TWI805224B - Carbon material for energy storage, method for producing the same, electrode for supercapacitor and supercapacitor - Google Patents
Carbon material for energy storage, method for producing the same, electrode for supercapacitor and supercapacitor Download PDFInfo
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本發明係有關於一種儲能用碳材、其製造方法、超電容器用電極片及超電容器，且特別是有關於一種具有低細粉含量之儲能用碳材、其製造方法，以及包含其之超電容器用電極片與超電容器。The present invention relates to a carbon material for energy storage, a manufacturing method thereof, an electrode sheet for a supercapacitor, and a supercapacitor, and in particular to a carbon material for energy storage with low fine powder content, a manufacturing method thereof, and a carbon material containing the same Electrode sheets and supercapacitors for supercapacitors.
超電容器係一種具有高功率密度及長循環充放電壽命之儲能元件。此超電容器可分為電雙層電容器(double layer capacitor)及擬電容器(pseudo-capacitor)。電雙層電容器係利用在電極與電解液的界面間之庫侖靜電力造成的電荷分離，以達成儲能的目的。電解液中之陰離子與陽離子分別吸附於超電容器之正電極及負電極的表面，故電極的表面特性影響超電容器的性能。A supercapacitor is an energy storage element with high power density and long cycle charge and discharge life. The supercapacitor can be divided into double layer capacitor and pseudo-capacitor. Electric double-layer capacitors use the charge separation caused by the Coulomb electrostatic force between the electrode and the electrolyte interface to achieve the purpose of energy storage. The anions and cations in the electrolyte are adsorbed on the surface of the positive electrode and the negative electrode of the supercapacitor respectively, so the surface characteristics of the electrodes affect the performance of the supercapacitor.
電極材料包含儲能用碳材，其具有高比表面積及特殊的孔洞性質，以使所製之電極片能夠具有良好的電化學特性，從而滿足超電容器的需求。然而，於循環充放電過程中，電解液分解而產生氣體，此氣體容易蓄積於碳材所製之電極片的碳膜中，故導致超電容器的阻抗隨著時間而劇烈增加，故降低超電容器的壽命。The electrode material includes carbon material for energy storage, which has a high specific surface area and special pore properties, so that the prepared electrode sheet can have good electrochemical properties, thereby meeting the needs of supercapacitors. However, during the cycle charge and discharge process, the electrolyte decomposes to generate gas, which is easy to accumulate in the carbon film of the electrode sheet made of carbon material, which causes the impedance of the supercapacitor to increase sharply with time, thus reducing the supercapacitor lifespan.
有鑑於此，亟需發展一種新的儲能用碳材之製造方法，以改善習知的儲能用碳材、超電容器用電極片及超電容器之上述缺點。In view of this, there is an urgent need to develop a new method of manufacturing carbon materials for energy storage to improve the above-mentioned shortcomings of conventional carbon materials for energy storage, electrode sheets for supercapacitors, and supercapacitors.
有鑑於上述之問題，本發明之一態樣是在提供一種儲能用碳材之製造方法。此製造方法係藉由特定平均粒徑之碳素原料及特定的活化溫度來製造具有特定平均粒徑及低細粉含量之儲能用碳材，從而增長所製之超電容器用電極片及超電容器的壽命。In view of the above problems, one aspect of the present invention is to provide a method for manufacturing a carbon material for energy storage. This manufacturing method is to manufacture carbon materials for energy storage with a specific average particle size and low fine powder content by using carbon raw materials with a specific average particle size and a specific activation temperature, thereby increasing the electrode sheets for supercapacitors and supercapacitors produced. life of the capacitor.
本發明之另一態樣是在提供一種儲能用碳材，其係利用前述之儲能用碳材之製造方法製得。Another aspect of the present invention is to provide a carbon material for energy storage, which is obtained by using the above-mentioned manufacturing method of the carbon material for energy storage.
本發明之又一態樣是在提供一種超電容器用電極片，其包含碳膜。此碳膜包含如前述之儲能用碳材。Another aspect of the present invention is to provide an electrode sheet for a supercapacitor, which includes a carbon film. The carbon film includes the aforementioned carbon material for energy storage.
本發明之又一態樣是在提供一種超電容器。此超電容器包含二電極片，其係如前述之超電容器用電極片。Another aspect of the present invention is to provide a supercapacitor. The supercapacitor includes two electrode sheets, which are electrode sheets for a supercapacitor as described above.
根據本發明之一態樣，提出一種儲能用碳材之製造方法。此製造方法係提供碳素原料，再於惰性氣體中，對碳素原料及活化處理劑進行活化處理，以獲得活化後碳材。碳素原料之平均粒徑為8μm至50μm，且活化處理之活化溫度為780℃至900℃，活化處理劑及碳素原料之重量比值為2至3。基於儲能用碳材之重量為100重量百分比，儲能用碳材之細粉含量為大於0重量百分比且不大於2重量百分比。According to an aspect of the present invention, a method for manufacturing a carbon material for energy storage is proposed. The manufacturing method is to provide carbon raw materials, and then activate the carbon raw materials and activation treatment agent in an inert gas to obtain activated carbon materials. The average particle diameter of the carbon raw material is 8 μm to 50 μm, and the activation temperature of the activation treatment is 780° C. to 900° C., and the weight ratio of the activation treatment agent to the carbon raw material is 2 to 3. Based on the weight of the carbon material for energy storage as 100% by weight, the fine powder content of the carbon material for energy storage is greater than 0% by weight and not greater than 2% by weight.
