TWI593849B - Improve the hydrophilicity and conductivity of carbon fiber cloth - Google Patents
Improve the hydrophilicity and conductivity of carbon fiber cloth Download PDFInfo
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- TWI593849B TWI593849B TW105103711A TW105103711A TWI593849B TW I593849 B TWI593849 B TW I593849B TW 105103711 A TW105103711 A TW 105103711A TW 105103711 A TW105103711 A TW 105103711A TW I593849 B TWI593849 B TW I593849B
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- carbon fiber
- fiber cloth
- plasma
- hydrophilicity
- plasma treatment
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 114
- 239000004744 fabric Substances 0.000 title claims description 101
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 94
- 239000004917 carbon fiber Substances 0.000 title claims description 93
- 238000009832 plasma treatment Methods 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
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- Chemical Or Physical Treatment Of Fibers (AREA)
Description
本發明是有關於一種提昇碳纖維布的親水性及導電性的方法,特別是指一種透過電漿處理提昇碳纖維布的親水性及導電性的方法。The present invention relates to a method for improving the hydrophilicity and electrical conductivity of a carbon fiber cloth, and more particularly to a method for improving the hydrophilicity and electrical conductivity of a carbon fiber cloth by plasma treatment.
台灣專利I318243揭露一種疏水性含碳材料的製法,是為了要得到一薄膜電極之氣體擴散層以及進一步應用於燃料電池中,所以使用電漿對活性碳纖維進行改質,以增加其疏水性。經電漿改質的活性碳纖維具有優異的疏水性,並可維持良好的多孔性供氣體擴散,可有效提高燃料電池的功率輸出。Taiwan Patent No. I318243 discloses a method for preparing a hydrophobic carbonaceous material in order to obtain a gas diffusion layer of a thin film electrode and further application in a fuel cell, so that the activated carbon fiber is modified with plasma to increase its hydrophobicity. The activated carbon fiber modified by the plasma has excellent hydrophobicity and can maintain good porosity for gas diffusion, and can effectively improve the power output of the fuel cell.
然而,該疏水性含碳材料的應用有限,無法適用於各種領域,例如以鉛酸電容電池領域來說,因鉛酸電容電池的電極是直接與硫酸電解液接觸,所以該疏水性含碳材料並不適合應用在鉛酸電池電容中。However, the hydrophobic carbonaceous material has limited application and cannot be applied to various fields. For example, in the field of lead-acid capacitor batteries, since the electrode of the lead-acid capacitor battery is directly in contact with the sulfuric acid electrolyte, the hydrophobic carbonaceous material is used. Not suitable for use in lead acid battery capacitors.
基於上述,仍有必要提出一種新穎的碳纖維布的改質方法。Based on the above, it is still necessary to propose a novel modification method of carbon fiber cloth.
因此,本發明之目的,即在提供一種提昇碳纖維布的親水性及導電性的方法。Accordingly, it is an object of the present invention to provide a method of improving the hydrophilicity and electrical conductivity of a carbon fiber cloth.
於是本發明提昇碳纖維布的親水性及導電性的方法,包含以下步驟: 對一碳纖維布施予一電漿處理,使該碳纖維布與一親水性物質反應而於該碳纖維布上形成親水性官能基團,以及使該碳纖維布中的碳纖維斷裂而形成鬆散結構,且該碳纖維布經電漿處理後的親水性及導電性大於該碳纖維布電漿處理前的親水性及導電性。Therefore, the method for improving the hydrophilicity and conductivity of the carbon fiber cloth comprises the following steps: applying a plasma treatment to the carbon fiber cloth, reacting the carbon fiber cloth with a hydrophilic substance to form a hydrophilic functional group on the carbon fiber cloth. The pellet and the carbon fiber in the carbon fiber cloth are broken to form a loose structure, and the hydrophilicity and conductivity of the carbon fiber cloth after the plasma treatment are greater than the hydrophilicity and conductivity before the plasma treatment of the carbon fiber cloth.
本發明之功效:透過該電漿處理使該碳纖維布與該親水性物質反應而於該碳纖維布上形成親水性官能基團,因此提昇該碳纖維布的親水性,以及透過該電漿處理使該碳纖維布中的碳纖維斷裂而形成鬆散結構,因此提昇該碳纖維布的導電性。The effect of the present invention is that the carbon fiber cloth is reacted with the hydrophilic substance to form a hydrophilic functional group on the carbon fiber cloth by the plasma treatment, thereby improving the hydrophilicity of the carbon fiber cloth and the plasma treatment. The carbon fibers in the carbon fiber cloth are broken to form a loose structure, thereby improving the electrical conductivity of the carbon fiber cloth.
