TWI678019B - Polymer fiber film and method for manufacturing polymer fiber film - Google Patents
Polymer fiber film and method for manufacturing polymer fiber film Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
一種高分子纖維薄膜及製備高分子纖維薄膜的方法。前述高分子纖維薄膜係由一高分子纖維組合物互交聯沉積形成，前述高分子纖維組合物由至少由尼龍，聚甲基丙烯酸甲酯(poly(methyl methacrylate),PMMA)和二氧化矽共聚反應而成。 A polymer fiber film and a method for preparing a polymer fiber film. The polymer fiber film is formed by cross-linking and depositing a polymer fiber composition. The polymer fiber composition is formed by copolymerizing at least nylon, poly (methyl methacrylate, PMMA), and silicon dioxide. Reacted.
Description
本發明係有關一種高分子纖維薄膜，尤指一種應用於鋰電池隔離膜的高分子纖維薄膜。 The present invention relates to a polymer fiber film, in particular to a polymer fiber film applied to a lithium battery separator.
近年來電子電動產品蓬勃發展，其中最重要的無非是動力供給的鋰電池，且目前已然成為最廣為使用的儲能系統，尤其電子手持裝置，例如智慧型手機、筆記型電腦及相機等無一沒有鋰電池的身影。基本的鋰電池設計包含四個要素，分別為正極、負極、電解液及隔離膜。鋰電池中電極所產生的離子可在電解液中流通產生電流，是將化學能轉換成電能的裝置，隔離膜的作用主要在隔離正、負極板，防止正負電極間發生短路，並且讓帶正電的離子自由通過。雖然隔離膜並不會參與電化學反應，但是其結構及性質會影響到鋰電池的效能。隔離膜本身的強度、厚度、微孔分佈與熱啟動性等品質指標，決定了電池電容量、電池循環壽命、安全性等因素。因此，在電池設計上，隔離膜是與安全息息相關的重要角色。 In recent years, electronic and electric products have been booming. The most important one is the lithium battery for power supply. It has now become the most widely used energy storage system, especially electronic handheld devices such as smart phones, notebook computers and cameras. No lithium battery. The basic lithium battery design includes four elements, namely the positive electrode, negative electrode, electrolyte and separator. The ions generated by the electrodes in the lithium battery can flow in the electrolyte to generate current. It is a device that converts chemical energy into electrical energy. The role of the isolation film is mainly to isolate the positive and negative plates, prevent short circuits between the positive and negative electrodes, and allow positive Electric ions pass freely. Although the separator does not participate in the electrochemical reaction, its structure and properties will affect the performance of lithium batteries. The quality index of the separator itself, such as its strength, thickness, micropore distribution, and hot startability, determine the battery capacity, battery cycle life, safety and other factors. Therefore, in battery design, the isolation film is an important role that is closely related to safety.
目前微孔聚烯烴膜為市面上最常使用的隔離膜，其具有良好 的化學穩定性及機械強度。常見的聚烯烴包含聚乙烯(Polyethylene,PE)與聚丙烯(Polypropylene,PP)。然而，低孔隙度的聚烯烴膜導致膜對於液體電解質的潤濕性和吸收率較差，會影響電量密度及充放電的電池倍率性能。此外，聚烯烴在高溫下有強烈收縮反應，可能會在充電或是過熱的情況下，導致內部短路而起火甚至***，使電池安全性降低。 At present, microporous polyolefin film is the most commonly used release film on the market. Chemical stability and mechanical strength. Common polyolefins include polyethylene (PE) and polypropylene (PP). However, the low porosity of the polyolefin film results in poor wettability and absorption of the liquid electrolyte to the liquid electrolyte, which may affect the charge density and battery rate performance of the charge and discharge. In addition, polyolefins have a strong shrinkage reaction at high temperatures, which may cause internal short circuits and catch fire or even explode when charged or overheated, reducing battery safety.
市售的聚烯烴隔離膜的製備方法可分為乾式或濕式製程，兩種製程方式皆為製成薄膜後透過拉伸的方式使其產生孔洞，但不同的是通常乾式製成式經由雙軸拉伸，所以產生的孔洞呈相互連結的圓形或橢圓形，濕式製程為單軸拉伸，則呈現狹縫狀的單向孔洞。然而，兩者皆有製程較為繁複成本較高問題。 The preparation method of the commercially available polyolefin insulation film can be divided into dry or wet processes. Both processes are made into a film through stretching to make holes, but the difference is that the dry method Axial stretching, so the resulting holes are circular or elliptical interconnected. The wet process is uniaxial stretching, which presents a unidirectional hole in the shape of a slit. However, both of them have a complicated process and a high cost.
1990年代起，靜電紡絲的技術遂被開發出來，係透過對聚合物溶液施加外部電場的作用而生成的連續奈米尺寸的聚合物纖維技術。近年來，已有許多研究指出因靜電紡絲纖維膜具有高孔隙度及其獨特的孔隙結構可被作為鋰電池隔離膜，且靜電紡絲製程相較於傳統聚烯烴隔離膜乾式或濕式製程簡易許多。然而，靜電紡絲纖維膜在鋰電池裝配的過程中，存在無法承受裝配過程中強大張力的問題。 Since the 1990s, electrospinning technology has been developed, which is a continuous nano-sized polymer fiber technology generated by applying an external electric field to a polymer solution. In recent years, many studies have pointed out that because of the high porosity and unique pore structure of electrospun fiber membranes, they can be used as lithium battery separators, and the electrostatic spinning process is dry or wet compared to traditional polyolefin separators. Much easier. However, in the process of assembling the lithium battery with the electrostatic spinning fiber membrane, there is a problem that it cannot withstand the strong tension during the assembly process.
本發明之主要目的，在於解決傳統聚烯烴隔離膜低孔隙度以及在高溫下有強烈收縮反應的問題。 The main purpose of the present invention is to solve the problems of low porosity and strong shrinkage reaction of the conventional polyolefin insulation film at high temperature.
為達上述目的，本發明提供一種高分子纖維組合物，係由至少由尼龍以及聚甲基丙烯酸甲酯(poly(methyl methacrylate),PMMA)共聚反應而成。 To achieve the above object, the present invention provides a polymer fiber composition made of at least nylon and poly (methyl methacrylate), PMMA) copolymerization reaction.
於一實施例中，該尼龍與該聚甲基丙烯酸甲酯的重量混合比例為2：1至1：2。 In one embodiment, the weight mixing ratio of the nylon to the polymethyl methacrylate is from 2: 1 to 1: 2.
於一實施例中，該高分子纖維組合物更包含有二氧化矽(SiO2)；其中，該二氧化矽的重量百分比為3%~12%。 In one embodiment, the polymer fiber composition further includes silicon dioxide (SiO 2 ); wherein the weight percentage of the silicon dioxide is 3% to 12%.
