TWI751055B - Silicon-carbon composite material for lithium ion battery, method of manufacturing the same and electrode for lithium ion battery - Google Patents
Silicon-carbon composite material for lithium ion battery, method of manufacturing the same and electrode for lithium ion battery Download PDFInfo
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Abstract
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本發明係有關於一種鋰離子電池用矽碳複合材料、其製造方法及鋰離子電池用電極，且特別是有關於一種可提升電極電容量及電池循環壽命之鋰離子電池用矽碳複合材料。The present invention relates to a silicon-carbon composite material for lithium ion batteries, a manufacturing method thereof, and an electrode for lithium ion batteries, and in particular, to a silicon-carbon composite material for lithium ion batteries that can improve electrode capacity and battery cycle life.
電池係將化學能或物理能直接變成電能的儲能裝置，且依據放電特性及工作性質，可大致分成一次電池(primary cell)及二次電池(secondary cell)。舉例而言，一次電池包含碳鋅電池、鹼性電池和鋰錳電池，而二次電池包含鋰離子電池、鉛酸電池和鎳氫電池。A battery is an energy storage device that directly converts chemical energy or physical energy into electrical energy, and can be roughly divided into primary cells and secondary cells according to discharge characteristics and working properties. For example, primary batteries include carbon-zinc batteries, alkaline batteries, and lithium-manganese batteries, and secondary batteries include lithium-ion batteries, lead-acid batteries, and nickel-metal hydride batteries.
就鋰離子電池而言，於充電時(即外加電壓時)，鋰離子從正極脫出，並經由電解液傳輸並嵌入負極。此時正極處於貧鋰狀態，負極則處於富鋰狀態。同時電子的補償電荷從正極經由外部迴路流向負極，以確保電荷平衡。於放電時，鋰離子由負極嵌出，經由電解液傳輸並進入正極，電子亦由負極釋出而流向正極。藉由鋰離子於正負兩極間來回地嵌入與嵌出，鋰離子電池進行可逆的電化學氧化還原反應，以反覆地充放電。For lithium-ion batteries, during charging (ie, when a voltage is applied), lithium ions are extracted from the positive electrode, transported through the electrolyte, and intercalated into the negative electrode. At this time, the positive electrode is in a lithium-poor state, and the negative electrode is in a lithium-rich state. At the same time, the compensation charge of the electrons flows from the positive electrode to the negative electrode via the external loop to ensure charge balance. During discharge, lithium ions are intercalated from the negative electrode, transported through the electrolyte and enter the positive electrode, and electrons are also released from the negative electrode and flow to the positive electrode. By intercalating and intercalating lithium ions back and forth between the positive and negative electrodes, the lithium ion battery undergoes a reversible electrochemical redox reaction to repeatedly charge and discharge.
目前，最普遍用於鋰離子電池的負極材料為石墨，且其電容量實測值已接近理論值(372mAh/g)。惟隨著電子產品及電動車之高性能化，鋰離子電池之電容量的要求亦逐漸提高。因此，需要導入電容量更高的負極材料，以提升全電池電容量。更高電容量的負極材料可包含純矽材料。當矽材料形成Li 15Si 4合金相時，理論重量電容量為3580mAh/g，而當其於高溫下形成Li 22Si 5合金相時，理論重量電容量更高達4200mAh/g。 At present, the most commonly used anode material for lithium-ion batteries is graphite, and the measured value of its capacitance is close to the theoretical value (372mAh/g). However, with the high performance of electronic products and electric vehicles, the requirements for the electric capacity of lithium-ion batteries are gradually increasing. Therefore, it is necessary to introduce anode materials with higher electric capacity to improve the electric capacity of the whole battery. Higher capacity anode materials may include pure silicon materials. When the silicon material forms the Li 15 Si 4 alloy phase, the theoretical gravimetric capacitance is 3580mAh/g, and when it forms the Li 22 Si 5 alloy phase at high temperature, the theoretical gravimetric capacitance is even higher than 4200mAh/g.
然而，於充放電過程中，導入矽材料的負極材料具有顯著之體積膨脹效應(例如：體積變化率為280%)，而易使矽材料的顆粒粉碎化，進而降低電池的循環壽命，並且在經過500次充放電後，其電容量維持率為小於75%。However, in the process of charging and discharging, the negative electrode material introduced with silicon material has a significant volume expansion effect (for example, the volume change rate is 280%), and the particles of the silicon material are easily pulverized, thereby reducing the cycle life of the battery. After 500 times of charge and discharge, the capacity retention rate is less than 75%.
有鑑於此，亟需發展一種新的鋰離子電池用矽碳複合材料、其製造方法及鋰離子電池用電極，以改善習知鋰離子電池之負極材料的上述缺點。In view of this, there is an urgent need to develop a new silicon-carbon composite material for lithium ion batteries, a method for manufacturing the same, and an electrode for lithium ion batteries, so as to improve the above-mentioned shortcomings of conventional negative electrode materials for lithium ion batteries.
有鑑於上述之問題，本發明之一態樣是在提供一種鋰離子電池用矽碳複合材料之製造方法。藉由特定粒徑之矽顆粒及特定軟化溫度之煤焦油系列瀝青，所製得之鋰離子電池用矽碳複合材料可抑制矽顆粒於充放電過程中粉碎化，從而提升電極的電容量及電池的循環壽命。In view of the above problems, one aspect of the present invention is to provide a method for manufacturing a silicon-carbon composite material for lithium ion batteries. The silicon-carbon composite material for lithium ion batteries can be inhibited from pulverizing silicon particles during charging and discharging by using silicon particles with a specific particle size and coal tar series pitch with a specific softening temperature, thereby improving the electric capacity of the electrode and the battery. cycle life.
本發明之另一態樣是在提供一種鋰離子電池用矽碳複合材料，其係利用前述之製造方法所製得。Another aspect of the present invention is to provide a silicon-carbon composite material for a lithium ion battery, which is prepared by the aforementioned manufacturing method.
