TWI805421B - Particles of silicon-carbon composite material and method of manufacturing the same - Google Patents
Particles of silicon-carbon composite material and method of manufacturing the same Download PDFInfo
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本發明係有關於一種矽碳複合材料顆粒及其製造方法,且特別是有關於一種具有特定尺寸及特定分佈密度的孔洞之矽碳複合材料顆粒及其製造方法。The present invention relates to a silicon-carbon composite material particle and a manufacturing method thereof, and in particular to a silicon-carbon composite material particle with holes of a specific size and a specific distribution density and a manufacturing method thereof.
電池包含一次電池(primary cell)及二次電池(secondary cell),且二次電池包含鋰離子電池。隨著可攜帶式電子用品及電動車之性能的提升,對於鋰離子電池之電容量的要求愈嚴苛。The battery includes a primary cell and a secondary cell, and the secondary cell includes a lithium ion battery. With the improvement of the performance of portable electronic appliances and electric vehicles, the requirements for the capacity of lithium-ion batteries are becoming more and more stringent.
常見之鋰離子電池的負極材料為石墨,其電容量之實測值已接近理論值(約372mAh/g),故必須導入具有更高電容量之負極材料(如矽材料),以提高整個鋰離子電池之電容量。就矽材料而言,純矽形成Li 15Si 4合金之電容量理論值為3580mAh/g。 The negative electrode material of the common lithium-ion battery is graphite, and the measured value of its capacitance is close to the theoretical value (about 372mAh/g), so it is necessary to introduce a negative electrode material with a higher capacitance (such as silicon material) to improve the entire lithium-ion battery. The capacity of the battery. As far as silicon material is concerned, the theoretical capacitance value of Li 15 Si 4 alloy formed from pure silicon is 3580mAh/g.
雖然矽材料可提高鋰離子電池之電容量,但是矽材料於充放電之過程中所引起之體積變化量高達280%。此體積變化所導致之應變容易造成矽材料之顆粒的粉碎,進而降低所製得之負極電極的電容量。Although silicon materials can increase the capacity of lithium-ion batteries, the volume change caused by silicon materials in the process of charging and discharging is as high as 280%. The strain caused by the volume change easily causes the particles of the silicon material to be pulverized, thereby reducing the capacitance of the prepared negative electrode.
有鑑於此,亟需發展一種新的矽碳複合材料及其製造方法,以改善上述缺點。In view of this, there is an urgent need to develop a new silicon-carbon composite material and its manufacturing method to improve the above-mentioned shortcomings.
有鑑於上述之問題,本發明之一態樣是在提供一種矽碳複合材料顆粒,其具有分散於碳基質中之複數個矽粒子及複數個孔洞,並且於矽碳複合材料顆粒之橫截面中,此些孔洞具有特定的尺寸及分佈密度,以提升所製得之負極電極的電容量。In view of the above-mentioned problems, one aspect of the present invention is to provide a silicon-carbon composite material particle, which has a plurality of silicon particles and a plurality of holes dispersed in the carbon matrix, and in the cross-section of the silicon-carbon composite material particle , these pores have a specific size and distribution density, so as to improve the capacitance of the negative electrode produced.
本發明之另一態樣是在提供一種矽碳複合材料顆粒之製造方法。此製造方法係用以製造前述之矽碳複合材料顆粒。Another aspect of the present invention is to provide a method for manufacturing silicon-carbon composite particles. This manufacturing method is used to manufacture the aforementioned silicon-carbon composite material particles.
根據本發明之一態樣,提出一種矽碳複合材料顆粒。此些矽碳複合材料顆粒包含碳基質,其具有複數個矽粒子及複數個孔洞。此些矽粒子之平均粒徑為45nm至55nm。此些孔洞之尺寸為小於1μm,且於此些矽碳複合材料顆粒之橫截面中,此些孔洞之分佈密度為不小於20個/μm 2。此些矽粒子及此些孔洞均勻分散於碳基質中。 According to an aspect of the present invention, a silicon-carbon composite particle is provided. These silicon-carbon composite material particles include carbon matrix, which has a plurality of silicon particles and a plurality of holes. The average particle size of these silicon particles is 45nm to 55nm. The size of these holes is less than 1 μm, and in the cross-section of these silicon-carbon composite particles, the distribution density of these holes is not less than 20/μm 2 . The silicon particles and the holes are uniformly dispersed in the carbon matrix.