以下將就本發明內容進行詳細說明:The contents of the present invention will be described in detail below:
於本文中,該親水性官能基團例如但不限於:C=O、O-C-O、COOH、OH等。該碳纖維布的種類並無特別限制,只要經電漿處理後能使碳纖維布中的多數碳纖維被活化並與該親水性物質反應而於該等碳纖維上連接親水性官能基團,以及經電漿處理能使該等碳纖維斷裂而產生鬆散結構的碳纖維布皆適用。較佳的,該碳纖維布為活性碳纖維布(activated carbon fiber)。該親水性物質並無特別限制,只要能與電漿處理後碳纖維布中被活化的碳纖維反應並形成親水性官能基團的親水性物質皆適用。較佳地,該親水性物質是含氧的物質。較佳地,該含氧的物質是源自於大氣、氧氣電漿,或此等一組合。Herein, the hydrophilic functional group is, for example but not limited to, C=O, O-C-O, COOH, OH, and the like. The type of the carbon fiber cloth is not particularly limited as long as a plurality of carbon fibers in the carbon fiber cloth are activated by the plasma treatment and reacted with the hydrophilic substance to bond the hydrophilic functional groups to the carbon fibers, and the plasma is plasma-treated. A carbon fiber cloth which can break the carbon fibers to produce a loose structure is suitable. Preferably, the carbon fiber cloth is activated carbon fiber. The hydrophilic substance is not particularly limited as long as it can be reacted with a hydrophilic substance which reacts with activated carbon fibers in the carbon fiber cloth after the plasma treatment to form a hydrophilic functional group. Preferably, the hydrophilic substance is an oxygen-containing substance. Preferably, the oxygen containing material is derived from the atmosphere, oxygen plasma, or a combination thereof.
較佳地,該電漿處理為常壓電漿處理,使用該常壓電漿處理時,較易於控制操作條件,以及有助於大面積的碳纖維布進行電漿處理。較佳地,該電漿處理的電漿是選自於氮氣電漿、氧氣電漿、氦氣電漿、氬氣電漿,或此等一組合。該電漿處理的條件參數,例如功率範圍、流速範圍、移動速率及工作距離等並無特別限制,只要能使該碳纖維布上形成親水性官能基團以及使該等碳纖維斷裂而產生鬆散結構即可。較佳地,該電漿處理的功率範圍為50瓦至700瓦,能夠更提昇該碳纖維布經電漿處理後的親水性及導電性。較佳地,該電漿處理對該碳纖維布的單位時間處理面積範圍為222 mm 2/sec至318 mm 2/sec,能夠更提昇該碳纖維布經電漿處理後的親水性及導電性。較佳地,該電漿處理對碳纖維布的單位面積處理功率量範圍為3.18 W/mm 2至63.6 W/mm 2,能夠更提昇該碳纖維布經電漿處理後的親水性及導電性。較佳地,當進行該電漿處理時,該電漿處理使得該碳纖維布的表面的溫度範圍為50至90℃,能夠更提昇該碳纖維布經電漿處理後的親水性及導電性。該電漿處理的電漿流速範圍例如但不限於5至70 ml/min。該電漿處理的工作距離範圍為5至25 mm。該電漿處理的電漿移動速率範圍例如但不限於1至700 mm/s。 Preferably, the plasma treatment is a normal piezoelectric slurry treatment, and when the normal piezoelectric slurry is used, it is easier to control the operating conditions and to facilitate the plasma treatment of the large-area carbon fiber cloth. Preferably, the plasma treated plasma is selected from the group consisting of nitrogen plasma, oxygen plasma, helium gas plasma, argon plasma, or a combination thereof. The condition parameters of the plasma treatment, such as the power range, the flow rate range, the moving speed, and the working distance, are not particularly limited as long as the hydrophilic functional groups are formed on the carbon fiber cloth and the carbon fibers are broken to form a loose structure. can. Preferably, the plasma treatment power ranges from 50 watts to 700 watts, which can further improve the hydrophilicity and electrical conductivity of the carbon fiber cloth after plasma treatment. Preferably, the plasma treatment area of the carbon fiber cloth per unit time is in the range of 222 mm 2 /sec to 318 mm 2 /sec, which can further improve the hydrophilicity and electrical conductivity of the carbon fiber cloth after the plasma treatment. Preferably, the plasma treatment power per unit area of the carbon fiber cloth ranges from 3.18 W/mm 2 to 63.6 W/mm 2 , which can further improve the hydrophilicity and conductivity of the carbon fiber cloth after the plasma treatment. Preferably, when the plasma treatment is performed, the plasma treatment causes the surface temperature of the carbon fiber cloth to range from 50 to 90 ° C, which can further improve the hydrophilicity and conductivity of the carbon fiber cloth after the plasma treatment. The plasma treated plasma flow rate range is, for example but not limited to, 5 to 70 ml/min. The plasma treatment has a working range of 5 to 25 mm. The range of plasma movement rates of the plasma treatment is, for example but not limited to, 1 to 700 mm/s.