依據本發明之一實施例，碳素原料包含煤焦油瀝青、石油瀝青、醛酚樹脂及/或經碳化的植物。According to an embodiment of the present invention, the carbon raw material includes coal tar pitch, petroleum pitch, aldehyde resin and/or carbonized plants.
依據本發明之另一實施例，活化處理劑包含鹼金族金屬及/或鹼土族金屬之氫氧化物。According to another embodiment of the present invention, the activation treatment agent includes hydroxides of alkali metals and/or alkaline earth metals.
依據本發明之又一實施例，活化處理之活化時間為3小時至7小時。According to another embodiment of the present invention, the activation time of the activation treatment is 3 hours to 7 hours.
依據本發明之又一實施例，於進行活化處理前，儲能用碳材之製造方法更包含預加熱步驟，以融化活化處理劑，且預加熱步驟之加熱溫度為不小於350℃。According to another embodiment of the present invention, before the activation treatment, the manufacturing method of the carbon material for energy storage further includes a preheating step to melt the activation treatment agent, and the heating temperature in the preheating step is not less than 350°C.
本發明之又一態樣係提供一種儲能用碳材。此儲能用碳材利用如前述之儲能用碳材之製造方法製得，其中儲能用碳材之平均粒徑為8μm至50μm。Another aspect of the present invention is to provide a carbon material for energy storage. The carbon material for energy storage is produced by the method for producing the carbon material for energy storage, wherein the average particle size of the carbon material for energy storage is 8 μm to 50 μm.
依據本發明之一實施例，於2.0nm至50nm的孔徑範圍內，儲能用碳材之中孔容積為0.8m 3/g至1.5m 3/g。 According to an embodiment of the present invention, within the pore diameter range of 2.0 nm to 50 nm, the mesopore volume of the carbon material for energy storage is 0.8 m 3 /g to 1.5 m 3 /g.
依據本發明之另一實施例，根據BET氮吸附法，儲能用碳材之比表面積為2000m 2/g至3000m 2/g。 According to another embodiment of the present invention, according to the BET nitrogen adsorption method, the specific surface area of the carbon material for energy storage is 2000m 2 /g to 3000m 2 /g.
本發明之又一態樣係提供一種超電容器用電極片。此超電容器用電極片包含基材及設置於基材上之碳膜，其中碳膜包含如前述之儲能用碳材。Yet another aspect of the present invention provides an electrode sheet for a supercapacitor. The electrode sheet for a supercapacitor includes a base material and a carbon film disposed on the base material, wherein the carbon film includes the aforementioned carbon material for energy storage.
本發明之又一態樣係提供一種超電容器。此超電容器包含容器、二電極片、隔離元件及電解液。此些電極片置於容器內，且係如前述之超電容器用電極片。隔離元件置於容器內，且位於此些電極片之間。電解液填充於容器內，且與此些電極片接觸。Yet another aspect of the present invention provides a supercapacitor. The supercapacitor includes a container, two electrode sheets, an isolation element and an electrolytic solution. These electrode sheets are placed in the container, and are the electrode sheets for supercapacitors as mentioned above. The isolation element is placed in the container and between the electrode sheets. The electrolyte solution is filled in the container and is in contact with the electrode sheets.
應用本發明之儲能用碳材及其製造方法，其中藉由特定平均粒徑之碳素原料及特定的活化溫度，以製造具有特定平均粒徑及低細粉含量之儲能用碳材，從而增長所製之超電容器用電極片及超電容器的壽命。Applying the carbon material for energy storage of the present invention and its manufacturing method, wherein the carbon material for energy storage with a specific average particle size and low fine powder content is produced by using a carbon raw material with a specific average particle size and a specific activation temperature, Thereby prolonging the service life of the manufactured electrode sheets for supercapacitors and supercapacitors.
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.