依據本發明之一實施例,此些矽碳複合材料顆粒之平均粒徑為6μm至8μm。According to an embodiment of the present invention, the average particle size of the silicon-carbon composite particles is 6 μm to 8 μm.
依據本發明之另一實施例,此些矽碳複合材料顆粒之比表面積為大於35m 2/g。 According to another embodiment of the present invention, the specific surface area of the silicon-carbon composite particles is greater than 35 m 2 /g.
依據本發明之另一實施例,此些矽碳複合材料顆粒之比表面積為大於35m 2/g且不大於50m 2/g。 According to another embodiment of the present invention, the specific surface area of the silicon-carbon composite particles is greater than 35 m 2 /g and not greater than 50 m 2 /g.
根據本發明之另一態樣,提出一種矽碳複合材料顆粒之製造方法。於此製造方法中,使用煤焦油系列瀝青對複數個矽粒子進行包覆步驟,以獲得複數個瀝青包覆顆粒,其中煤焦油系列瀝青之軟化溫度為75℃至95℃,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35重量百分比至45重量百分比,且此些矽粒子之平均粒徑為45nm至55nm。接著,對此些瀝青包覆顆粒進行碳化步驟,以獲得複數個矽碳複合顆粒。然後,對此些矽碳複合顆粒進行破碎步驟,以製得此些矽碳複合材料顆粒。According to another aspect of the present invention, a method for manufacturing silicon-carbon composite particles is proposed. In this manufacturing method, a plurality of silicon particles are coated with coal tar series pitch to obtain a plurality of pitch coated particles, wherein the softening temperature of coal tar series pitch is 75°C to 95°C, based on coal tar series pitch The weight is 100% by weight, the fixed carbon ratio of coal tar series pitch is 35% to 45% by weight, and the average particle size of these silicon particles is 45nm to 55nm. Then, a carbonization step is performed on these pitch-coated particles to obtain a plurality of silicon-carbon composite particles. Then, the crushing step is performed on the silicon-carbon composite particles to obtain the silicon-carbon composite material particles.
依據本發明之一實施例,在進行包覆步驟前,製造方法選擇性包含奈米化矽原料,以獲得此些矽粒子。According to an embodiment of the present invention, before performing the coating step, the manufacturing method optionally includes nanonized silicon raw materials to obtain the silicon particles.
依據本發明之另一實施例,煤焦油系列瀝青與此些矽粒子之重量比為1:1至1:3。According to another embodiment of the present invention, the weight ratio of the coal tar series pitch to the silicon particles is 1:1 to 1:3.
依據本發明之又一實施例,包覆步驟之包覆溫度為150℃至170℃。According to yet another embodiment of the present invention, the coating temperature in the coating step is 150°C to 170°C.
依據本發明之又一實施例,在碳化步驟之前,製造方法選擇性包含去除此些瀝青包覆顆粒所含有之溶劑。According to yet another embodiment of the present invention, prior to the carbonization step, the manufacturing method optionally includes removing the solvent contained in the pitch-coated particles.
依據本發明之又一實施例,碳化步驟之碳化溫度為800℃至1000℃。According to another embodiment of the present invention, the carbonization temperature in the carbonization step is 800°C to 1000°C.
應用本發明之矽碳複合材料顆粒及其製造方法,其中複數個矽粒子及複數個孔洞均勻分散於碳基質中。再者,於矽碳複合材料顆粒之橫截面中,此些孔洞具有特定的尺寸及分佈密度,以提升所製得之負極電極的電容量。The silicon-carbon composite particle and its manufacturing method are applied in the present invention, wherein a plurality of silicon particles and a plurality of holes are uniformly dispersed in the carbon matrix. Furthermore, in the cross-section of the silicon-carbon composite particle, the pores have specific size and distribution density, so as to increase the capacitance of the negative electrode produced.
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 making and using of embodiments of the 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 illustrative only and do not limit the scope of the invention.
本發明之矽碳複合材料顆粒包含碳基質,其中複數個矽粒子及複數個孔洞均勻分散於碳基質中。此些矽粒子具有特定平均粒徑,以降低矽粒子與鋰矽合金間的應變差異,而抑制矽粒子於充放電過程中粉碎化,並且矽粒子亦可縮短鋰離子擴散路徑,以提高矽碳複合材料顆粒之電容量,從而提升所製得之負極電極的電容量。The silicon-carbon composite particle of the present invention includes a carbon matrix, wherein a plurality of silicon particles and a plurality of holes are uniformly dispersed in the carbon matrix. These silicon particles have a specific average particle size to reduce the strain difference between the silicon particles and the lithium-silicon alloy, thereby inhibiting the pulverization of the silicon particles during the charging and discharging process, and the silicon particles can also shorten the diffusion path of lithium ions to improve the silicon carbon density. The capacitance of the composite material particles, thereby increasing the capacitance of the prepared negative electrode.
