are loaded into a lamination machine for lamination to obtain a bare cell. The above bare cells are encapsulated by aluminum plastic film, and then vacuum baked, liquid injected [1M LiPF ₆ in EC:DMC:EMC(1:1:1 vol.%)with 3wt.% FEC], encapsulated, left to stand, etc. After the steps, a lithium ion secondary battery can be obtained. The above secondary battery can be charged at 0.5C/discharged at 1C, with a voltage range of 3.0V-4.2V, for energy density tests at room temperature, and for loop stability tests at room temperature or 45°C. The results of the 1000-cycle charge-discharge cycle test of the full battery are shown in Figure 5. Figure 5 is a comparison diagram of the battery cycle test performed according to this example using the silicon carbon composite materials obtained in Comparative Examples 1-3 and Example 1 as negative electrode materials to perform 1000-cycle charge-discharge cycle tests. Among them, the X-axis is the number of cyclic test cycles; the Y-axis is the retention rate.

由第五圖可看出，範例1的測試結果又遠比使用比較例1-3所得到的矽碳複合材料所製成之扣式電池更優越。在經過1000次循環充放電之後，比較例1-2的保持率皆大幅下降，而比較例3的保持率約70%。更好的是，經過1000次循環充放電之後，範例1的保持率仍可維持約80%。 It can be seen from Figure 5 that the test results of Example 1 are far superior to the coin cells made by using the silicon-carbon composite materials obtained in Comparative Examples 1-3. After 1000 cycles of charge and discharge, the retention rates of Comparative Examples 1-2 all dropped significantly, while the retention rate of Comparative Example 3 was about 70%. Even better, after 1000 charge-discharge cycles, the retention rate of Example 1 can still be maintained at about 80%.

綜上所述，本說明書揭露一種二次造粒之矽碳基材電池負極材料及其製備方法。上述二次造粒之矽碳基材電池負極材料包含碳基材、複數個奈米矽、以及修飾層。上述的複數個奈米矽可以是分別嵌入於上述碳基材的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。在根據本說明書之一較佳範例中，上述的複數個奈米矽可以是分別擠壓嵌入於上述碳基材的表面孔隙，以形成表面孔隙嵌有奈米矽的碳基材。上述的修飾層可以是包覆於上述表面孔隙嵌有奈米矽的碳基材之上。在根據本說明書之一較佳範例中，複數個包覆有修飾層之表面孔隙嵌有奈米矽的碳基材可堆疊成一碳基材集合。上述二次造粒之矽碳基材電池負極結構之製備方法包含混合奈米矽與碳基材、添加黏合劑、造粒與碳化、解碎、以及過篩等步驟。在根據本說明書之一較佳範例中，上述混合碳基材與奈米矽的步驟更包含將奈米矽擠壓嵌入碳基材的步驟，以形成表面孔隙嵌有奈米矽的碳基材。根據本說明書之技術方案，藉由奈米矽與修飾層的使用，不僅可大幅提昇電池調漿時的均勻性與負極材料的滲液性，更好的是，上述二次造粒之矽碳基材電池負極材料及其製備方法相較於現有矽碳基材電池負極材料可有效提昇電池的循環性能、以及穩定性，進而可有效提昇產業競爭力之效果。 To sum up, this specification discloses a secondary granulated silicon carbon substrate battery negative electrode material and a preparation method thereof. The above-mentioned secondary granulated silicon carbon base battery negative electrode material includes a carbon base material, a plurality of nano-silicon, and a modification layer. The plurality of nano-silicons can be respectively embedded in the surface pores of the carbon substrate to form a carbon substrate with nano-silicon embedded in the surface pores. In a preferred example according to the present specification, the plurality of nano-silicons can be respectively extruded and embedded in the surface pores of the carbon substrate to form a carbon substrate with nano-silicon embedded in the surface pores. The above-mentioned modification layer may be coated on the above-mentioned carbon substrate with surface pores embedded with nano-silicon. In a preferred example according to the present specification, a plurality of carbon substrates coated with modified layers and with nano-silicon embedded in the surface pores can be stacked to form a carbon substrate set. The preparation method of the secondary granulated silicon carbon substrate battery negative electrode structure includes the steps of mixing nano-silicon and carbon substrate, adding a binder, granulating and carbonizing, disintegrating, and sieving. In a preferred example according to the present specification, the step of mixing the carbon substrate and the nano-silicon further includes the step of extruding the nano-silicon into the carbon substrate, so as to form a carbon substrate with surface pores embedded in the nano-silicon . According to the technical solution in this specification, the use of nano-silicon and the modified layer can not only greatly improve the uniformity of the battery and the liquid permeability of the negative electrode material during slurry mixing, but also better, the above-mentioned secondary granulation silicon carbon base Compared with the existing negative electrode materials of silicon carbon substrate batteries, the battery anode material and its preparation method can effectively improve the cycle performance and stability of the battery, and thus can effectively improve the production capacity. The effect of industry competitiveness.

顯然地，依照上面體系中的描述，本發明可能有許多的修正與差異。因此需要在其附加的權利要求項之範圍內加以理解，除了上述詳細的描述外，本發明還可以廣泛地在其他的體系中施行。上述僅為本發明之較佳體系而已，並非用以限定本發明之申請專利範圍；凡其它未脫離本發明所揭示之精神下所完成的等效改變或修飾，均應包含在下述申請專利範圍內。 Obviously, many modifications and variations of the present invention are possible in light of the description in the above system. It is therefore to be understood within the scope of the appended claims that the invention is broadly applicable to other systems than those detailed above. The above is only the preferred system of the present invention, and is not intended to limit the scope of the patent application of the present invention; all other equivalent changes or modifications completed without departing from the spirit disclosed in the present invention should be included in the following patent application scope Inside.