本發明之儲能用碳材之製造方法係藉由特定平均粒徑(例如：8μm至50μm)之碳素原料及特定的活化溫度(例如：780℃至900℃)來製造具有特定平均粒徑(例如：8μm至50μm)及低細粉含量(例如：大於0重量百分比且不大於2重量百分比)之儲能用碳材。具有特定平均粒徑的儲能用碳材所製得之漿料利於設置於基材上，所形成之碳膜不存在缺陷(例如：破裂)，且少量的儲能用碳材之細粉可填充於儲能用碳材之較大顆粒的孔隙中，以提高顆粒間的連結，且不阻礙電解溶液於充放電過程中所產生之氣體的釋出，從而增長所製之超電容器用電極片及超電容器的壽命。The manufacturing method of the carbon material for energy storage of the present invention is to manufacture a carbon material with a specific average particle size (for example: 8 μm to 50 μm) and a specific activation temperature (for example: 780°C to 900°C) Carbon materials for energy storage (for example: 8 μm to 50 μm) and low fine powder content (for example: greater than 0 weight percent and not greater than 2 weight percent). The slurry prepared from the carbon material for energy storage with a specific average particle size is beneficial to be placed on the substrate, the formed carbon film has no defects (such as: cracking), and a small amount of fine powder of the carbon material for energy storage can be Fill in the pores of larger particles of carbon materials for energy storage to improve the connection between particles and not hinder the release of gas generated by the electrolytic solution during charging and discharging, thereby increasing the electrode sheet for supercapacitors produced and the life of the supercapacitor.
請參閱圖1，儲能用碳材之製造方法100係先提供碳素原料，如操作110所示。碳素原料之平均粒徑為8μm至50μm。倘若碳素原料之平均粒徑小於8μm，所製之儲能用碳材之平均粒徑小於8μm，太小的儲能用碳材堆積緊密而形成結構密實之碳膜，不利於電極片在循環充放電過程中之電解液分解產生之氣體從碳膜排出，故縮短超電容器的壽命。倘若碳素原料之平均粒徑大於50μm，所製之碳膜結構鬆散，故於循環充放電時碳膜損壞，而縮短超電容器的壽命。較佳地，碳素原料之平均粒徑可為15μm至50μm，更佳可為20μm至30μm。Please refer to FIG. 1 , the
前述之碳素原料可包含但不限於煤焦油瀝青、石油瀝青、醛酚樹脂及/或經碳化的植物。舉例而言，利用大於800℃之高溫來碳化處理植物，即可獲得經碳化的植物，其中植物可包含但不限於綠色植物，例如：榕樹的葉子。此外，在一些具體例中，碳素原料可為活性碳，其可具有孔洞，而此孔洞的分佈可用來做為挑選植物之依據，此乃由於不同的植物具有不同尺寸之細胞，故碳化成具有不同孔洞分佈之活性碳。The aforementioned carbon raw materials may include but not limited to coal tar pitch, petroleum pitch, aldehyde phenol resin and/or carbonized plants. For example, carbonized plants can be obtained by carbonizing plants at a high temperature greater than 800° C., wherein the plants include but are not limited to green plants, such as leaves of banyan trees. In addition, in some specific examples, the carbon raw material can be activated carbon, which can have pores, and the distribution of the pores can be used as a basis for selecting plants. This is because different plants have cells of different sizes, so carbonization forms Activated carbon with different pore distribution.
於操作110後，在惰性氣體中，對碳素原料及活化處理劑進行活化處理，以獲得活化後碳材，如操作120所示。此惰性氣體係避免碳素原料於活化處理中劇烈氧化而耗盡(例如：燃燒)。在一些實施例中，惰性氣體可包含氮氣、氬氣及其組合物。在一些具體例中，前述活化處理劑可包含鹼金族金屬及/或鹼土族金屬之氫氧化物。具體而言，活化處理劑可為但不限於氫氧化鉀、氫氧化鈉、氫氧化鎂、氫氧化鈣及其組合物。After
活化處理係利用活化處理劑氧化碳素原料的表面，以製造高比表面積及高中孔容積之儲能用碳材。活化處理劑及碳素原料之重量比值為2至3。倘若活化處理劑及碳素原料之重量比值小於2，所製之儲能用碳材的比表面積及/或中孔容積過小，故降低所製之超電容器的功率及壽命。倘若活化處理劑及碳素原料之重量比值大於3，所製之儲能用碳材的平均粒徑過小及/或細粉含量過多，而導致所製之碳膜結構過於緊密，故不利於在循環充放電過程產生之氣體排出，故縮短超電容器的壽命。較佳地，活化處理劑及碳素原料之重量比值可為2.5至3.0。Activation treatment is to use an activation treatment agent to oxidize the surface of carbon raw materials to produce carbon materials for energy storage with high specific surface area and high and medium pore volume. The weight ratio of the activation treatment agent and the carbon raw material is 2-3. If the weight ratio of the activation treatment agent and the carbon raw material is less than 2, the specific surface area and/or mesopore volume of the produced carbon material for energy storage are too small, thus reducing the power and life of the produced supercapacitor. If the weight ratio of the activation treatment agent to the carbon raw material is greater than 3, the average particle size of the prepared carbon material for energy storage is too small and/or the fine powder content is too much, which will cause the prepared carbon film structure to be too tight, so it is not conducive to The gas generated during the cyclic charging and discharging process is discharged, which shortens the life of the supercapacitor. Preferably, the weight ratio of the activation treatment agent to the carbon raw material can be 2.5 to 3.0.