前述孔洞具有特定分佈密度,以緩衝負極電極於充放電過程中之矽碳複合材料顆粒與鋰離子反應所引起之體積變化(如膨脹及縮收),從而提升矽碳複合材料顆粒之結構的穩定性,並增長所製得之鋰離子電池的壽命,且孔洞可做為傳送鋰離子到矽粒子之快速通道,以提高矽碳複合材料顆粒之電容量。再者,孔洞可增加矽碳複合材料顆粒的反應活性,以使鋰離子電池具備快充性能,並提高首次充放電庫倫效率。The above-mentioned holes have a specific distribution density to buffer the volume change (such as expansion and contraction) caused by the reaction between the silicon-carbon composite material particles and lithium ions during the charge and discharge process of the negative electrode, thereby improving the stability of the structure of the silicon-carbon composite material particles properties, and increase the life of the lithium-ion battery produced, and the holes can be used as a fast channel to transport lithium ions to silicon particles, so as to improve the capacitance of silicon-carbon composite particles. Furthermore, the pores can increase the reactivity of the silicon-carbon composite particles, so that the lithium-ion battery has fast charging performance and improves the first-time charge-discharge Coulombic efficiency.
矽碳複合材料顆粒係利用具有特定軟化溫度及特定固定碳比例之煤焦油系列瀝青包覆矽粒子,並經碳化而製得矽碳複合材料顆粒,其中碳基質係由瀝青所碳化形成。此軟化溫度可控制瀝青的質地及流動性,以利於其與矽粒子均勻混合,從而完整且均勻地包覆矽粒子。故,矽粒子及孔洞彼此實質不接觸,以提高矽碳複合材料顆粒之電子導電性,並減少矽粒子與電解液直接接觸(即減少固液介面層)所發生之反應,從而提升負極電極的電容量。再者,此固定碳比例可使所製得之矽碳複合材料顆粒之碳基質中具備前述之特定的尺寸及分佈密度之孔洞,從而提高矽碳複合材料顆粒之電容量。Silicon-carbon composite material particles use coal tar series pitch with specific softening temperature and specific fixed carbon ratio to coat silicon particles, and then carbonize to obtain silicon-carbon composite material particles, in which the carbon matrix is formed by carbonization of pitch. This softening temperature can control the texture and fluidity of asphalt, so as to facilitate its uniform mixing with silicon particles, so as to completely and uniformly cover silicon particles. Therefore, the silicon particles and the pores do not contact each other substantially, so as to improve the electronic conductivity of the silicon-carbon composite material particles, and reduce the reaction of the silicon particles in direct contact with the electrolyte (that is, reduce the solid-liquid interface layer), thereby improving the negative electrode. capacitance. Furthermore, the fixed carbon ratio can make the carbon matrix of the obtained silicon-carbon composite material particles have the aforementioned specific size and distribution density of holes, thereby increasing the capacitance of the silicon-carbon composite material particles.