較佳地,該提昇碳纖維布的親水性及導電性的方法還包含一在該電漿處理之後的熱處理。透過該熱處理能使經該電漿處理後的該碳纖維布具有長效的導電性。該熱處理的操作環境並無特別限制,可在或不在真空或特定氣氛中進行。較佳地,該熱處理的溫度範圍為120至170℃。當該熱處理的溫度範圍為120至170℃時,能使得經該電漿處理後的該碳纖維布具有更長效的導電性。該熱處理的時間並無特別限制,例如但不限於2至3小時。Preferably, the method of enhancing the hydrophilicity and electrical conductivity of the carbon fiber cloth further comprises a heat treatment after the plasma treatment. The carbon fiber cloth treated by the plasma can have long-term conductivity by the heat treatment. The operating environment of the heat treatment is not particularly limited and may or may not be carried out in a vacuum or in a specific atmosphere. Preferably, the heat treatment has a temperature in the range of from 120 to 170 °C. When the temperature of the heat treatment is in the range of 120 to 170 ° C, the carbon fiber cloth treated by the plasma can be made to have longer-term conductivity. The time of the heat treatment is not particularly limited, and is, for example, but not limited to, 2 to 3 hours.
相較於未經該電漿處理的碳纖維布,經過該電漿處理的碳纖維布具有較高的親水性及導電性,其應用領域例如但不限於鉛酸電容電池。當經電漿處理的碳纖維布應用在鉛酸電容電池中,因為經電漿處理的碳纖維布中的碳纖維斷裂並形成鬆散結構所以具有較高的導電性,並且能夠吸附較多電解液中的電荷,以及因為經電漿處理的碳纖維布上形成有親水性官能基團而使電解液能夠更潤進於碳纖維布中,從而使鉛酸電容電池具有較高的電容值。Compared with the carbon fiber cloth which is not treated by the plasma, the carbon fiber cloth treated by the plasma has high hydrophilicity and electrical conductivity, and its application fields are, for example, but not limited to, lead-acid capacitor batteries. When the plasma-treated carbon fiber cloth is used in a lead-acid capacitor battery, since the carbon fiber in the plasma-treated carbon fiber cloth breaks and forms a loose structure, it has high conductivity and can adsorb more electric charge in the electrolyte. And because the hydrophilic functional group formed on the plasma-treated carbon fiber cloth enables the electrolyte to be more wetted into the carbon fiber cloth, so that the lead-acid capacitor battery has a higher capacitance value.
本發明將就以下實施例來進一步說明,但應瞭解的是,該實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。The invention is further illustrated by the following examples, which are to be construed as illustrative only and not to be construed as limiting.
[實施例1][Example 1]
電漿處理:將一活性碳纖維布(廠商:台碳科技股份有限公司,型號:AW-1114,平均比表面積為1100 m 2/g,尺寸為1030 × 1000 × 0.4 mm 3),以一常壓氮氣電漿裝置[筆式(pen-like),氮氣純度99.99%]對該活性碳纖維布施予一電漿處理,並使用一能X-Y二軸移動的控制裝置操控該常壓電漿裝置的移動。將該活性碳纖維布平放在該控制裝置的平台上後,先使該常壓電漿裝置的氮氣電漿順著該活性碳纖維布的緯線方向掃過該活性碳纖維布一次,再順著該活性碳纖維布的經線方向掃過該活性碳纖維布一次,以此做為掃描圈數「1圈」(「1圈」時的單位面積處理功率量為3.18 W/mm 2,每增加一圈,單位面積處理功率量即增一倍。)。其中,該電漿處理的功率為100瓦,該氮氣電漿的流速為15 ml/min,該氮氣電漿作用的直徑為4 mm,氮氣電漿與該活性碳纖維布間的工作距離為1.5 cm,該常壓電漿裝置的移動速率為30 mm/s。 Plasma treatment: a reactive carbon fiber cloth (manufacturer: Taiwan Carbon Technology Co., Ltd., model: AW-1114, average specific surface area of 1100 m 2 /g, size 1030 × 1000 × 0.4 mm 3 ), at a normal pressure A nitrogen plasma apparatus [pen-like, nitrogen purity of 99.99%] was subjected to a plasma treatment of the activated carbon fiber cloth, and the movement of the normal piezoelectric material device was manipulated using a control device capable of XY two-axis movement. After the activated carbon fiber cloth is placed on the platform of the control device, the nitrogen plasma of the normal piezoelectric device is swept through the activated carbon fiber cloth in the weft direction of the activated carbon fiber cloth, and then the activity is followed. The direction of the warp direction of the carbon fiber cloth is swept through the activated carbon fiber cloth once, and this is used as the number of scanning circles "1 circle" (the power per unit area when the "one circle" is 3.18 W/mm 2 , for each additional circle, the unit The amount of area processing power is doubled.). Wherein, the power of the plasma treatment is 100 watts, the flow rate of the nitrogen plasma is 15 ml/min, the diameter of the nitrogen plasma is 4 mm, and the working distance between the nitrogen plasma and the activated carbon fiber cloth is 1.5 cm. The normal piezoelectric slurry device has a moving speed of 30 mm/s.