活化處理之活化溫度為780℃至900℃。倘若活化溫度小於780℃，碳素原料活化不完全，故儲能用碳材的比表面積及/或中孔容積過小，而降低所製之超電容器的功率及壽命。倘若活化溫度大於900℃，碳素原料過度活化，而導致儲能用碳材的平均粒徑過小及/或細粉含量過多，不利於電解液產生之氣體排出，故縮短超電容器的壽命。較佳地，活化溫度可為800℃至900℃。The activation temperature of the activation treatment is 780°C to 900°C. If the activation temperature is lower than 780°C, the activation of the carbon material is incomplete, so the specific surface area and/or mesopore volume of the carbon material for energy storage are too small, which reduces the power and life of the supercapacitor produced. If the activation temperature is higher than 900°C, the carbon material will be overactivated, resulting in too small an average particle size of the energy storage carbon material and/or too much fine powder content, which is not conducive to the discharge of the gas generated by the electrolyte, thus shortening the life of the supercapacitor. Preferably, the activation temperature may be 800°C to 900°C.
在一些實施例中，活化時間可為3小時至7小時，且較佳可為4小時至6小時。當活化時間為前述之範圍時，利於製得高比表面積及高中孔容積之碳素原料，且使得所製之儲能用碳材具備低細粉含量，從而提升所製之超電容器的功率及壽命。In some embodiments, the activation time may be 3 hours to 7 hours, and preferably 4 hours to 6 hours. When the activation time is within the aforementioned range, it is beneficial to prepare carbon raw materials with high specific surface area and high and medium pore volume, and make the prepared carbon material for energy storage have low fine powder content, thereby improving the power and capacity of the prepared supercapacitor. life.
在一些具體例中，於活化處理前，儲能用碳材之製造方法可選擇性包含預加熱步驟，以融化活化處理劑，且預加熱步驟之加熱溫度為不小於350℃。當加熱溫度為不小於350℃時，利於融化活化處理劑，故易於混合碳素原料及活化處理劑，從而製得表面性質較均勻的儲能用碳材。此表面性質包含中孔容積及比表面積。表面性質較均勻的儲能用碳材可提升超電容器電極片的電化學活性，故更適於應用於超電容器電極片並增長超電容器的壽命。In some embodiments, before the activation treatment, the manufacturing method of the carbon material for energy storage may optionally include a preheating step to melt the activation treatment agent, and the heating temperature in the preheating step is not less than 350°C. When the heating temperature is not less than 350°C, it is beneficial to melt the activation treatment agent, so it is easy to mix the carbon raw material and the activation treatment agent, so as to obtain a carbon material for energy storage with relatively uniform surface properties. Such surface properties include mesopore volume and specific surface area. The carbon material for energy storage with a more uniform surface property can improve the electrochemical activity of the supercapacitor electrode sheet, so it is more suitable for use in the supercapacitor electrode sheet and prolongs the life of the supercapacitor.
基於儲能用碳材之重量為100重量百分比，儲能用碳材之細粉含量為大於0重量百分比且不大於2重量百分比。倘若細粉含量大於前述之範圍，過多的儲能用碳材料的細粉(即儲能用碳材料的較小顆粒，其粒徑小於1μm)填充於儲能用碳材料的較大顆粒之孔隙中，而大幅地降低活性碳電極片的孔隙度。在循環充放電過程中電解液分解產生之氣體將蓄積於電極片的碳膜中，而導致阻抗隨著時間劇烈增加，故縮短超電容器的壽命。Based on the weight of the carbon material for energy storage as 100% by weight, the fine powder content of the carbon material for energy storage is greater than 0% by weight and not greater than 2% by weight. If the fine powder content is greater than the aforementioned range, too much fine powder of the carbon material for energy storage (that is, smaller particles of the carbon material for energy storage, whose particle size is less than 1 μm) fills the pores of the larger particles of the carbon material for energy storage In the process, the porosity of the activated carbon electrode sheet is greatly reduced. During the cyclic charge and discharge process, the gas generated by the decomposition of the electrolyte will accumulate in the carbon film of the electrode sheet, resulting in a sharp increase in impedance over time, thus shortening the life of the supercapacitor.
請再參閱圖1，於操作120後，儲能用碳材之製造方法100可選擇性包含清潔步驟，以除去前述活化處理所殘餘的活化處理劑。Please refer to FIG. 1 again. After
本發明之另一態樣係提供一種儲能用碳材，其係利用前述之儲能用碳材之製造方法製得。儲能用碳材之平均粒徑為8μm至50μm。倘若儲能用碳材之平均粒徑小於8μm，過小之儲能用碳材料的總反應面積較大，而使電解液容易分解產生大量氣體。進而增大超電容器的阻抗且隨時間劇增，故縮短超電容器的壽命。前述儲能用碳材之平均粒徑較佳可為15μm至50μm，且更佳可為20μm至 30μm。 Another aspect of the present invention is to provide a carbon material for energy storage, which is produced by using the above-mentioned manufacturing method of the carbon material for energy storage. The average particle size of the carbon material for energy storage is 8 μm to 50 μm. If the average particle size of the carbon material for energy storage is less than 8 μm, the total reaction area of the carbon material for energy storage that is too small will be large, and the electrolyte will easily decompose and generate a large amount of gas. Furthermore, the impedance of the supercapacitor increases and increases sharply with time, so the life of the supercapacitor is shortened. The average particle size of the aforementioned carbon material for energy storage is preferably 15 μm to 50 μm, and more preferably 20 μm to 30 μm.