請參閱圖1,於矽碳複合材料顆粒之製造方法100中,使用煤焦油系列瀝青對複數個矽粒子進行包覆步驟,以獲得複數個瀝青包覆顆粒,如操作110所示。煤焦油系列瀝青之軟化溫度為75℃至95℃,且較佳可為80℃至90℃。倘若軟化溫度低於75℃,瀝青含有過多之易氣化的組成分,於後續之碳化步驟後,瀝青碳化後所形成之碳基質過薄或厚度不均勻,故對矽粒子之包覆效果不佳,而降低電極的充放電穩定性。反之,倘若軟化溫度高於95℃,瀝青的流動性較差,而不易均勻包覆矽粒子,故降低電極的充放電穩定性。基於煤焦油系列瀝青之重量為100重量百分比,瀝青之固定碳比例為35重量百分比至45重量百分比,且較佳可為38重量百分比至42重量百分比。倘若固定碳比例小於35重量百分比,碳化所形成之碳基質難以完整包覆矽粒子,或者孔洞之尺寸過大(如大於1μm)。反之,倘若固定碳比例大於45重量百分比,孔洞之分佈密度過低(如小於20個/μm
2),而降低矽碳複合材料顆粒之電容量。
Please refer to FIG. 1 , in the
在一些實施例中,於10°C/min之加熱速率下,瀝青之第一次、第二次及第三次之重量損失分別發生於260℃至265℃、370℃至375℃及480℃至485℃,且其失重率分別為22%至28%、16%至22%及13%至19%,較佳可為25%、19%及16%。當瀝青之重量損失溫度及失重率均符合前述之條件時,於後續碳化步驟中,瀝青中之低分子量有機物(如容易氣化之有機物)可氣化形成尺寸小於1μm且分佈密度不小於20個/μm 2的孔洞,故更提升電極之電容量。 In some embodiments, at a heating rate of 10°C/min, the first, second, and third weight losses of asphalt occur at 260°C to 265°C, 370°C to 375°C, and 480°C, respectively to 485°C, and the weight loss rates are 22% to 28%, 16% to 22% and 13% to 19%, preferably 25%, 19% and 16%. When the weight loss temperature and weight loss rate of asphalt meet the above conditions, in the subsequent carbonization step, the low molecular weight organic matter in the asphalt (such as organic matter that is easy to gasify) can be gasified to form a size of less than 1 μm and a distribution density of not less than 20 /μm 2 pores, so the capacitance of the electrode is further improved.
前述矽粒子之平均粒徑為45nm至55nm,且較佳可為50nm。倘若平均粒徑大於55nm,矽與鋰矽合金間的應變差異增大,於反覆充放電後,容易導致矽碳複合材料顆粒破碎,而降低電極之充放電穩定性。倘若平均粒徑小於45nm,矽粒子易聚集,而難以發揮奈米化之功效,因此無助於提升電容量與電極充放電穩定性。The average particle size of the aforementioned silicon particles is 45nm to 55nm, and preferably 50nm. If the average particle size is greater than 55nm, the strain difference between silicon and lithium-silicon alloy will increase, which will easily cause the silicon-carbon composite material particles to break after repeated charge and discharge, thus reducing the charge and discharge stability of the electrode. If the average particle size is less than 45nm, the silicon particles are easy to aggregate, and it is difficult to exert the effect of nanometerization, so it is not helpful to improve the capacitance and electrode charge and discharge stability.
在一些實施例中,瀝青與矽粒子之重量比為1:1至1:3,較佳可為1:1.5至1:2.5,且更佳可為1:2。當重量比為前述之範圍時,瀝青可完整包覆矽粒子,以提高電極之電容量。In some embodiments, the weight ratio of pitch to silicon particles is 1:1 to 1:3, preferably 1:1.5 to 1:2.5, and more preferably 1:2. When the weight ratio is within the aforementioned range, the pitch can completely cover the silicon particles to increase the capacitance of the electrode.
在一些實施例中,包覆步驟之包覆溫度為150℃至170℃。當包覆溫度為前述之範圍時,瀝青可完整包覆矽粒子,以提高電極之電容量。包覆時間沒有特別限制,惟以達成完整包覆矽粒子為目的。In some embodiments, the coating temperature in the coating step is 150°C to 170°C. When the coating temperature is in the above range, the pitch can completely cover the silicon particles to increase the capacitance of the electrode. The coating time is not particularly limited, but is for the purpose of completely coating the silicon particles.
在進行包覆步驟前,製造方法100可選擇性包含奈米化矽原料,以獲得矽粒子。奈米化沒有特別限制,惟以將矽原料製成平均粒徑為45nm至55nm之矽粒子為目的,且其條件可為具有通常知識者所習知的。Before performing the coating step, the
於操作110後,對瀝青包覆顆粒進行碳化步驟,以獲得矽碳複合物,如操作120所示。碳化步驟可於惰性氣體(如氮氣、氬氣、氦氣及其組合)之環境下進行。After
碳化步驟之碳化溫度為800℃至1000℃。當碳化溫度為前述之範圍時,碳化效果較完全,從而提升電極的導電性。碳化步驟之碳化時間以達成前述完全碳化效果為目的。The carbonization temperature in the carbonization step is 800°C to 1000°C. When the carbonization temperature is within the aforementioned range, the carbonization effect is relatively complete, thereby improving the conductivity of the electrode. The carbonization time of the carbonization step is aimed at achieving the aforementioned complete carbonization effect.