本發明更提供一種高分子纖維薄膜，高分子纖維組合物相互交聯沉積形成；其中該高分子纖維薄膜的平均孔徑為733nm-478nm；該高分子纖維薄膜的最快熱烈解溫度為450℃~460℃；該高分子纖維薄膜的拉伸強度為15.77MPa~29.10MPa；該高分子纖維薄膜的穿刺強度為4.9N-5.5N；該高分子纖維薄膜的熱收縮率為8-9%；該高分子纖維薄膜的孔隙度84.42~91.4%；該高分子纖維薄膜電解液攝取率為344.93~417.39%。 The invention further provides a polymer fiber film, and the polymer fiber composition is formed by cross-linking and depositing each other; wherein the average pore diameter of the polymer fiber film is 733nm-478nm; and the fastest thermal decomposition temperature of the polymer fiber film is 450 ° C ~ 460 ℃; the tensile strength of the polymer fiber film is 15.77MPa ~ 29.10MPa; the puncture strength of the polymer fiber film is 4.9N-5.5N; the thermal shrinkage of the polymer fiber film is 8-9%; The porosity of the polymer fiber film is 84.42 ~ 91.4%; the electrolyte uptake rate of the polymer fiber film is 344.93 ~ 417.39%.
本發明提供一種製備高分子纖維薄膜的方法，包含步驟有：混合尼龍，聚甲基丙烯酸甲酯(poly(methyl methacrylate)以及98%甲酸取得一混合液； The invention provides a method for preparing a polymer fiber film, comprising the steps of: mixing nylon, poly (methyl methacrylate) and 98% formic acid to obtain a mixed solution;
a).施以一電壓於該混合液，使該混合液表面分布電荷；以及 a) applying a voltage to the mixed liquid to distribute electric charges on the surface of the mixed liquid; and
b).輸出分布電荷的該混合液以形成一高分子纖維，固化沉積該高分子纖維於一收集板上並得到一高分子纖維薄膜。 b) outputting the mixed solution of distributed charge to form a polymer fiber, solidifying and depositing the polymer fiber on a collecting plate and obtaining a polymer fiber film.
c).於一實施例中，該製備高分子纖維薄膜的方法更包含 c) In an embodiment, the method for preparing a polymer fiber film further includes
d).疊合並熱壓二片高分子纖維薄膜，每一高分子纖維薄膜具有一纖維排列方向，該二高分子纖維薄膜的纖維排列方向彼此垂直；其中，該步驟d)的熱壓條件溫度為90℃~110℃，壓力為10~20kg/cm2，持續時間為5分鐘。 d) stacking and pressing two polymer fiber films, each polymer fiber film has a fiber arrangement direction, and the fiber arrangement directions of the two polymer fiber films are perpendicular to each other; wherein, the temperature of the hot pressing condition of step d) It is 90 ° C to 110 ° C, the pressure is 10 to 20 kg / cm 2 , and the duration is 5 minutes.
於一實施例中，步驟c)輸出該混合液的流速為0.020~0.030ml/min。 In an embodiment, the flow rate of the mixed solution in step c) is 0.020 ~ 0.030 ml / min.
於一實施例中，步驟b)施加電壓為17.5V~23V。 In an embodiment, the applied voltage in step b) is 17.5V ~ 23V.
於一實施例中，步驟a)的該尼龍與該聚甲基丙烯酸甲酯的重量混合比例為2：1至1：2。 In an embodiment, the weight mixing ratio of the nylon and the polymethyl methacrylate in step a) is from 2: 1 to 1: 2.
於一實施例中，步驟a)的混合液更包含有二氧化矽(SiO2)；其中該二氧化矽的重量百分比為3%~12%。 In one embodiment, the mixed solution of step a) further comprises silicon dioxide (SiO 2 ); wherein the weight percentage of the silicon dioxide is 3% -12%.
本發明高分子纖維組合物、高分子纖維薄膜及製備高分子纖維薄膜的方法，提供一種可以應用於鋰電池隔離膜的高機械強度以及熱穩定性的高分子聚合物。 The polymer fiber composition, the polymer fiber film, and the method for preparing the polymer fiber film of the present invention provide a high-molecular polymer with high mechanical strength and thermal stability that can be applied to a lithium battery separator.
S10、S20、S30、S40‧‧‧步驟 S10, S20, S30, S40 ‧‧‧ steps
圖1，係本發明製備高分子纖維薄膜的方法一實施例之步驟流程示意圖。 FIG. 1 is a schematic flowchart of steps of an embodiment of a method for preparing a polymer fiber film according to the present invention.
圖2a-2b，係本發明一實施例之不同紡絲混合液重之靜電紡 絲後纖維型態圖。 Figures 2a-2b show the electrospinning of different spinning mixtures according to an embodiment of the present invention. Fiber pattern after silk.
圖3a-3c，係本發明一實施例之不同尼龍66與PMMA比例紡絲混合液之靜電紡絲後纖維型態圖。 Figures 3a-3c are diagrams of fiber types after electrostatic spinning of different nylon 66 and PMMA ratio spinning mixtures according to an embodiment of the present invention.
圖4a-4c，係本發明一實施例之不同紡絲混合液流速進行靜電紡絲產生纖維形態圖。 Figures 4a-4c are morphological diagrams of fibers produced by electrospinning with different spinning mixture flow rates according to an embodiment of the present invention.
圖5a-5c，係本發明一實施例之施加不同電壓進行靜電紡絲產生纖維形態圖。 5a-5c are morphological diagrams of fibers produced by electrospinning under different voltages according to an embodiment of the present invention.
圖6a-6e，係本發明一實施例之不同紡絲混合液製備成的高分子纖維薄膜的5,000倍率下的SEM圖。 6a-6e are SEM images of a polymer fiber film prepared from different spinning mixtures according to an embodiment of the present invention at a magnification of 5,000.
圖7a-7d，係本發明一實施例之不同紡絲混合液製備成的高分子纖維薄膜的50,000倍率下的SEM圖。 7a-7d are SEM images of a polymer fiber film prepared from different spinning mixtures according to an embodiment of the present invention at a magnification of 50,000 times.
圖8，係本發明一實施例分別將尼龍66、PMMA及紡絲混合液NPS0以靜電紡絲抽成高分子纖維後進行熱重分析儀(TGA)的檢測分析比較圖。 FIG. 8 is a comparison diagram of detection and analysis of a thermogravimetric analyzer (TGA) after nylon 66, PMMA, and a spinning mixed solution NPS0 are drawn into polymer fibers by electrostatic spinning according to an embodiment of the present invention.
圖9，係本發明一實施例將紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12以靜電紡絲抽成高分子纖維後進行熱重分析儀(TGA)的檢測分析比較圖。 FIG. 9 is a comparison diagram of the detection and analysis of a thermogravimetric analyzer (TGA) after the spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12 are drawn into polymer fibers by electrostatic spinning according to an embodiment of the present invention.
有關本發明之詳細說明及技術內容，現就配合圖式說明如下：本發明提供一種高分子纖維組合物，係由至少由尼龍(Nylon)以及聚甲基丙烯酸甲酯(poly(methyl methacrylate),PMMA)共聚反應而成。 The detailed description and technical contents of the present invention are described below with reference to the drawings: The present invention provides a polymer fiber composition, which is composed of at least nylon (Nylon) and poly (methyl methacrylate), PMMA) copolymerization reaction.