在一些實施例中，儲能用碳材之中孔容積可為0.8m 3/g至1.5m 3/g，且較佳可為0.8m 3/g至1.2m 3/g。當中孔容積為前述之範圍時，可提升所製之超電容器的功率及壽命。承上，儲能用碳材之比表面積可為2000m 2/g至3000m 2/g。當比表面積為前述之範圍時，可提升所製之超電容器的功率及壽命。 In some embodiments, the mesopore volume of the carbon material for energy storage may be 0.8 m 3 /g to 1.5 m 3 /g, and preferably 0.8 m 3 /g to 1.2 m 3 /g. When the volume of the middle hole is in the aforementioned range, the power and life of the manufactured supercapacitor can be improved. Based on the above, the specific surface area of the carbon material for energy storage can be 2000m 2 /g to 3000m 2 /g. When the specific surface area is in the aforementioned range, the power and life of the manufactured supercapacitor can be improved.
本發明之又一態樣是在提供一種超電容器用電極片，其包含基材及設置於基材上之碳膜。此碳膜包含如前述之儲能用碳材。在一些實施例中，基材可包含導電基材，例如：碳片或金屬片。基材的厚度可為20μm至30μm。再者，形成碳膜之漿料的組成物可包含導電材料、導電輔助劑、黏結劑及接著促進劑，其中導電材料包含前述之儲能用碳材。Another aspect of the present invention is to provide an electrode sheet for a supercapacitor, which includes a substrate and a carbon film disposed on the substrate. The carbon film includes the aforementioned carbon material for energy storage. In some embodiments, the substrate may include a conductive substrate, such as a carbon sheet or a metal sheet. The thickness of the substrate may be 20 μm to 30 μm. Furthermore, the composition of the slurry for forming the carbon film may include a conductive material, a conductive auxiliary agent, a binder, and an adhesion accelerator, wherein the conductive material includes the aforementioned carbon material for energy storage.
在一些實施例中，導電材料可選擇性包含一維及/或二維之碳材料，例如：石墨烯或奈米石墨線。導電輔助劑的具體例可包含導電碳黑，黏結劑的具體例可包含聚偏二氟乙烯(PVDF)及N-甲基吡咯烷酮(NMP)，且接著促進劑的具體例可包含可對鋁箔進行微腐蝕之化學藥劑，例如：草酸，且接著促進劑的添加量可為整體漿料重量之0.1wt.%。碳膜可利用具有通常知識者所慣用的方式塗佈於基材，並經過乾燥而製得。在一些具體例中，碳膜的厚度可依照後續超電容器之組件來決定，例如：30μm至1000μm。In some embodiments, the conductive material may optionally include one-dimensional and/or two-dimensional carbon materials, such as graphene or graphite nanowires. Specific examples of the conductive auxiliary agent may include conductive carbon black, specific examples of the binder may include polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP), and then specific examples of the accelerator may include aluminum foil. Chemical agents for micro-corrosion, such as oxalic acid, and then the addition of accelerators can be 0.1wt.% of the weight of the overall slurry. The carbon film can be prepared by coating the substrate in a conventional manner and drying it. In some specific examples, the thickness of the carbon film can be determined according to the components of the subsequent supercapacitor, for example: 30 μm to 1000 μm.
本發明之又一態樣是在提供一種超電容器。此超電容器包含容器、置於容器內之二電極片、隔離元件及填充於容器內之電解液。此二電極片之至少一者係如前述之超電容器用電極片，而剩餘者可使用具有通常知識者所慣用的電極片。隔離元件位於前述二個電極片之間，且電解液與前述二個電極片接觸。在一些實施例中，超電容器可利用具有通常知識者所慣用的組件組裝而成。舉例而言，組裝成CR2032鈕扣電容器及360F超電容器。Another aspect of the present invention is to provide a supercapacitor. The supercapacitor includes a container, two electrode sheets placed in the container, an isolation element and electrolyte solution filled in the container. At least one of the two electrode sheets is the aforementioned electrode sheet for a supercapacitor, and the remaining electrode sheets can be used by those with ordinary knowledge. The isolation element is located between the aforementioned two electrode sheets, and the electrolyte is in contact with the aforementioned two electrode sheets. In some embodiments, ultracapacitors can be assembled using components conventional to those of ordinary skill. For example, assembled into CR2032 button capacitors and 360F supercapacitors.
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.