在一些實施例中,在碳化步驟之前,製造方法100可選擇性包含去除瀝青包覆顆粒所含有之溶劑,以利於獲得前述之特定平均粒徑的矽粒子。去除溶劑之方法可如加熱。In some embodiments, before the carbonization step, the
於操作120後,對矽碳複合顆粒進行破碎步驟,以製得矽碳複合材料顆粒,如操作130所示。破碎步驟無特別限制,惟以達成前述特定平均粒徑為目的。After
製造方法100可排除使用石墨及/或界面活性劑,故所製得矽碳複合材料顆粒之碳基質不具有石墨。此乃由於額外的石墨及界面活性劑均會影響矽粒子之包覆及孔洞的形成。此外,製造方法100亦可排除使用有機酸及/或無機酸。此乃由於本發明之煤焦油系列瀝青具有特定的軟化溫度及固定碳比例,故其所含之低分子量的有機物於乾燥步驟及/或碳化步驟中可被氣化或氧化成氣體(如二氧化碳或/及低碳數之氧化物的氣體)而留下孔洞,故無須使用酸來蝕刻及/或氧化碳基質來產生孔洞。The
請參閱圖2,由前述之製造方法所製得之矽碳複合材料顆粒200包含碳基質230,其具有複數個矽粒子210與複數個孔洞220。二者係均勻分佈於由前述瀝青碳化後所形成的碳基質230中。Please refer to FIG. 2 , the silicon-
矽粒子210為前述製造方法所使用之矽粒子,其具備高溫安定性,故經前述包覆步驟、碳化步驟、乾燥步驟及破碎步驟後,矽粒子210之平均粒徑d並未改變,如為45nm至55nm。The
孔洞220之尺寸為小於1μm,且較佳可為50nm至500nm。倘若此尺寸為不小於1μm,於充放電過程中,孔洞220不能緩衝矽碳複合材料顆粒200與鋰離子反應所引起之體積變化。The size of the
此外,於矽碳複合材料顆粒200之橫截面中,孔洞220之分佈密度為不小於20個/μm
2,且較佳可為大於30個/μm
2且不大於50個/μm
2。倘若分佈密度小於20個/μm
2,於充放電過程中,孔洞220不能緩衝前述之體積變化。當分佈密度為大於30個/μm
2且不大於50個/μm
2時,孔洞220除能緩衝前述之體積變化之外,且利於鋰離子更快傳輸至矽粒子210,以更提高矽碳複合材料顆粒200之電容量。
In addition, in the cross-section of the silicon-
矽碳複合材料顆粒200之比表面積係指單位重量之矽碳複合材料顆粒200的外部表面積與內部孔洞220的表面積之總和。在一些實施例中,矽碳複合材料顆粒200之比表面積為大於35m
2/g。當比表面積為前述之範圍時,可提高矽碳複合材料顆粒200的反應活性,以提高其電容量。較佳地,比表面積可為大於35m
2/g且不大於50m
2/g,且更佳可為35m
2/g至45m
2/g。
The specific surface area of the silicon-
在一些實施例中,矽碳複合材料顆粒200之平均粒徑D可為6μm至8μm。當平均粒徑D為前述之範圍時,於後續製備負極電極時,矽碳複合材料顆粒200可均勻分散於漿料中並利於漿料塗佈於基材上,故提升電極的電容量。In some embodiments, the average particle diameter D of the silicon-
在一些實施例中,基於矽碳複合材料顆粒200之重量為100重量百分比,矽碳複合材料顆粒200之矽含量可為71重量百分比至88重量百分比。當矽含量為前述之範圍時,提升矽碳複合材料顆粒200之電容量,從而提升電極的電容量。在一些具體例中,基於矽碳複合材料顆粒200之重量為100重量百分比,矽碳複合材料顆粒200之碳含量可為12重量百分比至29重量百分比。In some embodiments, based on 100% by weight of the silicon-
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 they are not intended to limit the present invention. Anyone skilled in this art can make various changes and modifications without departing from the spirit and scope of the present invention.