本發明使用的尼龍，係以尼龍66為例，亦可應用其他尼龍， 如尼龍6，尼龍510等。尼龍66是由六亞甲基二胺(Hexamethylene diamine,HMO)和己二酸(Adipic acid,AA)所縮合聚合而成，為一種線性結構的脂肪族聚醯胺，其分子鏈上有可形成氫鍵的醯胺基，使分子間作用力增大，且結構對稱易於結晶。聚甲基丙烯酸甲酯(Poly(methyl methacrylate),PMMA)，又稱壓克力，由甲基丙烯酸甲酯單體(PMMA)加成聚合而成，主鏈為非對稱的碳原子紊亂結構，呈無結晶的構造。 The nylon used in the present invention is nylon 66 as an example, and other nylons can also be applied. Such as nylon 6, nylon 510 and so on. Nylon 66 is a linear structured aliphatic polyamidoamine formed by the condensation and polymerization of hexamethylene diamine (HMO) and adipic acid (AA). Its molecular chain has hydrogen that can form hydrogen. Bonded amido groups increase the intermolecular force, and the structure is symmetrical and easy to crystallize. Poly (methyl methacrylate) (PMMA), also known as acrylic, is formed by the addition and polymerization of methyl methacrylate monomer (PMMA). The main chain has an asymmetric carbon atom disorder structure. It has a non-crystalline structure.
本發明該高分子纖維組合物更包含有二氧化矽(SiO2)；其中，該二氧化矽的重量百分比為3%~12%。 The polymer fiber composition of the present invention further comprises silicon dioxide (SiO 2 ); wherein the weight percentage of the silicon dioxide is 3% -12%.
本發明更提供一種高分子纖維薄膜，係由本發明高分子纖維組合物相互交聯沉積形成。 The present invention further provides a polymer fiber film, which is formed by cross-linking deposition of the polymer fiber composition of the present invention.
為了實現本發明，以下舉例提供一種製備高分子纖維薄膜的方法。如『圖1』所示，該製備高分子纖維薄膜的方法包含步驟至少有：步驟S10：混合尼龍，聚甲基丙烯酸甲酯(poly(methyl methacrylate)以及98%甲酸取得一混合液；步驟S20：施以一電壓於該混合液，使該混合液表面分布電荷(步驟S20)；以及步驟S30：輸出分布電荷的該混合液以形成一高分子纖維，固化沉積該高分子纖維於一收集板上並得到一高分子纖維薄膜。 To achieve the present invention, a method for preparing a polymer fiber film is provided below by way of example. As shown in [Figure 1], the method for preparing a polymer fiber film includes at least the steps of step S10: mixing nylon, poly (methyl methacrylate), and 98% formic acid to obtain a mixed solution; step S20 : Applying a voltage to the mixed solution to distribute charges on the surface of the mixed solution (step S20); and step S30: output the mixed solution to form a polymer fiber, and solidify and deposit the polymer fiber on a collecting plate And a polymer fiber film is obtained.
實施例一 Example one
本實施例探討尼龍66及聚甲基丙烯酸甲酯(PMMA)重量混合比例對於產生出來高分子纖維薄膜的影響。 In this embodiment, the influence of the weight mixing ratio of nylon 66 and polymethyl methacrylate (PMMA) on the production of the polymer fiber film is discussed.
於步驟S10中，將尼龍66(polyamide 66,Sigma-Alorich)與聚 甲基丙烯酸甲酯(poly(methyl methacrylate(PMMA),Sigma-Alorich)以及甲酸(formic acid,Katayama Chemical片山試藥株式會社，純度98~100%)以下表一的比例配製為配方A~D。 In step S10, nylon 66 (polyamide 66, Sigma-Alorich) and poly Polymethyl (meth methacrylate (PMMA), Sigma-Alorich) and formic acid (formic acid, Katayama Chemical Katayama Chemical Co., Ltd., purity 98 ~ 100%) are formulated in the proportions in Table 1 below as formulas A to D.
本實施例係利用靜電紡絲技術將前述配方A~D製備成高分子纖維薄膜。 In this embodiment, the foregoing formulations A to D are prepared into a polymer fiber film by using an electrostatic spinning technology.
靜電紡絲裝置包含有一微量注射幫浦(syringe pump(Fusion 2000),Chemyx Inc.)、高壓電源供應器(High Voltage Power Supply(AU-60P2.5),Matsusada Precision,Inc.)、滾筒收集板。該微量注射幫浦包含有一微量推進器以及一注射器。 The electrostatic spinning device includes a micro injection pump (Fusion 2000), Chemyx Inc., a high voltage power supply (AU-60P2.5), Matsada Precision, Inc., and a roller collection plate . The micro-injection pump includes a micro-propeller and a syringe.
首先將前述配方A~D裝填入該注射器內，並將該注射器接上鐵氟龍館及不鏽鋼針頭(19號針頭，外徑：1.06mm，內徑：0.70mm)。將該注射器置入該微量推進器中，並以寬10cm、長66cm之鋁箔紙固定於該滾筒收集板上。塗覆一層離形劑於該鋁箔紙上以利製作出來的高分子纖維從該鋁箔紙剝離。將該不銹鋼針頭前端調整面對該滾筒收集板。將該不銹鋼 針頭接上高壓電線，且將該滾筒收集板接上地線。 First, the aforementioned formulas A to D were filled into the syringe, and the syringe was connected with a Teflon hall and a stainless steel needle (19 gauge needle, outer diameter: 1.06 mm, inner diameter: 0.70 mm). The syringe was placed in the micro-propeller, and was fixed on the roller collection plate with aluminum foil paper with a width of 10 cm and a length of 66 cm. A layer of a release agent is coated on the aluminum foil paper to facilitate the produced polymer fibers to be peeled from the aluminum foil paper. The front end of the stainless steel needle is adjusted to face the roller collecting plate. The stainless steel The needle is connected to a high-voltage wire, and the drum collecting plate is connected to a ground wire.
本實施例靜電紡絲技術可以調整的工作參數包含電壓、流速以及收集轉速。 The working parameters that can be adjusted by the electrostatic spinning technology in this embodiment include voltage, flow rate, and collection speed.
電壓為靜電紡絲過程中一項重要的工作參數，只有施加電壓高於臨界電壓才能夠使泰勒錐發生射流。 Voltage is an important working parameter in the electrospinning process. Only when the applied voltage is higher than the threshold voltage can the Taylor cone be jetted.
流速為推進器設定之速度，與電壓為搭配值。找到最適當的流速，使針頭的泰勒錐形狀穩定不隨時間變化。通常靜電紡絲製程較適合低流速，因紡絲液會有較足夠的時間產生極化；如果流速過高，會因溶劑蒸發時間不足與拉伸力太低，導致形成較粗的珠狀纖維甚至溶解或破壞已固化之纖維結構。 The flow velocity is the speed set by the thruster, and the voltage is the matching value. Find the most appropriate flow rate to stabilize the Taylor cone shape of the needle over time. Generally, the electrospinning process is more suitable for low flow rates, because the spinning solution will have sufficient time to generate polarization; if the flow rate is too high, the solvent evaporation time is insufficient and the tensile force is too low, resulting in the formation of thick bead fibers Even dissolve or destroy the cured fiber structure.