熱處理:接著,將經電漿處理的活性碳纖維布放置在一不鏽鋼盤上,並置入一循環烘箱中,將該循環烘箱的溫度控制在150℃,熱處理2小時,得到一經改質活性碳纖維布。Heat treatment: Next, the plasma-treated activated carbon fiber cloth was placed on a stainless steel pan and placed in a circulating oven, and the temperature of the circulating oven was controlled at 150 ° C for 2 hours to obtain a modified activated carbon fiber cloth. .
[實施例2至4][Examples 2 to 4]
實施例2至4中電漿處理及熱處理的方式是與實施例1中相同,差別在於改變電漿處理的圈數。實施例1至4中電漿處理的圈數是如表1所示。The manner of plasma treatment and heat treatment in Examples 2 to 4 was the same as in Example 1, except that the number of turns of the plasma treatment was changed. The number of cycles of the plasma treatment in Examples 1 to 4 is shown in Table 1.
[比較例1][Comparative Example 1]
以市售且未經改質的活性碳纖維布(廠商:台碳科技股份有限公司,型號:AW-1114,平均比表面積為1100平方公尺/克)做為比較例1。A commercially available and unmodified activated carbon fiber cloth (manufacturer: Taiwan Carbon Technology Co., Ltd., model: AW-1114, average specific surface area: 1,100 m ^ 2 /g) was used as Comparative Example 1.
[經改質活性碳纖維布的應用]鈕扣型充電電池[Application of modified activated carbon fiber cloth] button type rechargeable battery
使用實施例1及2的經改質活性碳纖維布依照習知方式分別製備成CR2032鈕扣型電池,其中,鈕扣型充電電池的結構由下至上依序為:不鏽鋼下蓋、不銹鋼片、高親水性導電碳纖維布、PP隔離膜、高親水性導電碳纖維布、彈簧片,及不鏽鋼上蓋,並以濃度為1M的H 2SO 4做為電解液。 The modified carbon fiber cloth of Examples 1 and 2 was separately prepared into a CR2032 button type battery according to a conventional method, wherein the structure of the button type rechargeable battery was from bottom to top in order: stainless steel lower cover, stainless steel sheet, high hydrophilicity A conductive carbon fiber cloth, a PP separator, a highly hydrophilic conductive carbon fiber cloth, a spring piece, and a stainless steel upper cover, and a concentration of 1 M H 2 SO 4 as an electrolyte.
並使用比較例1未經改質活性碳纖維布依照相同的方式製備成CR2032鈕扣型電池。A CR2032 button type battery was prepared in the same manner using Comparative Example 1 unmodified activated carbon fiber cloth.
[評價項目][evaluation project]
1. 水接觸角Water contact angle
使用座滴法(Sessile Drop)量測實施例1至4的經改質活性碳纖維布,以及比較例1未經改質活性碳纖維布的水接觸角。水接觸角的結果如表1所示。The modified activated carbon fiber cloths of Examples 1 to 4 and the water contact angle of Comparative Example 1 unmodified activated carbon fiber cloth were measured using a Sessile Drop method. The results of the water contact angle are shown in Table 1.
2. X-射線光電子光譜(XPS)2. X-ray photoelectron spectroscopy (XPS)
以X光光電子能譜儀(廠商:ULVAC-PHI,型號:PHI 5000 Versaprobe II)量測實施例1至4的經改質活性碳纖維布,以及比較例1未經改質活性碳纖維布。X-射線光電子光譜的結果如表2及3所示。The modified activated carbon fiber cloths of Examples 1 to 4 and the unmodified activated carbon fiber cloth of Comparative Example 1 were measured by X-ray photoelectron spectrometer (manufacturer: ULVAC-PHI, model: PHI 5000 Versaprobe II). The results of the X-ray photoelectron spectroscopy are shown in Tables 2 and 3.
3. 傅里葉轉換紅外光譜(FTIR)3. Fourier transform infrared spectroscopy (FTIR)
以傅立葉轉換紅外線光譜分析儀(廠商:Thermo Scientific,型號:Nicilet 6700)量測實施例1至4的經改質活性碳纖維布。傅里葉轉換紅外光譜的結果如圖1及圖2所示。The modified activated carbon fiber cloths of Examples 1 to 4 were measured by a Fourier transform infrared spectrum analyzer (manufactured by Thermo Scientific, model: Nicilet 6700). The results of Fourier transform infrared spectroscopy are shown in Figures 1 and 2.