矽碳複合材料顆粒之製備Preparation of Silicon Carbon Composite Particles
實施例1Example 1
實施例1之矽碳複合材料的製備係以粒徑為0.05mm之釔穩定氧化鋯珠研磨微米級矽晶圓切削廢料,以獲得含有矽粒子之研磨液。於研磨液中加入煤焦油瀝青(型號為RBP-85,軟化溫度為85℃,固定碳為40重量百分比,製造商為中鋼碳素公司),加熱至160℃,攪拌30分鐘進行包覆,然後升溫至310℃除去溶劑,而獲得瀝青包覆顆粒。於氮氣下進行碳化,而獲得矽碳複合顆粒。然後,以震動研磨機粉碎矽碳複合顆粒,並以400網目之篩網過篩,以獲得矽碳複合材料顆粒,其矽含量為71至88重量百分比。然後,進行後述評價試驗。The silicon-carbon composite material in Example 1 was prepared by grinding micron-sized silicon wafer cutting waste with yttrium-stabilized zirconia beads with a particle size of 0.05 mm to obtain a grinding liquid containing silicon particles. Add coal tar pitch (model is RBP-85, softening temperature is 85°C, fixed carbon is 40% by weight, manufacturer is China Steel Carbon Co., Ltd.) into the grinding liquid, heated to 160°C, stirred for 30 minutes to coat, Then, the temperature was raised to 310° C. to remove the solvent to obtain pitch-coated particles. Carbonization is carried out under nitrogen to obtain silicon-carbon composite particles. Then, the silicon-carbon composite particles were pulverized by a vibrating grinder, and sieved with a 400-mesh sieve to obtain silicon-carbon composite particles, the silicon content of which was 71 to 88% by weight. Then, an evaluation test described later was performed.
實施例2及比較例1Embodiment 2 and Comparative Example 1
實施例2及比較例1之矽碳複合材料顆粒係以與實施例1相似的方法製造。不同的是,實施例2使用一半用量之瀝青,比較例1使用不同的瀝青(型號為HSP-260,軟化溫度為260℃,固定碳為60重量百分比,製造商為中鋼碳素公司)。實施例1至2及比較例1之具體條件及評價結果如下表1所示。The silicon-carbon composite material particles of Example 2 and Comparative Example 1 were produced in a method similar to that of Example 1. The difference is that Example 2 uses half the amount of pitch, and Comparative Example 1 uses different pitch (model is HSP-260, softening temperature is 260°C, fixed carbon is 60% by weight, and the manufacturer is Sinosteel Carbon Corporation). The specific conditions and evaluation results of Examples 1 to 2 and Comparative Example 1 are shown in Table 1 below.
鋰離子電池用電極Electrodes for lithium-ion batteries
應用例1Application example 1
基於矽碳複合材料顆粒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之矽碳複合材料顆粒均勻地混入介相瀝青石墨中,以獲得負極的活性物質。再將重量比為92:1.5:3:3.5之負極的活性物質、羧甲基纖維素、丁苯橡膠及導電碳黑(由特密高(TIMCAL)公司製造,且型號為super P)調配成水性漿料。然後,以刮刀將水性漿料塗佈於銅箔上,其塗覆量為6mg/cm 2。於110℃下,經8小時真空烘烤後,以製得應用例1之負極電極(亦稱作矽碳/石墨負極電極),並使用此負極電極組裝成鋰離子電池,以進行後續評價。 Based on the total weight of silicon-carbon composite material particles and mesophase pitch graphite as 100% by weight, application example 1 is to mix 14% by weight of silicon-carbon composite material particles of Example 1 into mesophase pitch graphite evenly to obtain negative electrode active substance. Then the active material of the negative electrode, carboxymethyl cellulose, styrene-butadiene rubber and conductive carbon black (manufactured by TIMCAL, and the model is super P) with a weight ratio of 92:1.5:3:3.5 were formulated into Water-based slurry. Then, the aqueous slurry was coated on the copper foil with a doctor blade in an amount of 6 mg/cm 2 . After vacuum baking at 110°C for 8 hours, the negative electrode (also known as silicon carbide/graphite negative electrode) of Application Example 1 was prepared, and the negative electrode was used to assemble a lithium-ion battery for subsequent evaluation.
應用例2及比較應用例1Application Example 2 and Comparative Application Example 1
應用例2及比較應用例1皆以與應用例1相似的方法進行。不同的是,應用例2及比較應用例1分別使用實施例2及比較例1之矽碳複合材料顆粒。應用例1至2及比較應用例1之評價結果如下表2所示。Both application example 2 and comparative application example 1 were carried out in a method similar to application example 1. The difference is that Application Example 2 and Comparative Application Example 1 use the silicon-carbon composite material particles of Example 2 and Comparative Example 1, respectively. The evaluation results of Application Examples 1 to 2 and Comparative Application Example 1 are shown in Table 2 below.