儲能用碳材料之製造Manufacture of carbon materials for energy storage
實施例1Example 1
實施例1之儲能用碳材料係混合由煤焦油瀝青所製之碳素原料(即活性碳顆粒)與KOH，KOH與碳素原料之重量比率為2.75，其中煤焦油瀝青之QI為大於95%，且碳素原料之平均粒徑為3.30μm。然後，於高溫爐中進行活化反應，其中第一階段於氮氣氣氛下，以0.5℃/min至3℃/min的升溫速率升溫至520℃，持溫2小時，再以0.5℃/min至2.5℃/min的升溫速率升溫至780℃，持溫1.5小時，再以0.1℃/min至1.0℃/min的升溫速率升溫至800℃，持溫5小時。完成活化反應後，通入水蒸氣5小時至8小時後，再依序經過濾、酸洗及熱水清洗步驟後，獲得實施例1之儲能用碳材料。然後以後述之評價方式進行評價。The carbon material for energy storage in Example 1 is mixed with carbon raw material (i.e. activated carbon particles) made of coal tar pitch and KOH, the weight ratio of KOH and carbon raw material is 2.75, wherein the QI of coal tar pitch is greater than 95 %, and the average particle size of the carbon raw material is 3.30 μm. Then, the activation reaction was carried out in a high-temperature furnace. In the first stage, under nitrogen atmosphere, the temperature was raised to 520°C at a rate of 0.5°C/min to 3°C/min, and the temperature was maintained for 2 hours, and then the temperature was raised to 2.5°C at a rate of 0.5°C/min to 2.5°C. The temperature was raised to 780°C at a heating rate of ℃/min, and the temperature was maintained for 1.5 hours, and then the temperature was raised to 800°C at a heating rate of 0.1°C/min to 1.0°C/min, and the temperature was maintained for 5 hours. After the activation reaction is completed, water vapor is introduced for 5 to 8 hours, and then filtered, pickled and washed with hot water in sequence to obtain the carbon material for energy storage in Example 1. Then, the evaluation was performed by the evaluation method described later.
實施例2至3及比較例1至4Examples 2 to 3 and Comparative Examples 1 to 4
實施例2至3及比較例1至4之儲能用碳材料係以與實施例1相似的方法製造。不同的是，實施例2至3及比較例1至4改變煤焦油瀝青的平均粒徑及活化處理的條件。前述實施例1至3及比較例1至4之具體條件及評價結果如下表1所示。The carbon materials for energy storage in Examples 2 to 3 and Comparative Examples 1 to 4 were produced in a method similar to that of Example 1. The difference is that in Examples 2 to 3 and Comparative Examples 1 to 4, the average particle size of coal tar pitch and the conditions of activation treatment were changed. The specific conditions and evaluation results of the aforementioned Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1 below.
鈕扣電容器及超電容器之製造Manufacture of button capacitors and supercapacitors
應用例1Application example 1
應用例1之鈕扣電容器係將實施例1之儲能用碳材料於120℃烘乾24小時，再依照表2所示之配方配製漿料，以製得黏度為2000cps至3000cps之漿料。接續，以塗佈棒塗佈漿料於厚度為20μm至30μm的鋁箔上，碳膜的厚度為180μm至200μm，於115℃烘烤40分鐘，再經裁切，以獲得厚度為100μm至120μm且面積約1.30cm 2(其寬度為10cm至20cm)的二片活性碳電極片。於此二片活性碳電極片間放置隔離紙後，滴入1M的四氟硼酸四乙基銨(tetraethylammonium tetrafluoroborate，TEABF4)之電解液，再以金屬套件組裝成應用例1之CR2032鈕扣電容。 The button capacitor of Application Example 1 is to dry the carbon material for energy storage in Example 1 at 120°C for 24 hours, and then prepare a slurry according to the formula shown in Table 2 to obtain a slurry with a viscosity of 2000cps to 3000cps. Next, use a coating bar to coat the slurry on an aluminum foil with a thickness of 20 μm to 30 μm, and a carbon film with a thickness of 180 μm to 200 μm, bake at 115° C. for 40 minutes, and then cut to obtain a thickness of 100 μm to 120 μm and Two activated carbon electrode sheets with an area of about 1.30cm 2 (with a width of 10cm to 20cm). After placing the release paper between the two activated carbon electrodes, drop 1M tetraethylammonium tetrafluoroborate (TEABF4) electrolyte, and then assemble the CR2032 button capacitor of application example 1 with the metal kit.
另外，拿取二片如前述之活性碳電極片，於此二片活性碳電極片間放置隔離紙後，捲繞夾著隔離紙的二片活性碳電極片成捲，再經乾燥後，於手套箱內滴入1M的TEABF4之電解液至此二片活性碳電極片間的空間內，再封蓋組裝，以獲得應用例1之超電容器。然後以後述之評價方式進行評價。In addition, take two activated carbon electrode sheets as mentioned above, place a release paper between the two activated carbon electrode sheets, wind the two activated carbon electrode sheets sandwiching the release paper into a roll, and then dry them in the Drop 1M TEABF4 electrolyte into the space between the two activated carbon electrodes in the glove box, and then cover and assemble to obtain the supercapacitor of application example 1. Then, the evaluation was performed by the evaluation method described later.