4.交流阻抗頻譜測試(EIS)4. AC Impedance Spectrum Test (EIS)
將上述使用實施例1及比較例1所製得的鈕扣型電池,以恆電位儀(廠商:Autolab,型號:PGSTAT30)進行交流阻抗頻譜測試,得到實施例1及比較例1所製得的鈕扣型電池的界面接觸阻抗(Rc),結果如表1所示。The button type battery obtained in the above Example 1 and Comparative Example 1 was subjected to an AC impedance spectrum test using a potentiostat (manufactured by Autolab, model: PGSTAT30), and buttons obtained in Example 1 and Comparative Example 1 were obtained. The interface contact resistance (Rc) of the battery was as shown in Table 1.
5.充放電測試5. Charge and discharge test
以恆電位儀(廠商:Autolab,型號:PGSTAT30)對上述使用實施例1、2及比較例1所製得的鈕扣型電池進行充放電測試。其中,在充放電電流密度為1.5 mA/cm 2時,實施例1、2及比較例1的鈕扣型電池的比電容值結果是如表1所示,實施例1及比較例1的鈕扣型電池的比電容對充放電電流密度的關係圖是如圖3所示。 The coin-type battery prepared in the above Examples 1 and 2 and Comparative Example 1 was subjected to charge and discharge tests by a potentiostat (manufactured by Autolab, model: PGSTAT30). In the case where the charge/discharge current density was 1.5 mA/cm 2 , the specific capacitance values of the button type batteries of Examples 1 and 2 and Comparative Example 1 were as shown in Table 1, and the button types of Example 1 and Comparative Example 1 were used. The relationship between the specific capacitance of the battery and the charge-discharge current density is shown in Fig. 3.
表1 <TABLE border="1" borderColor="#000000" width="_0001"><TBODY><tr><td> </td><td> 實施例1 </td><td> 實施例2 </td><td> 實施例3 </td><td> 實施例4 </td><td> 比較例1 </td></tr><tr><td> 電漿處理的圈數(圈) </td><td> 1 </td><td> 5 </td><td> 10 </td><td> 20 </td><td> 0 </td></tr><tr><td> 電漿處理對碳纖維布的 單位面積處理功率量 (單位:W/mm<sup>2</sup>) </td><td> 3.18 </td><td> 15.9 </td><td> 31.8 </td><td> 63.6 </td><td> 0 </td></tr><tr><td> 電漿處理對碳纖維布的 單位時間處理面積量 (單位:mm<sup>2</sup>/sec) </td><td> 318 </td><td> 318 </td><td> 318 </td><td> 318 </td><td> 0 </td></tr><tr><td> 水接觸角 (單位:度) </td><td> 0 </td><td> 0 </td><td> 0 </td><td> 0 </td><td> 120 </td></tr><tr><td> 鈕扣型電池的 界面接觸阻抗(R<sub>c</sub>) (單位:歐姆/cm<sup>2</sup>) </td><td> 0.22 </td><td> --- </td><td> --- </td><td> --- </td><td> 5.26 </td></tr><tr><td> 鈕扣型電池於充放電電流密度1.5mA/cm<sup>2</sup>的比電容值 (單位:F/g) </td><td> 102 </td><td> 87 </td><td> --- </td><td> --- </td><td> 75 </td></tr></TBODY></TABLE>註:「---」表示未量測。 Table 1 <TABLE border="1" borderColor="#000000" width="_0001"><TBODY><tr><td> </td><td> Example 1 </td><td> Example 2 </ Td><td> Example 3 </td><td> Example 4 </td><td> Comparative Example 1 </td></tr><tr><td> Number of cycles of plasma treatment (circle ) </td><td> 1 </td><td> 5 </td><td> 10 </td><td> 20 </td><td> 0 </td></tr>< Tr><td> The amount of power per unit area of the carbon fiber cloth treated by the plasma treatment (unit: W/mm<sup>2</sup>) </td><td> 3.18 </td><td> 15.9 </ Td><td> 31.8 </td><td> 63.6 </td><td> 0 </td></tr><tr><td> The amount of time per unit time of treatment of carbon fiber cloth by plasma treatment (unit :mm<sup>2</sup>/sec) </td><td> 318 </td><td> 318 </td><td> 318 </td><td> 318 </td>< Td> 0 </td></tr><tr><td> Water contact angle (unit: degree) </td><td> 0 </td><td> 0 </td><td> 0 < /td><td> 0 </td><td> 120 </td></tr><tr><td> Interface Contact Impedance of Button Cell (R<sub>c</sub>) (Unit: Ohm/cm<sup>2</sup>) </td><td> 0.22 </td><td> --- </td><td> --- </td><td> --- </td><td> 5.26 </td></tr><tr><td> Button battery has a charge and discharge current density of 1.5mA/cm<sup>2</ Sup> specific capacitance value (unit: F/g) </td><td> 102 </td><td> 87 </td><td> --- </td><td> --- < /td><td> 75 </td></tr></TBODY></TABLE> Note: "---" means unmeasured.