評價方式Evaluation method
1.軟化溫度與固定碳比例之試驗1. Test of softening temperature and fixed carbon ratio
軟化溫度與固定碳比例之試驗係使用熱重分析儀,於10°C/min的升溫速率下,量測瀝青之軟化溫度及其於850℃時之失重率,並以此表示瀝青之固定碳比例,其中熱重分析圖如圖3及圖4所示。The test of the softening temperature and the ratio of fixed carbon uses a thermogravimetric analyzer to measure the softening temperature of asphalt and its weight loss rate at 850°C at a heating rate of 10°C/min, and expresses the fixed carbon of the asphalt Ratio, wherein the thermogravimetric analysis diagram is shown in Figure 3 and Figure 4.
2.平均粒徑之試驗2. Test of average particle size
平均粒徑係使用電子顯微鏡所拍攝的矽粒子及矽碳複合材料顆粒之電子顯微鏡照片來量測。The average particle size is measured by electron micrographs of silicon particles and silicon-carbon composite particles taken by an electron microscope.
3.孔洞之尺寸及分佈密度之試驗3. Test of hole size and distribution density
孔洞之尺寸及分佈密度之試驗係以電子顯微鏡觀察矽碳複合材料顆粒之單一顆粒的橫截面影像,並量測單顆矽碳複合材料顆粒之內部孔洞的尺寸,以通過孔洞的橫截面影像之質量中心之直線中最長者與最短者之平均值表示此孔洞的尺寸,並使用多個量測值的平均值來表示單顆矽碳複合材料之內部孔洞尺寸。此外,於孔洞的橫截面影像中,計算於1μm 2之面積內之孔洞數量,以此表示單顆矽碳複合材料之內部孔洞的密度。 The test of the size and distribution density of the pores is to observe the cross-sectional image of a single particle of silicon-carbon composite material particles with an electron microscope, and measure the size of the internal pores of a single silicon-carbon composite material particle, so as to pass through the cross-sectional image of the hole The average value of the longest and shortest straight lines at the center of mass represents the size of the hole, and the average value of multiple measured values is used to represent the internal hole size of a single silicon-carbon composite material. In addition, in the cross-sectional image of the holes, the number of holes within an area of 1 μm 2 is calculated to represent the density of the inner holes of a single silicon-carbon composite material.
4.比表面積之試驗4. Test of specific surface area
比表面積之試驗係以比表面積分析儀且根據BET理論測得矽碳複合材料顆粒之比表面積。The specific surface area test is to measure the specific surface area of the silicon-carbon composite particles with a specific surface area analyzer and according to the BET theory.
5.電容量之試驗5. Capacitance test
電容量之試驗係將矽碳/石墨負極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個循環。如此重複3個循環,做為化成程序,以獲得矽碳/石墨負極電極的電容量。此外,使用石墨負極電極進行前述之4個循環,以測得石墨負極電極的電容量。然後,將矽碳/石墨負極電極的電容量扣除石墨負極電極的電容量,以計算出矽碳複合材料顆粒的電容量。Capacitance test is a CR2032 button half-cell composed of silicon carbide/graphite negative electrode and carbonate electrolyte. Then charge the half-cell with a charge-discharge machine (manufactured by Arbin Instruments, model BT 2043). First charge to 0.001V with a constant current of 0.1C, then charge at a constant voltage until the current is less than 0.01C, then discharge at a constant current of 0.1C to 1.5V, and then charge at a constant voltage until the current is less than 0.01C, this is one cycle. Repeat 3 cycles in this way as a formation procedure to obtain the capacitance of the silicon carbide/graphite negative electrode. In addition, the aforementioned 4 cycles were performed using the graphite negative electrode to measure the capacitance of the graphite negative electrode. Then, the capacitance of the silicon carbon/graphite negative electrode is deducted from the capacitance of the graphite negative electrode to calculate the capacitance of the silicon-carbon composite particle.
6.循環充放電電容量維持率及首次充放電庫倫效率之試驗6. The test of cycle charge and discharge capacity maintenance rate and first charge and discharge coulombic efficiency
循環充放電電容量維持率之試驗係以與電容量測試的相同方式進行,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,且重複100個循環,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,並且使用重複100個循環所測得之循環充放電容量維持率評價循環壽命。The test of the cycle charge and discharge capacity maintenance rate is carried out in the same way as the capacity 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 repeat 100 cycles , to measure the cycle charge-discharge capacity maintenance rate, where the ratio of the discharge capacity measured for the first time to the charge capacity is called the first charge-discharge coulombic efficiency, and the cycle charge-discharge capacity retention rate measured by repeating 100 cycles is used for evaluation cycle life.