本發明之又一態樣是在提供一種鋰離子電池用電極。此鋰離子電池用電極包含由前述之鋰離子電池用矽碳複合材料所形成之導電層，故所製得之電池具有較高的電容量與較佳的循環壽命。Another aspect of the present invention is to provide an electrode for a lithium ion battery. The electrode for lithium ion battery includes a conductive layer formed from the aforementioned silicon-carbon composite material for lithium ion battery, so the obtained battery has higher electric capacity and better cycle life.
根據本發明之一態樣，提出一種鋰離子電池用矽碳複合材料之製造方法。此製造方法係先使用煤焦油系列瀝青對矽顆粒進行包覆步驟，以獲得瀝青包覆顆粒，其中矽顆粒之平均粒徑為小於50nm，且煤焦油系列瀝青之軟化溫度為80℃至320℃。接著，對瀝青包覆顆粒進行碳化步驟，以獲得矽碳複合顆粒。然後，對矽碳複合顆粒進行破碎步驟，以製得鋰離子電池用矽碳複合材料。According to an aspect of the present invention, a method for manufacturing a silicon-carbon composite material for a lithium ion battery is provided. In this manufacturing method, the silicon particles are first coated with coal tar series pitch to obtain the asphalt coated particles, wherein the average particle size of the silicon particles is less than 50nm, and the softening temperature of the coal tar series pitch is 80°C to 320°C . Next, a carbonization step is performed on the pitch-coated particles to obtain silicon-carbon composite particles. Then, a crushing step is performed on the silicon-carbon composite particles to obtain a silicon-carbon composite material for lithium ion batteries.
依據本發明之一實施例，基於煤焦油系列瀝青之重量為100重量百分比，煤焦油系列瀝青之固定碳比例為50重量百分比至80重量百分比。According to an embodiment of the present invention, based on the weight of the coal tar series pitch being 100 weight percent, the fixed carbon ratio of the coal tar series pitch is 50 weight percent to 80 weight percent.
依據本發明之另一實施例，煤焦油系列瀝青與矽顆粒之重量比為0.2：1至1：1。According to another embodiment of the present invention, the weight ratio of coal tar series pitch and silicon particles is 0.2:1 to 1:1.
依據本發明之又一實施例，碳化步驟之碳化溫度為700℃至1100℃。According to another embodiment of the present invention, the carbonization temperature of the carbonization step is 700°C to 1100°C.
依據本發明之再一實施例，在進行包覆步驟前，製造方法選擇性包含進行研磨步驟，其中研磨步驟包含使用溶劑對矽微粒進行研磨，以獲得矽顆粒，其中溶劑之沸點為80℃至300℃。According to yet another embodiment of the present invention, before the coating step, the manufacturing method optionally includes a grinding step, wherein the grinding step includes using a solvent to grind the silicon particles to obtain the silicon particles, wherein the boiling point of the solvent is 80° C. to 300°C.
根據本發明之另一態樣，提出一種鋰離子電池用矽碳複合材料。此鋰離子電池用矽碳複合材料係利用前述之鋰離子電池用矽碳複合材料之製造方法所製得，其中基於鋰離子電池用矽碳複合材料之重量為100重量百分比，矽的含量為50重量百分比至80重量百分比。According to another aspect of the present invention, a silicon-carbon composite material for lithium ion batteries is provided. The silicon-carbon composite material for lithium-ion batteries is prepared by the aforementioned manufacturing method of silicon-carbon composite materials for lithium-ion batteries, wherein the weight of the silicon-carbon composite material for lithium-ion batteries is 100% by weight, and the content of silicon is 50%. Weight percent to 80 weight percent.
依據本發明之一實施例，鋰離子電池用矽碳複合材料之平均粒徑(D 50)為4μm至8μm。 According to an embodiment of the present invention, the average particle size (D 50 ) of the silicon-carbon composite material for a lithium ion battery is 4 μm to 8 μm.
根據本發明之又一態樣，提出一種鋰離子電池用電極，其包含導電基材及設置於導電基材上之導電層。此導電層包含活性物質、導電輔助材料及黏結劑。According to another aspect of the present invention, an electrode for a lithium ion battery is provided, which includes a conductive substrate and a conductive layer disposed on the conductive substrate. The conductive layer includes active substances, conductive auxiliary materials and binders.
依據本發明之另一實施例，基於導電層之重量為100重量百分比，鋰離子電池用矽碳複合材料之使用量為10重量百分比至15重量百分比。According to another embodiment of the present invention, based on the weight of the conductive layer being 100 weight percent, the usage amount of the silicon-carbon composite material for lithium ion battery is 10 weight percent to 15 weight percent.
依據本發明之另一實施例，基於導電層之重量為100重量百分比，黏結劑之使用量為4重量百分比至5重量百分比。According to another embodiment of the present invention, based on the weight of the conductive layer being 100% by weight, the amount of the adhesive used is 4% by weight to 5% by weight.
應用本發明之鋰離子電池用矽碳複合材料之製造方法，其中藉由特定粒徑之矽顆粒及特定軟化溫度之煤焦油系列瀝青，所製造之鋰離子電池用矽碳複合材料可抑制矽顆粒於充放電過程中粉碎化，從而提升電極的電容量及電池的循環壽命。Applying the manufacturing method of the silicon-carbon composite material for lithium-ion battery of the present invention, the silicon-carbon composite material for lithium-ion battery can suppress the silicon particles by using silicon particles of a specific particle size and coal tar series pitch of a specific softening temperature. It is pulverized during the charging and discharging process, thereby improving the electric capacity of the electrode and the cycle life of the battery.
以下仔細討論本發明實施例之製造和使用。然而，可以理解的是，實施例提供許多可應用的發明概念，其可實施於各式各樣的特定內容中。所討論之特定實施例僅供說明，並非用以限定本發明之範圍。The manufacture and use of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are provided for illustration only, and are not intended to limit the scope of the invention.