表2 <TABLE border="1" borderColor="#000000" width="_0002"><TBODY><tr><td> 區域(Region) </td><td> 相對含量(Relative content,%) </td></tr><tr><td> 實施例1 </td><td> 實施例2 </td><td> 實施例3 </td><td> 實施例4 </td><td> 比較例1 </td></tr><tr><td> C1s </td><td> 76.2 </td><td> 63.4 </td><td> 64 </td><td> 66.8 </td><td> 87.4 </td></tr><tr><td> O1s </td><td> 22.4 </td><td> 34.6 </td><td> 33.6 </td><td> 31.1 </td><td> 11.3 </td></tr><tr><td> N1s </td><td> 1.4 </td><td> 2.0 </td><td> 2.4 </td><td> 2.1 </td><td> 1.3 </td></tr></TBODY></TABLE>Table 2 <TABLE border="1" borderColor="#000000" width="_0002"><TBODY><tr><td> Region </td><td> Relative content (%) </td ></tr><tr><td> Example 1 </td><td> Example 2 </td><td> Example 3 </td><td> Example 4 </td><td > Comparative Example 1 </td></tr><tr><td> C1s </td><td> 76.2 </td><td> 63.4 </td><td> 64 </td><td> 66.8 </td><td> 87.4 </td></tr><tr><td> O1s </td><td> 22.4 </td><td> 34.6 </td><td> 33.6 </ Td><td> 31.1 </td><td> 11.3 </td></tr><tr><td> N1s </td><td> 1.4 </td><td> 2.0 </td>< Td> 2.4 </td><td> 2.1 </td><td> 1.3 </td></tr></TBODY></TABLE>
表3 <TABLE border="1" borderColor="#000000" width="_0003"><TBODY><tr><td> 區域(Region) </td><td> 波峰(Peak) </td><td> 位置 (Position) </td><td> 相對含量(Relative content,%) </td></tr><tr><td> 實施例1 </td><td> 實施例2 </td><td> 實施例3 </td><td> 實施例4 </td><td> 比較例1 </td></tr><tr><td> O1s </td><td> I(a) </td><td> 534.3 eV </td><td> 15 </td><td> 17 </td><td> 29 </td><td> 32 </td><td> 14 </td></tr><tr><td> II(a) </td><td> 532.5 eV </td><td> 67 </td><td> 62 </td><td> 60 </td><td> 63 </td><td> 57 </td></tr><tr><td> III(a) </td><td> 530.8 eV </td><td> 18 </td><td> 21 </td><td> 11 </td><td> 5 </td><td> 29 </td></tr><tr><td> C1s </td><td> I(b) </td><td> 289.3 eV </td><td> 16 </td><td> 16 </td><td> 12 </td><td> 18 </td><td> 23 </td></tr><tr><td> II(b) </td><td> 287.2 eV </td><td> 27 </td><td> 27 </td><td> 30 </td><td> 31 </td><td> 5 </td></tr><tr><td> III(b) </td><td> 285.8 eV </td><td> 14 </td><td> 11 </td><td> 11 </td><td> 10 </td><td> 13 </td></tr><tr><td> IV(b) </td><td> 284.7 eV </td><td> 23 </td><td> 26 </td><td> 27 </td><td> 24 </td><td> 26 </td></tr><tr><td> V(b) </td><td> 284.1 eV </td><td> 20 </td><td> 20 </td><td> 20 </td><td> 17 </td><td> 33 </td></tr></TBODY></TABLE>[註]: I(a):水氣吸附(adsorbed water); II(a):C-O,羥基中的氧原子; III(a):羰基中的C=O、羧基、醌(quinone)中的氧; I(b):羧基及酯基的碳; II(b):羰基、醌基及酮基的碳; III(b):醇基及醚基的碳; IV(b):石墨; V(b):碳化物(carbide)。 table 3 <TABLE border="1" borderColor="#000000" width="_0003"><TBODY><tr><td> Region </td><td> Peak </td><td> Position </td><td> Relative content (%) </td></tr><tr><td> Example 1 </td><td> Example 2 </td> <td> Example 3 </td><td> Example 4 </td><td> Comparative Example 1 </td></tr><tr><td> O1s </td><td> I( a) </td><td> 534.3 eV </td><td> 15 </td><td> 17 </td><td> 29 </td><td> 32 </td><td> 14 </td></tr><tr><td> II(a) </td><td> 532.5 eV </td><td> 67 </td><td> 62 </td><td > 60 </td><td> 63 </td><td> 57 </td></tr><tr><td> III(a) </td><td> 530.8 eV </td>< Td> 18 </td><td> 21 </td><td> 11 </td><td> 5 </td><td> 29 </td></tr><tr><td> C1s </td><td> I(b) </td><td> 289.3 eV </td><td> 16 </td><td> 16 </td><td> 12 </td><td > 18 </td><td> 23 </td></tr><tr><td> II(b) </td><td> 287.2 eV </td><td> 27 </td>< Td> 27 </td><td> 30 </td><td> 31 </td><td> 5 </td></tr><tr><td> III(b) </td>< Td> 285.8 eV </td><td> 14 </td><td> 11 </td><td> 11 </td><td> 10 </td><td> 13 </td></ Tr><tr><td> IV(b) </td><td> 284.7 eV </td><td> 23 </td><td> 26 </td><td> 27 </td><td> 24 </td><td> 26 < /td></tr><tr><td> V(b) </td><td> 284.1 eV </td><td> 20 </td><td> 20 </td><td> 20 </td><td> 17 </td><td> 33 </td></tr></TBODY></TABLE>[Note]: I(a): adsorbed water; II (a): CO, an oxygen atom in a hydroxyl group; III(a): C=O in a carbonyl group, a carboxyl group, an oxygen in a quinone; I(b): a carboxyl group and an ester group carbon; II(b) Carbon of a carbonyl group, a mercapto group and a ketone group; III (b): an alcohol group and an ether group; IV (b): graphite; V (b): a carbide.