收集轉速為可決定紡絲纖維的方向性的參數。射流在溶劑蒸發轉變為纖維的過程中，由於同性電荷的排斥力產生擺動，因此落於收集器上的纖維呈無方向性且繁亂的樣子，然而對於一些應用，如縫合線、傷口修復支架及燃料電池的膜等，需要奈米纖維呈現有序陣列。纖維落於收集器時尚未完全固化，而收集器的旋轉使得纖維進一步細化，因此纖維直徑隨著轉速增高而變小。 The collection speed is a parameter that determines the directivity of the spinning fiber. During the process of the evaporation of the solvent into fibers, the jet oscillates due to the repulsive force of the same charge, so the fibers falling on the collector appear non-directional and messy. However, for some applications, such as sutures, wound repair brackets, and Fuel cell membranes and the like require nanofibers to present an ordered array. When the fiber falls on the collector, it is not completely solidified, and the rotation of the collector makes the fiber further refined, so the fiber diameter becomes smaller as the rotation speed increases.
於本實施例中，配方A~D進行靜電紡絲技術的工作條件為電壓17.5kV、滾筒收集板與針頭距離12cm、滾筒收集板轉速1500rpm、溶液流速0.030ml/min。其結果可參『圖2a-2b』、『圖3a-3c』所示。 In this embodiment, the working conditions of the electrospinning technology for the formulations A to D are a voltage of 17.5 kV, a distance between the roller collection plate and the needle 12 cm, a rotation speed of the roller collection plate at 1500 rpm, and a solution flow rate of 0.030 ml / min. The results are shown in "Figure 2a-2b" and "Figure 3a-3c".
『圖2a-2b』為配方A、B靜電紡絲後纖維型態，配方A(圖2a)及配方B(圖2b)可明顯看出配方A的纖維量較配方B少且較不平整，但兩種配方皆有溶劑尚未揮發而將纖維溶掉的痕跡及纖維表面突起。『圖3a-3c』為配方B、C、D靜電紡絲後纖維形態。固定溶液總重為30g，改變尼龍66與PMMA比例。發現配方C(圖3b)較配方B(圖3a)、配方D(圖3c)較為平整，而未揮發溶劑痕跡則為配方D較少。由以上比較可知在液體總重量30g的情況下，配方C(尼龍66：PMMA比例為2：1)的纖維表面最平整。 [Figure 2a-2b] are the fiber types of Formula A and B after electrospinning. Formula A (Figure 2a) and Formula B (Figure 2b) clearly show that the fiber content of Formula A is less and less flat than Formula B. However, both formulations have traces of the solvent that has not evaporated and the fibers have been dissolved and the surface of the fibers has been raised. [Figures 3a-3c] are the fiber morphology of the formulations B, C, and D after electrostatic spinning. The total weight of the fixing solution was 30 g, and the ratio of nylon 66 to PMMA was changed. It was found that Formula C (Figure 3b) was smoother than Formula B (Figure 3a) and Formula D (Figure 3c), and the traces of non-volatile solvents were less in Formula D. From the above comparison, it can be seen that in the case of a total liquid weight of 30 g, the fiber surface of Formula C (the ratio of nylon 66: PMMA is 2: 1) is the flattest.
實施例二 Example two
此實施例討論靜電紡絲工作參數，包含流速以及電壓對於產生出來高分子纖維薄膜的影響。 This embodiment discusses the working parameters of electrospinning, including the influence of flow rate and voltage on the produced polymer fiber film.
於本實施例，先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，加入98%甲酸中，混合成30g的紡絲混合液。將該紡絲混合液進行靜電紡絲，該靜電紡絲的參數如下，紡絲混合液流速分別以0.020ml/min、0.025ml/min、0.030ml/min，電壓17.5kV，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，其纖維如『圖4a-4c』所示。結果顯示以0.020ml/min(圖4a)紡出的纖維未揮發溶劑的痕跡最少，其次為0.025ml/min(圖4b)，痕跡最多為0.030ml/min(圖4c)的纖維。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are firstly added to 98% formic acid in a ratio of 2: 1 (2.6 g: 1.3 g), and mixed into 30 g of a spinning mixture. The spinning mixture was subjected to electrospinning. The parameters of the electrospinning were as follows. The flow rate of the spinning mixture was 0.020 ml / min, 0.025 ml / min, 0.030 ml / min, and the voltage was 17.5 kV. The roller collection plate and needle The distance is 12cm, the rotation speed of the drum collecting plate is 1,500rpm, and the fibers are as shown in "Fig. 4a-4c". The results showed that the traces of the non-volatile solvent spun at 0.020 ml / min (Fig. 4a) were the smallest, followed by 0.025 ml / min (Fig. 4b), and the traces were at most 0.030 ml / min (Fig. 4c).
再者討論電壓參數，電壓選用17.5kV、20kV、23kV 做比較，其餘參數為流速0.025ml/min、收集板與針頭距離12cm、收集板轉速1500rpm進行紡絲，紡絲後纖維如『圖5a-5c』所示。電壓為17.5kV(圖5a)之纖維，溶劑痕跡最多，而20kV(圖5b)之纖維圖片中較不明顯，但以肉眼觀察仍有少許痕跡，23kV(圖5c)之纖維型態則最為完整。 Let's discuss the voltage parameters. The voltage is 17.5kV, 20kV, 23kV. For comparison, the remaining parameters are spinning at a flow rate of 0.025 ml / min, the distance between the collecting plate and the needle is 12 cm, and the rotating speed of the collecting plate is 1500 rpm for spinning. The fibers after spinning are as shown in "Figure 5a-5c". The fiber with a voltage of 17.5kV (Figure 5a) has the most solvent traces, while the fiber picture of 20kV (Figure 5b) is less obvious, but there are still a few traces when viewed with the naked eye. The fiber type of 23kV (Figure 5c) is the most complete .
實施例三 Example three
本實施例更進一步揭露在步驟S30得到一高分子纖維薄膜之後，疊合並熱壓二片高分子纖維薄膜的步驟S40，如『圖1』所示。每一高分子纖維薄膜具有一纖維排列方向，該二高分子纖維薄膜的纖維排列方向彼此垂直。 This embodiment further discloses step S40 of superimposing and pressing two polymer fiber films after obtaining a polymer fiber film in step S30, as shown in FIG. 1. Each polymer fiber film has a fiber arrangement direction, and the fiber arrangement directions of the two polymer fiber films are perpendicular to each other.