本發明之鋰離子電池用矽碳複合負極材料之製造方法係藉由縮小矽顆粒的平均粒徑，以降低矽顆粒與鋰矽合金間的應變差異，進而抑制矽顆粒於充放電過程中粉碎化。其次，矽顆粒之平均粒徑愈小，鋰離子擴散路徑愈短，而電容量的效果愈容易完全地呈現。再者，此製造方法利用碳層包覆技術(即於包覆瀝青之矽顆粒經碳化後，瀝青可形成碳層)，以提高材料導電度，並減少矽與電解液直接接觸發生副反應，而產生過多的固態電解質界面層，從而提升電極的電容量且增長電池的循環壽命。The manufacturing method of the silicon-carbon composite negative electrode material for lithium ion batteries of the present invention reduces the strain difference between the silicon particles and the lithium-silicon alloy by reducing the average particle size of the silicon particles, thereby inhibiting the pulverization of the silicon particles during the charging and discharging process. . Secondly, the smaller the average particle size of the silicon particles, the shorter the diffusion path of lithium ions, and the easier and more complete the effect of the capacitance is. Furthermore, this manufacturing method utilizes the carbon layer coating technology (that is, after the silicon particles covering the asphalt are carbonized, the asphalt can form a carbon layer) to improve the conductivity of the material and reduce the side reactions caused by the direct contact between the silicon and the electrolyte. However, excessive solid-state electrolyte interfacial layers are generated, thereby increasing the capacitance of the electrode and prolonging the cycle life of the battery.
請參閱圖1，其係繪示根據本發明之一實施例的鋰離子電池用矽碳複合負極材料之製造方法的流程圖。在此製造方法100中，使用煤焦油系列瀝青對矽顆粒進行包覆步驟，以獲得瀝青包覆顆粒，如操作110所示。Please refer to FIG. 1 , which is a flowchart illustrating a method for manufacturing a silicon-carbon composite negative electrode material for lithium ion batteries according to an embodiment of the present invention. In this
本發明之煤焦油系列瀝青可為煉焦的副產品，以提升其再利用性。此煤焦油系列瀝青之軟化溫度為80℃至320℃，且較佳為80℃至100℃。申言之，軟化溫度會影響瀝青的質地及流動性，例如，軟化溫度愈低，瀝青質地愈軟且流動性愈高，故易與矽顆粒混合均勻，而有利於包覆矽顆粒。反之則相反。The coal tar series pitch of the present invention can be a by-product of coking, so as to improve its reusability. The softening temperature of the coal tar series pitch is 80°C to 320°C, and preferably 80°C to 100°C. In other words, the softening temperature will affect the texture and fluidity of asphalt. For example, the lower the softening temperature, the softer the asphalt texture and the higher the fluidity, so it is easy to mix with silicon particles uniformly, which is beneficial to coating silicon particles. The opposite is true.
當煤焦油系列瀝青之軟化溫度小於80℃時，煤焦油系列瀝青含有過多的易氣化的組成分，所以經過後續之碳化步驟後，瀝青所形成之碳層過薄或不均勻，故包覆效果不佳，使矽與電解液產生大量固態電解質界面層，因此電容量衰退。反之，當煤焦油系列瀝青之軟化溫度大於320℃時，煤焦油系列瀝青的流動性較差，而不易均勻地包覆矽顆粒，故包覆效果亦不佳，且同樣存在前述之產生大量固態電解質界面層的問題。When the softening temperature of the coal tar series pitch is less than 80°C, the coal tar series pitch contains too many components that are easy to gasify, so after the subsequent carbonization step, the carbon layer formed by the pitch is too thin or uneven, so the coating The effect is not good, causing a large amount of solid electrolyte interface layer between silicon and electrolyte, so the capacitance declines. On the contrary, when the softening temperature of coal tar series pitch is higher than 320℃, the fluidity of coal tar series pitch is poor, and it is not easy to coat the silicon particles uniformly, so the coating effect is also not good, and there is also a large amount of solid electrolyte as mentioned above. interface layer problems.
在一些實施例中，基於煤焦油系列瀝青之重量為100重量百分比，煤焦油系列瀝青之固定碳比例為50重量百分比至80重量百分比，且較佳為50重量百分比至60重量百分比。當煤焦油系列瀝青之固定碳比例為50重量百分比至80重量百分比時，瀝青經碳化後形成之碳層具有適當的厚度，而可均勻地包覆矽顆粒，以降低體積膨脹效應，從而提升電極的電容量且增長電池的循環壽命。In some embodiments, the fixed carbon ratio of the coal tar series pitch is 50 to 80 wt %, preferably 50 to 60 wt %, based on 100 wt % of the coal tar series pitch. When the fixed carbon ratio of the coal tar series pitch is 50% to 80% by weight, the carbon layer formed by the carbonization of the pitch has an appropriate thickness, and can evenly coat the silicon particles, so as to reduce the volume expansion effect and improve the electrode. capacity and increase the cycle life of the battery.
在一些實施例中，煤焦油系列瀝青與矽顆粒之重量比為0.2：1至1：1，且較佳為0.5：1至0.7：1。當煤焦油系列瀝青與矽顆粒之重量比為前述之範圍時，瀝青可完全且均勻地包覆矽顆粒，且所形成之碳層具有適當的厚度，故可抑制矽與電解液直接接觸發生副反應，從而提升電極的電容量且增長電池的循環壽命。In some embodiments, the weight ratio of coal tar series pitch to silicon particles is 0.2:1 to 1:1, and preferably 0.5:1 to 0.7:1. When the weight ratio of coal tar series pitch and silicon particles is within the aforementioned range, the pitch can completely and uniformly coat the silicon particles, and the formed carbon layer has an appropriate thickness, so the direct contact between the silicon and the electrolyte can be prevented from causing side effects. reaction, thereby increasing the capacitance of the electrode and increasing the cycle life of the battery.