從表1中水接觸角的結果可知,實施例1至4的經改質活性碳纖維布的水接觸角為0度,表示實施例1至4的經改質活性碳纖維布具有很高的親水性。比較例1未經改質活性碳纖維布的水接觸角為120度,代表實施例1未經改質活性碳纖維布的親水性較差。證明透過電漿處理確實能使得碳纖維布經電漿處理後的親水性大於碳纖維布電漿處理前的親水性。From the results of the water contact angles in Table 1, it is understood that the modified contact carbon fiber cloths of Examples 1 to 4 have a water contact angle of 0 degrees, indicating that the modified activated carbon fiber cloths of Examples 1 to 4 have high hydrophilicity. . The water contact angle of the unmodified activated carbon fiber cloth of Comparative Example 1 was 120 degrees, which represented that the hydrophilicity of the unmodified activated carbon fiber cloth of Example 1 was poor. It is proved that the hydrophilicity of the carbon fiber cloth after the plasma treatment can be made higher than that of the carbon fiber cloth before the plasma treatment by the plasma treatment.
從表2的結果可知,實施例1至4的經改質活性碳纖維布的「O1s」峰值表示的相對含量為22.4%至34.6%,而比較例1的未經改質活性碳纖維布的「O1s」峰值表示的相對含量為11.3%,證明透過電漿處理確實能使得碳纖維布中的多數碳纖維被活化並與氧反應而使得碳纖維布上的氧增加。並配合圖1及2可知,實施例1至4經改質活性碳纖維布具有親水性官能基(O-H、C=O、C-O、-COOH),證明透過該電漿處理確實能使得碳纖維布中的多數碳纖維被活化並與親水性物質反應而於該等碳纖維上連接親水性官能基團。From the results of Table 2, it is understood that the "O1s" peak of the modified activated carbon fiber cloths of Examples 1 to 4 represents a relative content of 22.4% to 34.6%, and the "O1s of the unmodified activated carbon fiber cloth of Comparative Example 1". The peak indicates a relative content of 11.3%, which proves that the plasma treatment does allow most of the carbon fibers in the carbon fiber cloth to be activated and react with oxygen to increase the oxygen on the carbon fiber cloth. 1 and 2, the modified activated carbon fiber cloths of Examples 1 to 4 have hydrophilic functional groups (OH, C=O, CO, -COOH), which proves that the treatment by the plasma can indeed make the carbon fiber cloth Most of the carbon fibers are activated and react with hydrophilic materials to attach hydrophilic functional groups to the carbon fibers.
配合表2及表3中的「O1s峰位的I(a)」相對含量可知,實施例1經改質活性碳纖維布所吸附水氣的相對含量為3.36%(0.15×0.224×100%),實施例2經改質活性碳纖維布所吸附水氣的相對含量為5.88%(0.17×0.346×100%),實施例3經改質活性碳纖維布所吸附水氣的相對含量為9.74%(0.29×0.336×100%),實施例4經改質活性碳纖維布所吸附水氣的相對含量為9.95%(0.32×0.311×100%),皆高於比較例1未經改質活性碳纖維布所吸附水氣的相對含量為1.58%(0.15×1.13×100%),證明透過電漿處理確實能使得碳纖維布經電漿處理後的親水性大於該碳纖維布電漿處理前的親水性。According to the relative content of I(a) of the peak position of O1s in Tables 2 and 3, the relative content of water vapor adsorbed by the modified activated carbon fiber cloth of Example 1 was 3.36% (0.15×0.224×100%). The relative content of water vapor adsorbed by the modified activated carbon fiber cloth of Example 2 was 5.88% (0.17×0.346×100%), and the relative content of water vapor adsorbed by the modified activated carbon fiber cloth of Example 3 was 9.74% (0.29×). 0.336×100%), the relative content of water vapor adsorbed by the modified activated carbon fiber cloth of Example 4 was 9.95% (0.32×0.311×100%), which was higher than that of the unmodified activated carbon fiber cloth of Comparative Example 1. The relative content of gas is 1.58% (0.15×1.13×100%), which proves that the hydrophilicity of the carbon fiber cloth after the plasma treatment can be made greater than the hydrophilicity of the carbon fiber cloth before the plasma treatment.