於本實施例中，先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，加入98%甲酸中，混合成30g的紡絲混合液。在將該紡絲混合液進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)所得到高分子纖維薄膜。將紡絲後的高分子纖維薄膜裁剪成寬10cm、長10cm的正方形，並將兩片具方向性的纖維以90度正交重疊進行熱壓，使用熱壓機(Cometech，型號QC-601T)將兩片壓為一片，熱壓條件溫度為90℃、110℃；壓力為10、15、20kg/cm2，持續時間為5分鐘。各種熱壓條件對纖維孔隙度的影響如下表二所示。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are firstly added to 98% formic acid in a ratio of 2: 1 (2.6 g: 1.3 g), and mixed into 30 g of a spinning mixture. This spinning mixture was subjected to electrospinning (the working condition was a voltage of 23 V, the distance between the cylinder collecting plate and the needle was 12 cm, the rotation speed of the cylinder collecting plate was 1,500 rpm, and the flow rate of the spinning mixture was 0.0250 ml / min) to obtain a polymer fiber film. The polymer fiber film after spinning is cut into a square of 10 cm in width and 10 cm in length, and two pieces of directional fibers are overlapped orthogonally at 90 degrees for hot pressing. A hot press (Cometech, model QC-601T) is used. The two pieces are pressed into one piece, and the temperature of the hot pressing conditions is 90 ° C and 110 ° C; the pressure is 10, 15, 20 kg / cm 2 , and the duration is 5 minutes. The effects of various hot-pressing conditions on fiber porosity are shown in Table 2 below.
孔隙度定義為孔隙的體積與材料總體積的比率，本實施例採液體吸收法來測量孔隙度的大小。液體吸收法係根據ASTM D2873將多孔試樣浸入容易滲透入試樣孔隙的液體中，再經由下式(1)計算出孔隙度。其中Ww為濕式樣之重量，Wd為乾式樣之重量，ρ為液體密度，V為試樣之體積。 Porosity is defined as the ratio of the volume of pores to the total volume of the material. In this embodiment, the liquid absorption method is used to measure the porosity. The liquid absorption method is based on ASTM D2873. A porous sample is immersed in a liquid that easily penetrates into the pores of the sample, and the porosity is calculated by the following formula (1). Where Ww is the weight of the wet pattern, Wd is the weight of the dry pattern, ρ is the liquid density, and V is the volume of the sample.
先以尺規裁剪已知面積之試樣，再以膜厚計量測試樣厚度，計算其體積；將試樣烘乾去除多餘水分測量乾試樣之重量後，再將試樣浸入丙二醇計時一分鐘並觀察試片呈半透明，擦乾至無水漬痕跡測量濕試樣之重量，將取的的數值代入式(1)。 First cut a sample of known area with a ruler, then measure the thickness of the test sample with the film thickness, and calculate its volume; dry the sample to remove excess moisture and measure the weight of the dry sample, and then immerse the sample in propylene glycol for one minute And observe that the test piece is translucent, wipe it dry to leave no traces of water stains, measure the weight of the wet sample, and substitute the value taken into formula (1).
由表二中得知熱壓溫度90℃較110℃之纖維空隙度大；在壓力方面，溫度為110℃時壓力越大則空隙度越小；但溫度為90℃時卻是15kg/cm2時孔隙度為最大，其次是壓力 10kg/cm2，而孔隙度最小的為壓力20kg/cm2。 According to Table 2, it is known that the fiber porosity of the hot-pressing temperature 90 ° C is greater than 110 ° C. In terms of pressure, the porosity is smaller when the temperature is 110 ° C, but it is 15kg / cm 2 at 90 ° C. When the porosity is the largest, the pressure is 10 kg / cm 2 , and when the porosity is the smallest, the pressure is 20 kg / cm 2 .
本實施例更進一步檢測該高分子纖維薄膜的機械性質。 This embodiment further tests the mechanical properties of the polymer fiber film.
機械性檢測是要測量隔離膜的拉伸強度、穿刺強度。拉伸強度使用萬能拉力試驗機(型號HT-2402，弘達儀器)即可測得，其定義為拉伸強度是指材料在拉斷前所能承受的最大應力，一般結果以MPa表示，計算如式(2)。其中F0=試樣在斷裂前的最大外力(N)，A0=試樣原來的截面積(mm2)。 The mechanical test is to measure the tensile strength and puncture strength of the separator. The tensile strength can be measured using a universal tensile tester (model HT-2402, Hongda Instrument). The tensile strength is defined as the maximum stress that the material can withstand before breaking. The general result is expressed in MPa. Equation (2). Where F0 = the maximum external force (N) of the sample before fracture, and A0 = the original cross-sectional area (mm 2 ) of the sample.
測試方法為將試片規格為長4cm，寬1cm的長條試片，伸長速率為10mm/min，達50%破斷點即停止。 The test method is to lengthen a test piece with a length of 4cm and a width of 1cm, and the elongation rate is 10mm / min, and it will stop when it reaches the 50% breaking point.
將前述靜電紡絲製成的高分子先為薄膜利用不同熱壓條件進行機械性質的檢測，每一條件皆測定三次取平均值，結果列於下表三。 The polymer produced by the aforementioned electrospinning was first tested for mechanical properties under different hot-pressing conditions. Each condition was measured three times and the average value was obtained. The results are shown in Table III below.
由表三得知，以溫度為90℃而言，當壓力為10kg/cm2時其拉伸強度為最佳，但試片斷裂時可明顯看出分層且唯有單層膜斷裂，當壓力20kg/cm2時亦是此種現象，而壓力15kg/cm2時，雙層隔離膜皆被拉斷但亦可明顯看出分層，由結果確定溫度90℃，無法將隔離膜良好結合。對溫度為110℃而言，其最大負重及拉伸強度則隨壓力增加而增強，伸長量及彈性係數皆無太大變化。 From Table 3, it is known that for a temperature of 90 ° C, the tensile strength is the best when the pressure is 10 kg / cm 2 , but when the test piece is broken, it is obvious that the layer is broken and only the single-layer film is broken. pressure of 20kg / cm 2 when this is also a phenomenon, a pressure 15kg / cm 2, the two-layer insulating film are pulled off but also apparent stratification, determined from the results of temperature 90 ℃, the separator can not bind well . For a temperature of 110 ° C, its maximum load and tensile strength increase with increasing pressure, and the elongation and elastic coefficient do not change much.
實施例四 Embodiment 4
本實施例討論添加二氧化矽(SiO2)於尼龍66/PMMA混合液對於高分子纖維形態的影響。本實施例利用掃描式電子顯微鏡(Field Emission Scanning Electron Microscope(FE-SEM))的方式來觀察本發明高分子纖維的表面形態，使用的掃描式電子顯微鏡為JEOL所製的JSM-7000F型號。 This embodiment discusses the effect of adding silicon dioxide (SiO 2 ) to a nylon 66 / PMMA mixed solution on the morphology of polymer fibers. In this embodiment, a scanning electron microscope (Field Emission Scanning Electron Microscope (FE-SEM)) is used to observe the surface morphology of the polymer fiber of the present invention. The scanning electron microscope used is a JSM-7000F model manufactured by JEOL.