矽顆粒之平均粒徑與矽與鋰矽合金間的應變差異及鋰離子擴散路徑有關。本發明之矽顆粒的平均粒徑為小於50nm，且較佳為小於46nm。當矽顆粒之平均粒徑不小於50nm時，矽與鋰矽合金間的應變差異增大，而導致矽顆粒於充放電過程中容易粉碎，故降低電極的電容量及電池的循環壽命。在其他實施例中，矽顆粒之平均粒徑為大於40nm且小於50nm，其中當矽顆粒之平均粒徑為前述之範圍時，所製得之電池更具有優越的首次充放電電容量及循環充放電電容量維持率。The average particle size of the silicon particles is related to the strain difference between silicon and lithium-silicon alloys and the diffusion paths of lithium ions. The average particle size of the silicon particles of the present invention is less than 50 nm, and preferably less than 46 nm. When the average particle size of the silicon particles is not less than 50 nm, the strain difference between silicon and lithium-silicon alloys increases, and the silicon particles are easily crushed during the charging and discharging process, thus reducing the capacitance of the electrode and the cycle life of the battery. In other embodiments, the average particle size of the silicon particles is greater than 40 nm and less than 50 nm, and when the average particle size of the silicon particles is within the aforementioned range, the prepared battery has superior initial charge-discharge capacity and cycle charge. Discharge capacity retention rate.
請再參閱圖1，於操作110後，對瀝青包覆顆粒進行碳化步驟，以獲得矽碳複合顆粒，如操作120所示。此碳化步驟係於高溫下碳化瀝青包覆顆粒中之瀝青，以在矽顆粒之外表面形成碳層。Referring to FIG. 1 again, after
在一些實施例中，碳化溫度可為700℃至1100℃，且較佳可為900℃至950℃。碳化步驟可於惰性氣體之環境下進行，以避免矽顆粒發生氧化現象，藉此保留原本矽材料之高電容量特性。舉例而言，惰性氣體可包含但不限於氮氣、氬氣、氦氣及其任意組合。In some embodiments, the carbonization temperature may be 700°C to 1100°C, and preferably 900°C to 950°C. The carbonization step can be performed in an inert gas environment to avoid oxidation of the silicon particles, thereby retaining the high capacitance characteristics of the original silicon material. For example, inert gases may include, but are not limited to, nitrogen, argon, helium, and any combination thereof.
當碳化溫度為700℃至1100℃時，碳化效果較完全，而不殘留未碳化的瀝青，從而提升電極的導電性，並且所製得之矽碳複合材料具有較佳的電化學活性，以利於與鋰離子進行反應，故可提升電極的電容量且增長電池的循環壽命。When the carbonization temperature is 700°C to 1100°C, the carbonization effect is more complete, and no uncarbonized pitch remains, thereby improving the conductivity of the electrode, and the obtained silicon-carbon composite material has better electrochemical activity, which is beneficial to It reacts with lithium ions, so it can increase the electric capacity of the electrode and prolong the cycle life of the battery.
於操作120後，對矽碳複合顆粒進行破碎步驟，以製得鋰離子電池用矽碳複合材料，如操作130所示。此破碎步驟係用以破碎矽碳複合顆粒，以使其成為具有特定平均粒徑(D
50)的顆粒(即鋰離子電池用矽碳複合材料)。舉例而言，但不以此為限，此特定平均粒徑可為4μm至8μm。
After
在一些實施例中，破碎步驟可藉由但不限於機械式粉碎設備來進行，例如，振動式研磨機、衝擊式粉碎機、旋轉筒式球磨機或具有通常知識者慣用之設備等。In some embodiments, the crushing step may be performed by, but not limited to, mechanical crushing equipment, such as, for example, a vibratory mill, an impact mill, a rotating drum ball mill, or equipment commonly used by those of ordinary skill.
請再參閱圖1，在進行操作110(即包覆步驟)前，製造方法100可選擇性包含進行研磨步驟，其中研磨步驟包含使用溶劑對矽微粒進行研磨，以獲得平均粒徑小於50nm之矽顆粒。在一些實施例中，矽微粒的來源(即矽材料)可為但不限於矽晶圓切削廢料，以達到廢物利用之環保目的。Please refer to FIG. 1 again, before performing the operation 110 (ie, the coating step), the
在一些實施例中，研磨步驟可採用乾式或濕式研磨，且較佳為濕式研磨。此濕式研磨係利用研磨液來進行，其中研磨液可包含溶劑及分散劑等助劑。In some embodiments, the grinding step may use dry or wet grinding, and preferably wet grinding. This wet grinding is carried out using a polishing liquid, wherein the polishing liquid may contain auxiliary agents such as a solvent and a dispersant.
此濕式研磨所使用的溶劑之沸點為80℃至300℃，且較佳為210℃至250℃。當溶劑之沸點為80℃至300℃時，此溶劑可於整個研磨過程中保持液態，而不汽化，以幫助研磨矽微粒，從而獲得平均粒徑小於50nm之矽顆粒。較佳地，此溶劑對於瀝青具有良好的相容性，以便於在不除去溶劑的情況下，於研磨後可直接進行後續之包覆步驟。此外，溶劑之具體例可包含但不限於具有芳香環結構之有機溶劑。The boiling point of the solvent used in this wet grinding is 80°C to 300°C, and preferably 210°C to 250°C. When the boiling point of the solvent is 80°C to 300°C, the solvent can remain liquid during the entire grinding process without vaporizing, so as to help grind the silicon particles, thereby obtaining silicon particles with an average particle size of less than 50 nm. Preferably, the solvent has good compatibility with the bitumen, so that the subsequent coating step can be carried out directly after grinding without removing the solvent. In addition, specific examples of the solvent may include, but are not limited to, organic solvents having an aromatic ring structure.
在另一些實施例中，前述之分散劑係利用自身化學結構的立體效應，幫助矽顆粒分散於前述溶劑中，並避免矽顆粒聚集，以利於矽顆粒的奈米化。分散劑之具體例可包含但不限於含有丙烯酸或丙烯酸鹽的單體單元之均聚物或共聚物。In other embodiments, the aforementioned dispersant utilizes the steric effect of its own chemical structure to help the silicon particles to disperse in the aforementioned solvent, and to prevent the silicon particles from agglomerating, so as to facilitate the nanoization of the silicon particles. Specific examples of dispersants may include, but are not limited to, homopolymers or copolymers containing monomeric units of acrylic acid or acrylate.