應用例2至3及比較應用例1至4Application Examples 2 to 3 and Comparative Application Examples 1 to 4
應用例2至3及比較應用例1至4之鈕扣電容器及超電容器係以與應用例1相似的方法製造。不同的是，應用例2至3及比較應用例1至4分別使用實施例2至3及比較例1至4之儲能用碳材料。前述應用例1至3及比較應用例1至4之鈕扣電容器及超電容器之具體條件及評價結果如下表2至4所示。The button capacitors and supercapacitors of Application Examples 2 to 3 and Comparative Application Examples 1 to 4 were manufactured in a method similar to Application Example 1. The difference is that application examples 2 to 3 and comparative application examples 1 to 4 respectively use the carbon materials for energy storage in examples 2 to 3 and comparative examples 1 to 4. The specific conditions and evaluation results of the aforementioned application examples 1 to 3 and comparative application examples 1 to 4 of the button capacitors and supercapacitors are shown in Tables 2 to 4 below.
評價方式Evaluation method
1.儲能用碳材料的平均粒徑之試驗1. Test of the average particle size of carbon materials for energy storage
儲能用碳材料的平均粒徑之試驗係以粒徑分析儀(由Malvern公司製造，且型號為Mastersizer 3000)量測儲能用碳材料的平均粒徑，其試驗條件如具有通常知識者所慣用之條件。The test of the average particle size of the carbon material for energy storage is to measure the average particle size of the carbon material for energy storage with a particle size analyzer (manufactured by Malvern, and the model is Mastersizer 3000), and the test conditions are as known by those with ordinary knowledge. customary conditions.
2.儲能用碳材料的比表面積之試驗2. Test of specific surface area of carbon materials for energy storage
儲能用碳材料的比表面積之試驗係以比表面積分析儀，並藉由BET法(Brunauer-Emmett-Teller Method)計算出儲能用碳材料的比表面積，其試驗條件如具有通常知識者所慣用之條件。The specific surface area of the carbon material for energy storage is tested with a specific surface area analyzer, and the specific surface area of the carbon material for energy storage is calculated by the BET method (Brunauer-Emmett-Teller Method). The test conditions are as known by those with ordinary knowledge. customary conditions.
3.儲能用碳材料的中孔容積之試驗3. Test of mesopore volume of carbon materials for energy storage
儲能用碳材料的中孔容積之試驗係以孔洞分析儀(由micromeritics公司製造，且型號為Tristar)，並藉由BJH法(Barrett-Joyner-Halenda Method)計算出儲能用碳材料於2.0nm至50nm的孔徑範圍內之中孔容積，其試驗條件如具有通常知識者所慣用之條件。The test of the mesopore volume of the carbon material for energy storage is based on a pore analyzer (manufactured by micromeritics, and the model is Tristar), and the carbon material for energy storage is calculated at 2.0 by the BJH method (Barrett-Joyner-Halenda Method). Mesopore volume in the range of pore diameters from nm to 50nm, the test conditions are those commonly used by those with ordinary knowledge.
4.儲能用碳材料的細粉含量之試驗4. Test of fine powder content of carbon materials for energy storage
儲能用碳材料的細粉含量之試驗係以10000目的篩網過篩儲能用碳材料，以獲得粒徑小於1μm的儲能用碳材料顆粒，並以其重量佔全部儲能用碳材料的重量百分比表示細粉含量。The test for the fine powder content of carbon materials for energy storage is to sieve the carbon materials for energy storage with a 10,000-mesh sieve to obtain carbon material particles for energy storage with a particle size of less than 1 μm, and account for the weight of the carbon materials for energy storage The weight percentage of represents the fine powder content.
5.鈕扣電容器及超電容器的阻抗試驗5. Impedance test of button capacitors and supercapacitors
鈕扣電容及超電容器的阻抗試驗係使用電化學分析儀(由CH Instruments公司製造，且型號為CHI 6273D)，以50mV/s的掃描速率進行電流/伏特之電化學掃描，以量測鈕扣電容器及超電容器的阻抗。The impedance test of button capacitance and supercapacitor uses an electrochemical analyzer (manufactured by CH Instruments, and the model is CHI 6273D) to perform electrochemical scanning of current/volt at a scan rate of 50mV/s to measure button capacitors and supercapacitors. The impedance of the supercapacitor.
6.超電容器的壽命試驗6. Life test of supercapacitor
超電容器的壽命試驗係於65℃下，維持電壓在2.7V，並使用充放電儀(由Arbin公司製造，且型號為BT2043)量測超電容器的阻抗隨著老化時間的變化(即阻抗上升率)，以阻抗上升率評價超電容器的抗老化能力，並由抗老化能力來預估超電容器的壽命。當2000小時的老化時間之阻抗上升率不大於50%時，此超電容器具有良好的抗老化能力，而具備長壽命。The life test of the supercapacitor is at 65°C, the voltage is maintained at 2.7V, and the charge and discharge instrument (manufactured by Arbin, and the model is BT2043) is used to measure the change of the impedance of the supercapacitor with the aging time (ie, the impedance rise rate ), the anti-aging ability of the supercapacitor is evaluated by the impedance rising rate, and the life of the supercapacitor is estimated by the anti-aging ability. When the impedance increase rate of the 2000-hour aging time is not more than 50%, the supercapacitor has good aging resistance and long life.