於本實施例中，先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，不同重量百分比的二氧化矽(SiO2)(0%、3%、6%、9%、12%)，以及加入98%甲酸中，分別混合成30g的紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12。再將該紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12各別進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)得到高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are firstly used in a ratio of 2: 1 (2.6 g: 1.3 g), and different weight percentages of silicon dioxide (SiO 2 ) (0%, 3 %, 6%, 9%, 12%), and added to 98% formic acid, and mixed into 30g of spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12. The spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12 were each subjected to electrostatic spinning (the working condition was a voltage of 23V, the distance between the roller collection plate and the needle was 12 cm, the rotation speed of the roller collection plate was 1,500 rpm, and the flow rate of the spinning mixture solution was 0.0250. ml / min) to obtain polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12.
將待測的高分子纖維薄膜剪成適當大小，貼在一金屬載台上，把該金屬載台放置在鍍金機中抽真空鍍上白金60秒，增加高分子纖維薄膜的導電能力。將金屬載台放入電子顯微鏡的腔體內，設定加速電壓 15kV，倍率設定為×5,000或×50,000。取10個直徑數據取平均，直徑大小量測可以利用和SEM連線的電腦軟體在圖片上畫線量測，或使用Image J軟體畫線量測直徑大小。 The polymer fiber film to be tested is cut to an appropriate size, affixed to a metal stage, and the metal stage is placed in a gold plating machine and vacuum-plated with platinum for 60 seconds to increase the conductivity of the polymer fiber film. Place the metal stage in the cavity of the electron microscope and set the acceleration voltage 15kV, the magnification is set to × 5,000 or × 50,000. Take 10 diameter data and average them. The diameter can be measured by using computer software connected to the SEM to draw a line on the picture, or use the Image J software to draw a line to measure the diameter.
請參閱『圖6a-6e』所示，為尚未熱壓的高分子纖維薄膜NPS0(圖6a)、NPS3(圖6b)、NPS6(圖6c)、NPS9(圖6d)、NPS12(圖6e)的5,000倍率下的SEM圖。每個高分子纖維薄膜皆呈現高度的多孔纖維網絡並且具方向性。再參閱『圖7a-7d』，為高分子纖維薄膜NPS3(圖7a)、NPS6(圖7b)、NPS9(圖7c)、NPS12(圖7d)之50,000倍率下SEM圖，圖中於纖維表面上的顆粒為二氧化矽(SiO2)奈米粒子，也就是說加入二氧化矽(SiO2)於紡絲混合液中其奈米粒子可附於纖維上。 Please refer to "Figure 6a-6e" for the polymer fiber film NPS0 (Figure 6a), NPS3 (Figure 6b), NPS6 (Figure 6c), NPS9 (Figure 6d), NPS12 (Figure 6e) SEM image at 5,000x magnification. Each polymer fiber film presents a highly porous fiber network and is directional. Refer to "Figures 7a-7d" again for SEM images of polymer fiber films NPS3 (Figure 7a), NPS6 (Figure 7b), NPS9 (Figure 7c), and NPS12 (Figure 7d) at a magnification of 50,000 times on the fiber surface The particles are silicon dioxide (SiO 2 ) nano particles, that is, the silicon particles (SiO 2 ) added to the spinning mixture can be attached to the fibers.
高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12之平均纖維直徑及平均孔徑列於下表四。纖維直徑由Image J圖像處理軟體測定放大5,000倍率之SEM圖，而孔徑也是同樣使用Image J圖像處理軟體以Threshold方法將像素轉換為奈米尺度測定。 The average fiber diameter and average pore diameter of the polymer fiber films NPS0, NPS3, NPS6, NPS9, and NPS12 are listed in Table 4 below. The fiber diameter was measured by Image J image processing software at a magnification of 5,000 times, and the aperture was also measured by Image J image processing software using Threshold method to convert pixels to nanometer scale measurement.
由表四可知，未添加SiO2的高分子纖維薄膜NPS0平均纖維直徑為319nm，加入3%、6%、9%、12% SiO2的高分子纖維薄膜NPS3、NPS6、NPS9、NPS12的平均纖維直徑分別為282、277、248、220nm。可明顯看出平均纖維直徑隨著二氧化矽含量的增加而降低。在平均孔徑方面，高分子 纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12的平均孔徑分別為733、672、594、506、478nm。由此結果得知添加二氧化矽不僅會降低纖維直徑，也會導致孔徑縮小。 As can be seen from Table 4, the average fiber diameter of the polymer fiber film NPS0 without adding SiO 2 is 319 nm, and the average fibers of 3%, 6%, 9%, and 12% SiO 2 polymer fiber films NPS3, NPS6, NPS9, and NPS12 are added. The diameters are 282, 277, 248, and 220 nm, respectively. It can be clearly seen that the average fiber diameter decreases with increasing silica content. In terms of average pore diameter, the average pore diameters of the polymer fiber films NPS0, NPS3, NPS6, NPS9, and NPS12 are 733, 672, 594, 506, and 478nm, respectively. From this result, it was learned that the addition of silicon dioxide not only reduced the fiber diameter, but also caused the pore diameter to decrease.
實施例五 Example 5
本實施例著重於本發明高分子纖維薄膜的熱穩定性質分析。 This embodiment focuses on the thermal stability analysis of the polymer fiber film of the present invention.
於本實施例中，先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，不同重量百分比的二氧化矽(SiO2)(0%、3%、6%、9%、12%)，以及加入98%甲酸中，分別混合成30g的紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12。再將該紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12各別進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)得到高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are firstly used in a ratio of 2: 1 (2.6 g: 1.3 g), and different weight percentages of silicon dioxide (SiO 2 ) (0%, 3 %, 6%, 9%, 12%), and added to 98% formic acid, and mixed into 30g of spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12. The spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12 were each subjected to electrostatic spinning (the working condition was a voltage of 23V, the distance between the roller collection plate and the needle was 12 cm, the rotation speed of the roller collection plate was 1,500 rpm, and the flow rate of the spinning mixture solution was 0.0250. ml / min) to obtain polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12.
本實施例透過熱重分析儀(Thermogravimetric Analyzer，簡稱TGA)來分析本發明不同高分子纖維薄膜在不同的溫度下，紀錄薄膜的重量變化。本實施例的熱重分析儀為Perkin Elmer所製TGA 4000型號。該熱重分析儀主要為溫度控制系統和重量量測元件(微量天平)所組成。測量方式為設定通入氮氣流量20ml/min、程序溫度至600℃及升溫速率10°C/min，用火焰將陶瓷盤上的殘餘物或髒汙燃燒做清潔的手續，置入熱重分析儀(TGA)腔體秤重歸零，再秤量8~10毫克的試樣放入陶瓷盤內，放置熱重分析儀(TGA)腔體後，開始量測。 In this embodiment, a thermogravimetric analyzer (TGA) is used to analyze the weight changes of different polymer fiber films of the present invention at different temperatures. The thermogravimetric analyzer of this embodiment is a TGA 4000 model manufactured by Perkin Elmer. The thermogravimetric analyzer is mainly composed of a temperature control system and a weight measuring element (microbalance). The measurement method is to set the nitrogen flow rate of 20ml / min, the program temperature to 600 ° C, and the heating rate of 10 ° C / min, and use flame to clean the residue or dirt on the ceramic plate and put it into the thermogravimetric analyzer. (TGA) The cavity weighs back to zero, and then weigh 8 to 10 mg of the sample into a ceramic plate. After placing the thermogravimetric analyzer (TGA) cavity, the measurement is started.