在一些實施例中，基於研磨液的重量為100重量百分比，矽顆粒的使用量為10重量百分比。當矽顆粒的使用量為10重量百分比時，所製得之矽顆粒的平均粒徑可小於50nm，以抑制矽顆粒於充放電過程中粉碎化並縮短鋰離子擴散路徑，從而提升電極的電容量及電池的循環壽命。In some embodiments, the amount of silicon particles used is 10 weight percent based on 100 weight percent of the slurry. When the amount of silicon particles used is 10% by weight, the average particle size of the prepared silicon particles can be less than 50 nm, which can inhibit the pulverization of silicon particles during the charging and discharging process and shorten the diffusion path of lithium ions, thereby improving the capacitance of the electrode. and battery cycle life.
此外，在一些實施例中，研磨步驟可包含複數個研磨階段。舉例而言，可先使用較大顆的研磨珠，進行第一研磨階段，再使用較小顆的研磨珠，進行第二研磨階段。惟，本發明不以前述條件為限制，而以達到前述之矽顆粒的平均粒徑小於50nm為必要的目的。此外，此研磨珠的具體例包含釔穩定氧化鋯珠。Furthermore, in some embodiments, the grinding step may comprise a plurality of grinding stages. For example, the first grinding stage may be performed using larger-sized grinding beads, and then the second grinding stage may be performed using smaller-sized grinding beads. However, the present invention is not limited to the aforementioned conditions, and it is a necessary objective to achieve the aforementioned average particle size of the silicon particles less than 50 nm. In addition, specific examples of the grinding beads include yttrium-stabilized zirconia beads.
在一些應用例中，前述鋰離子電池用矽碳複合材料之製造方法可製得本發明之鋰離子電池用矽碳複合材料。基於此矽碳複合材料之重量為100重量百分比，矽的含量為50重量百分比至80重量百分比，且較佳為70重量百分比至80重量百分比。由於矽材料較碳材料具有更高的電容量，所以矽碳複合材料中的矽的含量會影響電極的電容量。In some application examples, the silicon-carbon composite material for lithium-ion batteries of the present invention can be obtained by the above-mentioned manufacturing method of the silicon-carbon composite material for lithium-ion batteries. Based on the weight of the silicon-carbon composite material being 100% by weight, the content of silicon is 50% by weight to 80% by weight, and preferably 70% by weight to 80% by weight. Since silicon material has higher capacitance than carbon material, the content of silicon in the silicon-carbon composite material will affect the capacitance of the electrode.
若矽含量小於50重量百分比時，所製得之矽碳複合材料的電容量過低，而降低電極之電容量。反之，當矽的含量大於80重量百分比時，包覆矽顆粒之碳層的厚度過薄，且包覆效果不佳，而難以抑制矽與電解液直接接觸所產生過多的固態電解質界面層，故縮短電池的循環壽命。If the silicon content is less than 50 weight percent, the capacitance of the prepared silicon-carbon composite material is too low, thereby reducing the capacitance of the electrode. On the contrary, when the content of silicon is greater than 80 weight percent, the thickness of the carbon layer covering the silicon particles is too thin, and the coating effect is not good, and it is difficult to suppress the excessive solid electrolyte interface layer generated by the direct contact between silicon and the electrolyte. Shorten the cycle life of the battery.
在一些實施例中，鋰離子電池用矽碳複合材料之平均粒徑(D 50)為4μm至8μm，且較佳為4μm至5μm。當此平均粒徑(D 50)為4μm至8μm時，矽碳複合材料中之矽顆粒與碳層間接觸緊密，而提升電極的電容量，並且矽碳複合材料可均勻地分散於水性漿料中，從而利於後續加工操作性(即水性漿料塗佈於導電基材上)。 In some embodiments, the average particle size (D 50 ) of the silicon-carbon composite material for lithium ion batteries is 4 μm to 8 μm, and preferably 4 μm to 5 μm. When the average particle size (D 50 ) is 4 μm to 8 μm, the silicon particles in the silicon-carbon composite material are in close contact with the carbon layer, thereby improving the capacitance of the electrode, and the silicon-carbon composite material can be uniformly dispersed in the aqueous slurry. , so as to facilitate the subsequent processing operability (ie, the aqueous slurry is coated on the conductive substrate).
本發明之鋰離子電池用電極包含導電基材及導電層，其中導電層包含活性物質、導電輔助材料及黏結劑，且活性物質包含前述之鋰離子電池用矽碳複合材料。The electrode for lithium ion battery of the present invention includes a conductive substrate and a conductive layer, wherein the conductive layer includes an active material, an auxiliary conductive material and a binder, and the active material includes the aforementioned silicon-carbon composite material for lithium ion battery.
申言之，導電基材係做為電流收集器。在一些實施例中，導電基材可包含但不限於金屬導體或非金屬導體，並且導電基材的形狀可包含，但不限於，片狀或棒狀。舉例而言，金屬導體可包含銀、銅、金、鎳、鐵或鉛，並且非金屬導體可包含石墨。In other words, the conductive substrate acts as a current collector. In some embodiments, the conductive substrate may include, but is not limited to, a metallic conductor or a non-metallic conductor, and the shape of the conductive substrate may include, but is not limited to, a sheet or rod. For example, metallic conductors may include silver, copper, gold, nickel, iron, or lead, and non-metallic conductors may include graphite.