表1 Table 1
表2 Table 2
請參閱表1及圖3至8,相較於使用過高的軟化溫度及固定碳比例的瀝青之比較例1,實施例1至2使用適當的軟化溫度及固定碳比例的瀝青,故製得之矽碳複合材料顆粒具有多孔結構,碳基質包覆矽粒子,且於矽碳複合材料顆粒之橫截面中,實施例1之孔洞(如圖5所示)及實施例2之孔洞(如圖6至7所示)具有適當的尺寸及分佈密度,從而提升負極電極的電容量。然而,比較例1之矽碳複合材料顆粒不具有多孔結構(如圖8所示),故降低負極電極的電容量。Please refer to Table 1 and Figures 3 to 8, compared with Comparative Example 1 using too high softening temperature and fixed carbon ratio pitch, Examples 1 to 2 use appropriate softening temperature and fixed carbon ratio pitch, so obtained The silicon-carbon composite material particles have a porous structure, and the carbon matrix coats the silicon particles, and in the cross-section of the silicon-carbon composite material particles, the holes in Example 1 (as shown in Figure 5) and the holes in Example 2 (as shown in Figure 5) 6 to 7) have appropriate size and distribution density, thereby improving the capacitance of the negative electrode. However, the silicon-carbon composite particles of Comparative Example 1 do not have a porous structure (as shown in FIG. 8 ), thus reducing the capacitance of the negative electrode.
綜上所述,本發明之矽碳複合材料顆粒及其製造方法係利用均勻分散於碳基質中之複數個矽粒子及複數個孔洞,以及於矽碳複合材料顆粒之橫截面中,此些孔洞所具有之特定的尺寸及特定的分佈密度,以提升所製得之負極電極的電容量。In summary, the silicon-carbon composite particle and its manufacturing method of the present invention utilize a plurality of silicon particles and a plurality of holes uniformly dispersed in the carbon matrix, and in the cross-section of the silicon-carbon composite particle, these holes It has a specific size and a specific distribution density to improve the capacitance of the prepared negative electrode.
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 above in terms of implementation, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various modifications and changes without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.
100:方法
110,120,130:操作
200:矽碳複合材料顆粒
210:矽粒子
220:孔洞
d,D:粒徑
230:碳基質
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一實施例的矽碳複合材料顆粒之製造方法的流程圖。 圖2係繪示根據本發明之一實施例的矽碳複合材料顆粒之示意圖。 圖3係繪示根據本發明之實施例1及實施例2的煤焦油系列瀝青之熱重分析圖。 圖4係繪示根據本發明之比較例1的煤焦油系列瀝青之熱重分析圖。 圖5係顯示根據本發明之實施例1的矽碳複合材料顆粒之橫截面的電子顯微鏡照片。 圖6與圖7係顯示根據本發明之實施例2的矽碳複合材料顆粒之橫截面的電子顯微鏡照片。 圖8係顯示根據本發明之比較例1的矽碳複合材料顆粒之橫截面的電子顯微鏡照片。 In order to have a more complete understanding of the embodiments of the present invention and their advantages, please refer to the following descriptions together with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of relevant diagrams are explained as follows: FIG. 1 is a flowchart illustrating a method for manufacturing silicon-carbon composite material particles according to an embodiment of the present invention. FIG. 2 is a schematic diagram illustrating silicon-carbon composite material particles according to an embodiment of the present invention. FIG. 3 is a thermogravimetric analysis diagram of coal tar series pitch according to Embodiment 1 and Embodiment 2 of the present invention. Fig. 4 is a graph showing the thermogravimetric analysis of the coal tar series pitch according to Comparative Example 1 of the present invention. FIG. 5 is an electron micrograph showing the cross-section of the silicon-carbon composite particle according to Example 1 of the present invention. 6 and 7 are electron micrographs showing the cross-section of the silicon-carbon composite particle according to Example 2 of the present invention. FIG. 8 is an electron micrograph showing the cross-section of the silicon-carbon composite particle according to Comparative Example 1 of the present invention.
200:矽碳複合材料顆粒 200: silicon carbon composite particles
210:矽粒子 210: silicon particles
220:孔洞 220: hole
d,D:粒徑 d, D: particle size
230:碳基質 230: carbon matrix
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