本實施例以扣除水含量損失後，熱重損失10wt%為初始裂解溫度，再以儀器軟體做微分處理得知最快熱裂解溫度，分別將尼龍66、 PMMA及紡絲混合液NPS0以靜電紡絲抽成高分子纖維後進行熱重分析儀(TGA)的檢測分析，如『圖8』所示。 In this embodiment, after deducting the loss of water content, the thermal weight loss of 10wt% is used as the initial cracking temperature, and then the differential processing is performed by the instrument software to obtain the fastest thermal cracking temperature. PMMA and spinning mixed solution NPS0 are drawn into polymer fibers by electrostatic spinning, and then analyzed by thermogravimetric analyzer (TGA), as shown in "Figure 8".
由圖中可知，紡絲混合液NPS0生產出的高分子纖維薄膜並無明顯的兩個裂解峰，可說明尼龍66及PMMA很好的結合在一起，該高分子纖維薄膜NPS0的初始裂解溫度為388℃，尼龍66及PMMA的初始裂解溫度分別為425℃、295℃，表示尼龍66與PMMA成絲時相互作用的影響下，使高分子纖維薄膜NPS0有著良好的熱穩定性。 It can be seen from the figure that the polymer fiber film produced by the spinning mixed solution NPS0 has no obvious two cracking peaks, which can explain that nylon 66 and PMMA are well combined. The initial cracking temperature of the polymer fiber film NPS0 is The initial cracking temperatures of 388 ° C, nylon 66 and PMMA are 425 ° C and 295 ° C, respectively, which indicates that the polymer fiber film NPS0 has good thermal stability under the influence of the interaction between nylon 66 and PMMA filaments.
再者，請參閱『圖9』所示，為紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12以靜電紡絲抽成高分子纖維後進行熱重分析儀(TGA)的檢測分析比較圖。圖中顯示各紡絲混合液的熱穩定曲線圖相似重疊，皆於溫度約為70℃時，有溶劑抑或是水約2wt%的熱重損失。下表五列出為紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12製成之高分子纖維之初始裂解溫度、最快熱裂解溫度及殘餘量的分析。 Furthermore, please refer to "Figure 9", which is a comparison chart of the detection and analysis of the spinning mixture NPS0, NPS3, NPS6, NPS9, and NPS12 by electrostatic spinning after drawing polymer fibers with a thermogravimetric analyzer (TGA). The figure shows that the thermal stability curves of the spinning mixtures overlap similarly, and there is a thermogravimetric loss of solvent or water of about 2wt% at a temperature of about 70 ° C. Table 5 below lists the analysis of the initial cracking temperature, the fastest thermal cracking temperature, and the residual amount of polymer fibers made of the spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12.
由表五可知，紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12製成之高分子纖維之初始裂解溫度並無明顯差異，約介於378~388℃間，而最快熱裂解溫度為450、452、454、459、460℃，其隨著二氧化矽(SiO2)的含量增加而上升，由於二氧化矽絕佳的耐熱性，可說明是因二氧化矽的添加而增強了隔離膜的熱穩定性。 As can be seen from Table 5, the initial cracking temperature of the polymer fibers made from the spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12 was not significantly different, ranging from 378 to 388 ° C, and the fastest thermal cracking temperature was 450. , 452, 454, 459, and 460 ° C, which rises with the increase in the content of silicon dioxide (SiO 2 ). Due to the excellent heat resistance of silicon dioxide, it can be explained that the isolation film is enhanced by the addition of silicon dioxide Thermal stability.
實施例六 Example Six
本實施例探討加入不同量二氧化矽對於本發明高分子纖維薄膜拉伸強度的影響。 This embodiment discusses the effect of adding different amounts of silicon dioxide on the tensile strength of the polymer fiber film of the present invention.
於本實施例中，同樣先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，不同重量百分比的二氧化矽(SiO2)(0%、3%、6%、9%、12%)，以及加入98%甲酸中，分別混合成30g的紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12。再將該紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12各別進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)得到高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are also used at a ratio of 2: 1 (2.6 g: 1.3 g), and different weight percentages of silicon dioxide (SiO 2 ) (0%, 3%, 6%, 9%, 12%), and added to 98% formic acid, mixed into 30g of spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12. The spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12 were each subjected to electrostatic spinning (the working condition was a voltage of 23V, the distance between the roller collection plate and the needle was 12 cm, the rotation speed of the roller collection plate was 1,500 rpm, and the spinning mixture flow rate was 0.0250 ml / min) to obtain polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12.
本實施例的拉伸強度測試的方法與前述實施例三相同。先將高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12裁切為1cm×4cm的長條狀，其上下皆由鋁箔包覆以利儀器檢測，包覆之長度約為1cm，每個試樣皆進行三次檢測取其平均值。下表六為不同高分子纖維薄膜檢測結果之比較。 The method for testing the tensile strength in this embodiment is the same as that in the third embodiment. First cut the polymer fiber film NPS0, NPS3, NPS6, NPS9, NPS12 into long strips of 1cm × 4cm, and the upper and lower sides are covered with aluminum foil to facilitate detection by the instrument. All three tests were performed to obtain the average value. Table 6 below is a comparison of the test results of different polymer fiber films.
如表六所示，本發明高分子纖維薄膜最大負重、拉伸強度及彈性係數皆隨著二氧化矽(SiO2)含量增加而升高，直到二氧化矽含量6%達到 最高，接著又隨著二氧化矽含量增加而降低；其中拉伸強度最高為二氧化矽含量6%的29.10MPa，而最小拉伸強度為二氧化矽含量12%的15.77MPa。一般圓筒型鋰電池的製程張力約為13MPa，顯然本發明高分子纖維薄膜即使不加入二氧化矽仍足以承受該製程張力。 As shown in Table 6, the maximum load, tensile strength, and elastic coefficient of the polymer fiber film of the present invention all increased with the increase in the content of silicon dioxide (SiO 2 ), until the content of silicon dioxide reached 6%, and then increased with As the silicon dioxide content increases, it decreases; the highest tensile strength is 29.10 MPa with a silicon dioxide content of 6%, and the minimum tensile strength is 15.77 MPa with a silicon dioxide content of 12%. Generally, the process tension of a cylindrical lithium battery is about 13 MPa. Obviously, the polymer fiber film of the present invention is sufficient to withstand the process tension even without adding silicon dioxide.
此外，本發明高分子纖維薄膜的伸長量則隨著SiO2含量增加而增加，顯見二氧化矽(SiO2)的添加確實會增強本發明高分子纖維薄膜的延展性。 In addition, the elongation of the polymer fiber film of the present invention increases as the content of SiO 2 increases. It is obvious that the addition of silicon dioxide (SiO 2 ) will indeed enhance the ductility of the polymer fiber film of the present invention.