黏結劑係用於將活性物質黏結於導電基材上。在一些實施例中，黏結劑與活性物質均勻混合，以形成水性漿料，再塗佈於導電基材上，並經過烘烤，以製得鋰離子電池用電極。此外，黏結劑之具體例可包含但不限於羧甲基纖維素(CMC)、丁苯橡膠(SBR)、聚氧化乙烯、聚乙烯醇、聚二氧乙烯噻吩、聚丙烯酸、聚醯亞胺及其任意組合。The binder is used to bind the active material to the conductive substrate. In some embodiments, the binder and the active material are uniformly mixed to form an aqueous slurry, which is then coated on the conductive substrate and baked to prepare an electrode for a lithium ion battery. In addition, specific examples of the binder may include, but are not limited to, carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyethylene oxide, polyvinyl alcohol, polydioxyethylene thiophene, polyacrylic acid, polyimide, and any combination thereof.
在一些實施例中，基於導電層之重量為100重量百分比，黏結劑之使用量為4重量百分比至5重量百分比，且較佳為4.3重量百分比至4.7重量百分比。當黏結劑之使用量為4重量百分比至5重量百分比時，黏結劑可分散活性物質，並將其黏結於導電基材上，從而提升電極的導電性及電容量，且增長電池的循環壽命。In some embodiments, based on the weight of the conductive layer as 100 wt %, the amount of the binder used is 4 to 5 wt %, and preferably 4.3 to 4.7 wt %. When the amount of the binder used is 4 to 5 wt%, the binder can disperse the active material and bond it to the conductive substrate, thereby improving the conductivity and capacitance of the electrode, and prolonging the cycle life of the battery.
在鋰離子電池用電極中，基於導電層之重量為100重量百分比，鋰離子電池用矽碳複合材料之使用量為10重量百分比至15重量百分比，且較佳為12重量百分比至13.5重量百分比。當矽碳複合材料之使用量為10重量百分比至15重量百分比時，所形成之水性漿料具有適當黏度，而可均勻地塗佈於導電基材上，且可黏結矽碳複合材料至導電基材上，故電子可在矽碳與外部電路之間傳導。In the electrode for lithium ion battery, based on the weight of the conductive layer being 100 wt %, the usage amount of the silicon carbon composite material for lithium ion battery is 10 wt % to 15 wt %, and preferably 12 wt % to 13.5 wt %. When the amount of the silicon-carbon composite material used is 10 to 15 weight percent, the formed aqueous slurry has a suitable viscosity, which can be uniformly coated on the conductive substrate, and can bond the silicon-carbon composite material to the conductive substrate. On the material, so electrons can conduct between the silicon carbon and the external circuit.
在一些實施例中，導電層包含導電輔助材料，導電輔助材料係用以輔助導電，以提升電極的導電性。導電輔助材料之具體例可包含但不限於導電碳黑(由特密高(TIMCAL)公司製造，且型號為super P)。In some embodiments, the conductive layer includes a conductive auxiliary material, and the conductive auxiliary material is used to assist conduction, so as to improve the conductivity of the electrode. Specific examples of the conductive auxiliary material may include, but are not limited to, conductive carbon black (manufactured by TIMCAL, and the model is super P).
基於導電層之重量為100重量百分比，導電輔助材料之使用量為2重量百分比至5重量百分比，且較佳為3重量百分比至4重量百分比。當導電輔助材料之使用量為2重量百分比至5重量百分比時，電極的導電性增加，從而提升電極的電容量，且增長電池的循環壽命。Based on the weight of the conductive layer being 100% by weight, the amount of the conductive auxiliary material used is 2% by weight to 5% by weight, and preferably 3% by weight to 4% by weight. When the amount of the conductive auxiliary material used is 2 to 5 weight percent, the conductivity of the electrode is increased, thereby increasing the electric capacity of the electrode and prolonging the cycle life of the battery.
以下利用實施例以說明本發明之應用，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。The following examples are used to illustrate the application of the present invention, but it is not intended to limit the present invention. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention.
鋰離子電池用矽碳複合材料之製造Manufacture of silicon-carbon composite materials for lithium-ion batteries
實施例1Example 1
使用濕式研磨機研磨矽晶圓切削廢料，其中基於研磨液的重量為100重量百分比，矽晶圓切削廢料的使用量為10重量百分比，且研磨液中之溶劑的沸點為210℃至250℃。於研磨步驟中，先以0.1mm的釔穩定氧化鋯珠研磨9小時，以獲得平均粒徑為77nm的矽顆粒，再以0.05mm的釔穩定氧化鋯珠研磨2小時，以獲得平均粒徑為45nm的矽顆粒。Use a wet grinder to grind silicon wafer cutting waste, wherein the amount of silicon wafer cutting waste is 10% by weight based on the weight of the polishing liquid, and the boiling point of the solvent in the polishing liquid is 210°C to 250°C . In the grinding step, 0.1 mm yttrium-stabilized zirconia beads were firstly ground for 9 hours to obtain silicon particles with an average particle size of 77 nm, and then 0.05 mm yttrium-stabilized zirconia beads were ground for 2 hours to obtain an average particle size of 77 nm. 45nm silicon particles.
於反應釜(由Parr Instrument公司製造，且型號為4848)中，混合煤焦油系列瀝青(由中碳公司製造，固定碳比例為55重量百分比，且軟化溫度為85℃至100℃)與45nm的矽顆粒(未除去研磨液)，其中煤焦油系列瀝青與矽顆粒之重量比為0.5：1至0.7：1。接著，升溫並進行攪拌。然後，持溫於280℃(或大於280℃)下，去除溶劑並降低煤焦油系列瀝青的黏滯性，均勻混合瀝青與矽顆粒，並同時持續通入氮氣，以抑制矽顆粒氧化，從而獲得瀝青包覆顆粒。In a reaction kettle (manufactured by Parr Instrument Company, and the model is 4848), mix coal tar series pitch (manufactured by China Carbon Company, the fixed carbon ratio is 55% by weight, and the softening temperature is 85 ° C to 100 ° C) and 45nm. Silicon particles (without removing the grinding fluid), wherein the weight ratio of coal tar series pitch and silicon particles is 0.5:1 to 0.7:1. Next, it heated up and stirred. Then, keep the temperature at 280°C (or more than 280°C), remove the solvent and reduce the viscosity of coal tar series pitch, mix the pitch and silicon particles uniformly, and continuously pass nitrogen gas at the same time to inhibit the oxidation of silicon particles. Asphalt coated particles.