表1
表2
表3
表4
請參閱表1及3，相較於比較例1，實施例1至3之儲能用碳材料之製造方法使用適當的平均粒徑(23.8μm至48.25μm)之煤焦油瀝青，故所製之儲能用碳材料的平均粒徑落於23.80μm至48.52μm之範圍內，且細粉含量不大於2重量百分比，而使所製之鈕扣電容及超電容(即應用例1至3)具有較低的阻抗與較佳的抗老化能力。Please refer to Tables 1 and 3. Compared with Comparative Example 1, the manufacturing method of carbon materials for energy storage in Examples 1 to 3 uses coal tar pitch with an appropriate average particle size (23.8 μm to 48.25 μm), so the prepared The average particle size of the carbon material for energy storage falls within the range of 23.80 μm to 48.52 μm, and the fine powder content is not more than 2 weight percent, so that the button capacitors and supercapacitors (i.e. application examples 1 to 3) made have relatively high Low impedance and better anti-aging ability.
相較於比較例2，實施例1至3之儲能用碳材料之製造方法未進行粉碎處理，故其所製之儲能用碳材料的細粉含量較低。因此，應用例1與3之鈕扣電容及超電容的阻抗不隨時間劇烈增加，且具有較佳之抗老化能力。Compared with Comparative Example 2, the manufacturing methods of the carbon materials for energy storage in Examples 1 to 3 are not pulverized, so the fine powder content of the carbon materials for energy storage produced is lower. Therefore, the impedance of the button capacitors and supercapacitors in Application Examples 1 and 3 does not increase sharply with time, and has better anti-aging ability.
相較於比較例3及4，實施例1至3之儲能用碳材料之製造方法使用適當的活化處理條件(包含800℃至900℃的活化溫度)，故所製之儲能用碳材料具有適當之的平均粒徑與細粉含量，而使所製之鈕扣電容及超電容(即應用例1至3)具有較低的阻抗與較佳的抗老化能力。Compared with Comparative Examples 3 and 4, the manufacturing methods of the carbon materials for energy storage in Examples 1 to 3 use appropriate activation treatment conditions (including an activation temperature of 800°C to 900°C), so the prepared carbon materials for energy storage With appropriate average particle size and fine powder content, the button capacitors and supercapacitors (that is, application examples 1 to 3) have lower impedance and better anti-aging ability.
綜上所述，本發明之儲能用碳材及其製造方法，其中藉由特定平均粒徑之碳素原料及特定的活化溫度，以製造具有特定平均粒徑及低細粉含量之儲能用碳材，從而增長所製之超電容器用電極片及超電容器的壽命。To sum up, the carbon material for energy storage and its manufacturing method of the present invention, wherein the carbon raw material with a specific average particle size and a specific activation temperature are used to manufacture energy storage materials with a specific average particle size and low fine powder content Carbon material is used, thereby prolonging the service life of the electrode sheets for supercapacitors and supercapacitors produced.
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:操作 100: method 110,120: operation
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儲能用碳材之製造方法的流程圖。 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 a carbon material for energy storage according to an embodiment of the present invention.
100:方法 100: method
110,120:操作 110,120: operation
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| CN108538625A (en) * | 2010-12-28 | 2018-09-14 | 巴斯福股份公司 | Include the carbon material of the electrochemical properties of enhancing |
| TW202026236A (en) * | 2018-08-03 | 2020-07-16 | 日商積水化學工業股份有限公司 | Carbon material and method for producing same, electrode material for electrical storage device, and electrical storage device |
| TW202035132A (en) * | 2018-09-21 | 2020-10-01 | 日商日本貴彌功股份有限公司 | Electrode body, electrolytic capacitor including electrode body, and method of manufacturing electrode body |
| TW202127482A (en) * | 2019-12-18 | 2021-07-16 | 日商日本貴彌功股份有限公司 | Electrolytic capacitor |
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- 2022-02-15 TW TW111105338A patent/TWI805224B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108538625A (en) * | 2010-12-28 | 2018-09-14 | 巴斯福股份公司 | Include the carbon material of the electrochemical properties of enhancing |
| TW202026236A (en) * | 2018-08-03 | 2020-07-16 | 日商積水化學工業股份有限公司 | Carbon material and method for producing same, electrode material for electrical storage device, and electrical storage device |
| TW202035132A (en) * | 2018-09-21 | 2020-10-01 | 日商日本貴彌功股份有限公司 | Electrode body, electrolytic capacitor including electrode body, and method of manufacturing electrode body |
| TW202127482A (en) * | 2019-12-18 | 2021-07-16 | 日商日本貴彌功股份有限公司 | Electrolytic capacitor |
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