200:二次造粒矽之碳基材電池負極材料 200: Carbon-based battery negative electrode material of secondary granulated silicon

220:碳基材 220: carbon substrate

240:奈米矽 240: Nano Silicon

260:修飾層 260: Retouch layer

Claims

一種二次造粒之矽碳基材電池負極材料，其係由：一碳基材；複數個奈米矽，上述奈米矽分別擠壓嵌入於上述碳基材之表面孔隙，形成表面孔隙嵌有奈米矽的碳基材；以及一修飾層所構成，上述修飾層包覆於上述表面孔隙嵌有奈米矽的碳基材之上。 A secondary granulated silicon carbon substrate battery negative electrode material, which is composed of: a carbon substrate; a plurality of nano-silicons, the nano-silicons are respectively extruded and embedded in the surface pores of the carbon substrate to form surface pores embedded A carbon substrate with nano-silicon; and a modification layer, the modification layer is coated on the carbon substrate with nano-silicon embedded in the surface pores.

根據申請專利範圍第1項之二次造粒之矽碳基材電池負極材料，其中上述碳基材係選自下列群組之一者或其組合：天然石墨、人造石墨、石墨烯、奈米碳管(CNT)、以及氣相成長碳纖維(VGCF)、中間相碳微球材料(MCMB)。 According to the second granulated silicon-carbon base battery negative electrode material in the first item of the patent application scope, the carbon base material is selected from one of the following groups or a combination thereof: natural graphite, artificial graphite, graphene, nanometer Carbon tube (CNT), vapor grown carbon fiber (VGCF), and mesocarbon microsphere material (MCMB).

根據申請專利範圍第1項之二次造粒之矽碳基材電池負極材料，其中上述修飾層包含黏合劑，其中上述黏合劑係選自下列群組之一者或其組合：瀝青、酚醛樹酯。 According to the second granulated silicon carbon base battery negative electrode material of the first claim, wherein the modification layer comprises a binder, wherein the binder is selected from one of the following groups or a combination thereof: pitch, phenolic tree ester.

根據申請專利範圍第1項之二次造粒之矽碳基材電池負極材料，其中複數個上述包覆有修飾層之表面孔隙嵌有奈米矽的碳基材可堆疊成一碳基材集合。 According to the secondary granulated silicon-carbon base battery negative electrode material of the first claim, a plurality of the above-mentioned carbon base materials with nano-silicon embedded in the surface pores covered with the modification layer can be stacked to form a carbon base material set.

一種二次造粒之矽碳基材電池負極材料之製備方法，其包含：混合碳基材與奈米矽，和將該奈米矽擠壓嵌入該碳基材，以形成表面孔隙嵌有奈米矽的碳基材；將黏合劑添加至上述表面孔隙嵌有奈米矽的碳基材，以得到表面孔隙嵌有奈米矽的碳基材與黏合劑之混合物；對上述混合物進行造粒與碳化，其中上述混合物在升溫過程中形成複數個包覆有修飾層之表面孔隙嵌有奈米矽的碳基材，並在造粒與碳化步驟中形成碳化後的包覆有修飾層之表面孔隙嵌有奈米矽的碳基材；對碳化後的包覆有修飾層之表面孔隙嵌有奈米矽的碳基材進行解碎；以及對解碎後的包覆有修飾層之表面孔隙嵌有奈米矽的碳基材進行過篩。 A preparation method of a secondary granulated silicon carbon base material for battery negative electrode material, comprising: mixing a carbon base material and nano-silicon, and extruding the nano-silicon into the carbon base material to form surface pores embedded with nano-silicon A carbon substrate of nano-silicon; adding a binder to the carbon substrate with nano-silicon embedded in the surface pores to obtain A mixture of a carbon substrate with nano-silicon embedded in the surface pores and a binder; the above-mentioned mixture is granulated and carbonized, wherein the above-mentioned mixture forms a plurality of surface pores covered with a modified layer during the heating process. A carbon substrate, and in the granulation and carbonization steps, a carbon substrate with nano-silicon embedded in the surface pores of the carbonized coating covered with the modified layer is formed; the surface pores of the carbonized coated with the modified layer are embedded with nanometer The silicon carbon substrate is disintegrated; and the disintegrated carbon substrate covered with the modification layer and the surface pores embedded with nano-silicon is screened.

根據申請專利範圍第5項之二次造粒之矽碳基材電池負極材料之製備方法，其中上述奈米矽之佔比為0.1-20wt%之碳基材。 According to item 5 of the scope of the patent application, the preparation method of the negative electrode material of the secondary granulated silicon-carbon base battery, wherein the proportion of the above-mentioned nano-silicon is 0.1-20wt% of the carbon base material.

根據申請專利範圍第5項之二次造粒之矽碳基材電池負極材料之製備方法，其中上述黏合劑之重量比約為表面孔隙嵌有奈米矽的碳基材之5-15wt%。 According to item 5 of the scope of the patent application, the method for preparing a negative electrode material of a silicon-carbon base battery by secondary granulation, wherein the weight ratio of the binder is about 5-15wt% of the carbon base material whose surface pores are embedded with nano-silicon.

根據申請專利範圍第5項之二次造粒之矽碳基材電池負極材料之製備方法，其中造粒與碳化步驟係在迴轉爐中完成。 According to item 5 of the scope of the patent application, the method for preparing a negative electrode material for a silicon carbon base battery by secondary granulation, wherein the steps of granulation and carbonization are completed in a rotary kiln.