接著，將瀝青包覆矽之顆粒於氮氣環境下加熱到900℃至950℃，再持溫8小時，以進行碳化，從而獲得矽碳複合顆粒。最後，使用振動研磨機粉碎矽碳複合顆粒，並以400目篩網過篩，以製得實施例1之鋰離子電池用矽碳複合材料。Next, the asphalt-coated silicon particles are heated to 900° C. to 950° C. in a nitrogen atmosphere, and the temperature is maintained for 8 hours for carbonization, thereby obtaining silicon-carbon composite particles. Finally, the silicon-carbon composite particles were pulverized by a vibration mill and sieved with a 400-mesh sieve to obtain the silicon-carbon composite material for lithium ion batteries of Example 1.
比較例1及2Comparative Examples 1 and 2
比較例1及2皆以與實施例1相同的方法進行製造。不同的是，比較例1及2係改變矽顆粒的平均粒徑與參數條件，其中比較例1未進行濕式研磨，且比較例2僅進行一個階段的濕式研磨(即僅使用尺寸為0.1mm的釔穩定氧化鋯珠)，其具體條件如表1所示。Both Comparative Examples 1 and 2 were produced in the same manner as in Example 1. The difference is that in Comparative Examples 1 and 2, the average particle size and parameter conditions of the silicon particles were changed, in which Comparative Example 1 did not perform wet grinding, and Comparative Example 2 only performed one stage of wet grinding (that is, only using a size of 0.1 mm of yttrium-stabilized zirconia beads), and the specific conditions are shown in Table 1.
鋰離子電池用電極Electrodes for Lithium Ion Batteries
應用例1Application example 1
基於鋰離子電池用矽碳複合材料與介相瀝青石墨之總重量為100重量百分比，應用例1係將14重量百分比的實施例1之鋰離子電池用矽碳複合材料均勻地混入介相瀝青石墨，以獲得負極的活性物質。再將負極的活性物質、羧甲基纖維素(CMC)、丁苯橡膠(SBR)、導電碳黑(由特密高(TIMCAL)公司製造，且型號為super P)(重量比為92：1.5：3：3.5)調配成水性漿料。然後，以刮刀將水性漿料塗佈於銅箔上(水性漿料的塗覆量為6mg/cm 2)，於110℃下，經8小時真空烘烤後，以製得應用例1之鋰離子電池用電極，並進行後續之評價，且結果如表2所示。 Based on the total weight of the silicon-carbon composite material for lithium ion batteries and the mesophase pitch graphite being 100 weight percent, Application Example 1 is to uniformly mix 14 weight percent of the silicon carbon composite material for lithium ion batteries of Example 1 into the mesophase pitch graphite , to obtain the active material of the negative electrode. Then the active material of the negative electrode, carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), conductive carbon black (manufactured by TIMCAL, and the model is super P) (weight ratio is 92:1.5) : 3: 3.5) is formulated into an aqueous slurry. Then, the aqueous slurry was coated on the copper foil with a doctor blade (the coating amount of the aqueous slurry was 6 mg/cm 2 ), and after vacuum baking at 110° C. for 8 hours, the lithium of Application Example 1 was obtained. Electrodes for ion batteries were evaluated, and the results are shown in Table 2.
比較應用例1及2Comparative Application Examples 1 and 2
比較應用例1及2皆以與應用例1相同的方法，進行製造。不同的是，比較應用例1及2分別使用比較例1及2之鋰離子電池用矽碳複合材料，而其評價結果如表2所示。Comparative Application Examples 1 and 2 were produced in the same manner as in Application Example 1. The difference is that Comparative Application Examples 1 and 2 use the silicon-carbon composite materials for lithium ion batteries of Comparative Examples 1 and 2 respectively, and the evaluation results are shown in Table 2.
評價方式Evaluation method
1.矽顆粒及矽碳複合材料的平均粒徑1. Average particle size of silicon particles and silicon-carbon composites
本發明所稱之平均粒徑係使用穿透式電子顯微鏡與影像軟體(Image J)分析鑑定矽顆粒及矽碳複合材料的平均粒徑，其結果如表1及圖2A至2C所示。The average particle size referred to in the present invention refers to the analysis and identification of the average particle size of the silicon particles and the silicon-carbon composite material using a transmission electron microscope and image software (Image J). The results are shown in Table 1 and Figures 2A to 2C.
2.電容量測試2. Capacitance test
將鋰離子電池用電極與碳酸酯類電解液組成CR2032鈕扣半電池。再以充放電機(由Arbin Instruments公司製造，且型號為BT 2043)對此半電池進行充電。先以0.1C定電流充電至0.001V，再轉定電壓充電至電流小於0.01C為止，接著以0.1C定電流放電至1.5V，再轉定電壓充電至電流小於0.01C為止，此為1圈過程。如此循環4圈過程，做為化成程序，以獲得矽碳/石墨負極的電容量，其結果如表2所示。此外，使用石墨負極片進行前述之4圈過程，以測得石墨負極片的電容量。然後，將矽碳/石墨負極的電容量扣除石墨負極片的電容量，以計算出矽碳複合材料的電容量，其結果如表2所示。A CR2032 button half-cell is formed by combining the lithium-ion battery electrode and carbonate electrolyte. This half-cell was then charged with a charge-discharger (manufactured by Arbin Instruments, model BT 2043). First charge at 0.1C constant current to 0.001V, then switch to constant voltage to charge until the current is less than 0.01C, then discharge at 0.1C constant current to 1.5V, then switch to constant voltage to charge until the current is less than 0.01C, this is 1 turn process. This cycle of 4 cycles was used as the formation procedure to obtain the capacitance of the silicon carbon/graphite negative electrode. The results are shown in Table 2. In addition, the above-mentioned 4-cycle process was performed with a graphite negative electrode sheet to measure the capacitance of the graphite negative electrode sheet. Then, the capacitance of the silicon carbon/graphite negative electrode was deducted from the capacitance of the graphite negative electrode sheet to calculate the capacitance of the silicon carbon composite material. The results are shown in Table 2.