由表1中界面接觸阻抗的結果可知,實施例1所製得的鈕扣型電池具有較低的界面接觸阻抗,比較例1所製得的鈕扣型電池具有較高的界面接觸阻抗。以及由表1中充放電測試的結果可知,實施例1與實施例2所製得的鈕扣型電池能承受較快的充電速率,比較例1所製得的鈕扣型電僅可承受較慢的充電速率。並由圖3可知,實施例1所製得的鈕扣型電池具有較高的比電容,比較例1製得的鈕扣型電池具有較低的比電容。證明透過該電漿處理確實能使得碳纖維布經電漿處理後的的導電性大於該碳纖維布電漿處理前的導電性,從而使得鈕扣型電池具有較佳的性能。From the results of the interface contact resistance in Table 1, it is understood that the button type battery obtained in Example 1 has a low interface contact resistance, and the button type battery obtained in Comparative Example 1 has a high interface contact resistance. As can be seen from the results of the charge and discharge tests in Table 1, the button type batteries produced in Example 1 and Example 2 can withstand a faster charging rate, and the button type electric power produced in Comparative Example 1 can only withstand slower speeds. Charging rate. As can be seen from FIG. 3, the button type battery produced in Example 1 has a higher specific capacitance, and the button type battery obtained in Comparative Example 1 has a lower specific capacitance. It is proved that the electrical conductivity of the carbon fiber cloth after the plasma treatment can be made greater than the conductivity of the carbon fiber cloth before the plasma treatment, so that the button type battery has better performance.
由圖4至7證明,透過電漿處理確實使得碳纖維布中的碳纖維斷裂而形成鬆散結構。It is demonstrated by Figs. 4 to 7 that the plasma treatment does cause the carbon fibers in the carbon fiber cloth to be broken to form a loose structure.
綜上所述,透過該電漿處理能使該碳纖維布與該親水性物質反應而於該碳纖維布上形成親水性官能基團,因此提昇該碳纖維布的親水性,以及透過該電漿處理使該碳纖維布中的碳纖維斷裂而形成鬆散結構,因此提昇該碳纖維布的導電性,故確實能達成本發明之目的。In summary, the carbon fiber cloth can react with the hydrophilic substance to form a hydrophilic functional group on the carbon fiber cloth by the plasma treatment, thereby improving the hydrophilicity of the carbon fiber cloth and the plasma treatment. Since the carbon fibers in the carbon fiber cloth are broken to form a loose structure, the conductivity of the carbon fiber cloth is improved, and the object of the present invention can be achieved.
惟以上所述者,僅為本發明之實施例而已,當不能以此限定本發明實施之範圍,凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.
本發明之其他的特徵及功效,將於參照圖式的實施方式中清楚地呈現,其中: [圖1]是實施例1至4在氮氣(N 2)環境下的傅里葉轉換紅外光譜圖; [圖2]是實施例1至4在大氣環境下的傅里葉轉換紅外光譜圖;及 [圖3]是實施例1以及比較例1的鈕扣型電池充放電測試結果,為在充放電電流密度為1.5 mA/cm 2時的一比電容對充放電電流密度的關係圖; [圖4]是實施例1的掃描式電子顯微鏡的照片; [圖5]是實施例2的掃描式電子顯微鏡的照片; [圖6]是實施例3的掃描式電子顯微鏡的照片;及 [圖7]是實施例4的掃描式電子顯微鏡的照片。 Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a Fourier-transition infrared spectrum of Examples 1 to 4 in a nitrogen (N 2 ) environment. [Fig. 2] is a Fourier-transition infrared spectrum of Examples 1 to 4 in an atmospheric environment; and [Fig. 3] is a charge and discharge test result of the button type battery of Example 1 and Comparative Example 1, in charge and discharge Fig. 4 is a photograph of a scanning electron microscope of Example 1 when the current density is 1.5 mA/cm 2 ; [Fig. 5] is a scanning electron of the embodiment 2 Photograph of the microscope; [Fig. 6] is a photograph of the scanning electron microscope of Example 3; and Fig. 7 is a photograph of the scanning electron microscope of Example 4.
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