3.循環壽命測試3. Cycle life test
循環壽命測試係以與電容量測試相同方式進行，且截止條件亦為相同，不同之處在於，循環壽命測試係將充放電流調整為0.5C，且循環100圈，以測得循環充放電容量維持率，其中首次測得之放電電容量與充電電容量的比值稱作首次充放電庫倫效率，並且使用循環100圈所測得之循環充放電容量維持率與下述之標準評價循環壽命，其結果如表2所示。 ○：80%≦循環充放電容量維持率。 ╳：循環充放電容量維持率＜80%。 The cycle life test is carried out in the same way as the capacitance test, and the cut-off conditions are also the same, the difference is that the cycle life test is to adjust the charge and discharge current to 0.5C, and cycle for 100 cycles to measure the cycle charge and discharge capacity The maintenance rate, in which the ratio of the discharge capacity and the charge capacity measured for the first time is called the coulomb efficiency of the first charge and discharge, and the cycle life is evaluated using the cycle charge-discharge capacity maintenance rate measured for 100 cycles and the following criteria, which The results are shown in Table 2. ○: 80%≦Cyclic charge-discharge capacity retention rate. ╳: Cycle charge-discharge capacity retention rate <80%.
4.矽碳複合材料的矽含量4. Silicon content of silicon carbon composites
矽碳複合材料的矽含量係採用本發明所屬技術領域中具有通常知識者所慣用之方法測得。The silicon content of the silicon-carbon composite material is measured by a method commonly used by those with ordinary knowledge in the technical field to which the present invention pertains.
表1
表2
請參閱表1及圖2A至2C，圖2A至2C分別為實施例1、比較例1及比較例2之矽碳複合材料的穿透式電子顯微鏡照片，其顯示實施例1、比較例1及比較例2之矽顆粒的平均粒徑分別為45nm、132nm及77nm。Please refer to Table 1 and FIGS. 2A to 2C. FIGS. 2A to 2C are transmission electron microscope photographs of the silicon-carbon composite materials of Example 1, Comparative Example 1 and Comparative Example 2, respectively, which show Example 1, Comparative Example 1 and The average particle diameters of the silicon particles of Comparative Example 2 were 45 nm, 132 nm and 77 nm, respectively.
請參閱表1及表2，相較於較大的矽顆粒之比較例，使用較小的矽顆粒之實施例1所製得之矽碳複合材料的電容量較高，包含其之電極的電容量較高，且首次充放電庫倫效率及循環充放電容量維持率較佳。由此可知，特定平均粒徑之矽顆粒可避免矽碳複合材料的矽顆粒於充放電過程中粉碎化，從而提升電極的電容量，且增加電池的循環壽命。Please refer to Table 1 and Table 2. Compared with the comparative example with larger silicon particles, the silicon-carbon composite material prepared in Example 1 using smaller silicon particles has higher capacitance, and the electrode comprising the same has higher capacitance. The capacity is higher, and the first charge and discharge Coulomb efficiency and cycle charge and discharge capacity retention rate are better. It can be seen that the silicon particles with a specific average particle size can prevent the silicon particles of the silicon-carbon composite material from being pulverized during the charging and discharging process, thereby increasing the electric capacity of the electrode and increasing the cycle life of the battery.
綜上所述，本發明之鋰離子電池用矽碳複合材料之製造方法，其中藉由特定粒徑之矽顆粒及特定軟化溫度之煤焦油系列瀝青，由此製造方法所製造之鋰離子電池用矽碳複合材料可抑制矽顆粒粉碎化，從而提升電極的電容量且增長電池的循環壽命。To sum up, the manufacturing method of the silicon-carbon composite material for lithium ion batteries of the present invention, wherein the silicon particles with a specific particle size and the coal tar series pitch with a specific softening temperature are used for the lithium ion battery manufactured by the manufacturing method. The silicon-carbon composite material can inhibit the pulverization of silicon particles, thereby increasing the capacitance of the electrode and prolonging the cycle life of the battery.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the appended patent application.
100:方法
110,120,130:操作
100:
為了對本發明之實施例及其優點有更完整之理解，現請參照以下之說明並配合相應之圖式。必須強調的是，各種特徵並非依比例描繪且僅係為了圖解目的。相關圖式內容說明如下： 圖1係繪示根據本發明之實施例1的鋰離子電池用矽碳複合負極材料之製造方法的流程圖。 圖2A係本發明之一實施例之矽碳複合材料的穿透式電子顯微鏡照片。 圖2B及圖2C分別係本發明之比較例1及2之矽碳複合材料的穿透式電子顯微鏡照片。 In order to have a more complete understanding of the embodiments of the present invention and their advantages, please refer to the following description together with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustrative purposes only. The relevant diagrams are described as follows: FIG. 1 is a flow chart illustrating a method for manufacturing a silicon-carbon composite negative electrode material for a lithium ion battery according to Embodiment 1 of the present invention. FIG. 2A is a transmission electron microscope photograph of a silicon-carbon composite material according to an embodiment of the present invention. 2B and 2C are transmission electron microscope photographs of the silicon-carbon composite materials of Comparative Examples 1 and 2 of the present invention, respectively.
100:方法 100: Method
110,120,130:操作 110, 120, 130: Operation
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| CN112234179A (en) * | 2020-10-26 | 2021-01-15 | 郑州中科新兴产业技术研究院 | Preparation method of high-capacity silicon-based negative electrode material |
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| CN111224078A (en) * | 2018-11-27 | 2020-06-02 | 广州汽车集团股份有限公司 | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode |
| CN112234179A (en) * | 2020-10-26 | 2021-01-15 | 郑州中科新兴产业技术研究院 | Preparation method of high-capacity silicon-based negative electrode material |
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