實施例七 Example Seven
本實施例要討論加入不同量二氧化矽對於本發明高分子纖維薄膜的耐穿刺性影響。 In this embodiment, the effect of adding different amounts of silicon dioxide on the puncture resistance of the polymer fiber film of the present invention is discussed.
於本實施例中，同樣先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，不同重量百分比的二氧化矽(SiO2)(0%、3%、6%、9%、12%)，以及加入98%甲酸中，分別混合成30g的紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12。再將該紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12各別進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)得到高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are also used at a ratio of 2: 1 (2.6 g: 1.3 g), and different weight percentages of silicon dioxide (SiO 2 ) (0%, 3%, 6%, 9%, 12%), and added to 98% formic acid, mixed into 30g of spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12. The spinning mixtures NPS0, NPS3, NPS6, NPS9, and NPS12 were each subjected to electrostatic spinning (the working condition was a voltage of 23V, the distance between the roller collection plate and the needle was 12 cm, the rotation speed of the roller collection plate was 1,500 rpm, and the flow rate of the spinning mixture solution was 0.0250. ml / min) to obtain polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12.
本實施例穿刺強度是依ASTM F1306-1990規範內容做檢測，將高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12送至財團法人紡織產業綜合研究(Taiwan Textile Research Institute)所進行委託測試，穿刺強力委託測試之結果如下表七所示。 In this example, the puncture strength is tested in accordance with the specifications of ASTM F1306-1990. The polymer fiber films NPS0, NPS3, NPS6, NPS9, and NPS12 are sent to the Taiwan Textile Research Institute for consignment testing and puncture. The results of the strong commission test are shown in Table 7 below.
根據表七的結果，本發明高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12的穿刺強力結果差異不大，彼此間趨勢與拉伸強度相似，隨二氧化矽(SiO2)含量增加先上升後下降，其中加入二氧化矽6%的高分子纖維薄膜NPS6的穿刺強力最高為5.5N，以無加入二氧化矽的高分子纖維薄膜NPS0最低則為4.9N。 According to the results in Table 7, the puncture strength results of the polymer fiber films of the present invention NPS0, NPS3, NPS6, NPS9, and NPS12 are not significantly different, and the trends and tensile strengths are similar to each other, and they increase first as the content of silicon dioxide (SiO 2 ) increases. After the drop, the puncture strength of the polymer fiber film NPS6 with 6% of silicon dioxide added was the highest at 5.5N, and the polymer fiber film with no silicon dioxide added at the lowest NPS0 was 4.9N.
實施例八 Example eight
本實施例在探討即使在電池過熱的情況下，高分子纖維薄膜必須維持其形狀及大小，以確保電池兩極不會相互接觸，因此進行尺寸熱收縮試驗。 In this embodiment, even when the battery is overheated, the polymer fiber film must maintain its shape and size to ensure that the two poles of the battery will not contact each other, so a dimensional heat shrinkage test is performed.
於本實施例中，同樣先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，不同重量百分比的二氧化矽 (SiO2)(0%、3%、6%、9%、12%)，以及加入98%甲酸中，分別混合成30g的紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12。再將該紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12以及聚丙烯(polypropylene,PP)各別進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)得到高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12以及聚丙烯薄膜。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are also used at a ratio of 2: 1 (2.6 g: 1.3 g), and different weight percentages of silicon dioxide (SiO 2 ) (0%, 3%, 6%, 9%, 12%), and added to 98% formic acid, mixed into 30g of spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12. The spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12, and polypropylene (PP) were each subjected to electrostatic spinning (the working condition was a voltage of 23V, the distance between the roller collecting plate and the needle was 12cm, and the rotating speed of the roller collecting plate was 1,500. rpm, spinning mixture flow rate 0.0250ml / min) to obtain polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12 and polypropylene films.
將前述高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12與聚丙烯薄膜剪裁為2cm×2cm之大小，放入高溫爐(FuData，型號FD-303)加熱在150℃下暴露30分鐘。使用Image J圖像處理軟體以Threshold方法將像素轉換為厘米尺度測定加熱前後之高分子纖維薄膜面積得以求得收縮率，如式(3)，結果如表八。 The aforementioned polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12, and polypropylene film were cut to a size of 2 cm × 2 cm, placed in a high-temperature furnace (FuData, model FD-303), and exposed at 150 ° C. for 30 minutes. Image J image processing software was used to convert pixels to centimeter scale by Threshold method to measure the area of the polymer fiber film before and after heating to obtain the shrinkage rate, as shown in formula (3). The results are shown in Table 8.
其中Ab為加熱前面積，Aa為加熱後面積。 Where A b is the area before heating and A a is the area after heating.
聚丙烯薄膜在加熱後已失去膜的型態，甚至出現熔解的現象，而本發明高分子纖維薄膜NPS3及NPS9有些微蜷縮的現象，從上表八中 結果而言高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12的收縮率皆為8-9%之間。 The polypropylene film has lost its shape and even melted after being heated. The polymer fiber films NPS3 and NPS9 of the present invention have a slight shrinkage phenomenon. As a result, the shrinkage rates of the polymer fiber films NPS0, NPS3, NPS6, NPS9, and NPS12 were all between 8-9%.
實施例九 Example Nine
本實施例企圖討論加入不同量二氧化矽對於本發明高分子纖維薄膜的孔隙度以及電解液攝取率的影響。 This embodiment attempts to discuss the effect of adding different amounts of silicon dioxide on the porosity and electrolyte uptake rate of the polymer fiber film of the present invention.
於本實施例中，同樣先將尼龍66與聚甲基丙烯酸甲酯(PMMA)以2：1的比例(2.6g：1.3g)，不同重量百分比的二氧化矽(SiO2)(0%、3%、6%、9%、12%)，以及加入98%甲酸中，分別混合成30g的紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12。再將該紡絲混合液NPS0、NPS3、NPS6、NPS9、NPS12以及聚丙烯(polypropylene,PP)各別進行靜電紡絲(工作條件為電壓23V，滾筒收集板與針頭距離12cm、滾筒收集板轉速1,500rpm，紡絲混合液流速0.0250ml/min)得到高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12以及聚丙烯薄膜。 In this embodiment, nylon 66 and polymethyl methacrylate (PMMA) are also used at a ratio of 2: 1 (2.6 g: 1.3 g), and different weight percentages of silicon dioxide (SiO 2 ) (0%, 3%, 6%, 9%, 12%), and added to 98% formic acid, mixed into 30g of spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12. The spinning mixtures NPS0, NPS3, NPS6, NPS9, NPS12, and polypropylene (PP) were each subjected to electrostatic spinning (the working condition was a voltage of 23V, the distance between the roller collecting plate and the needle was 12cm, and the rotating speed of the roller collecting plate was 1,500. rpm, spinning mixture flow rate 0.0250ml / min) to obtain polymer fiber films NPS0, NPS3, NPS6, NPS9, NPS12 and polypropylene films.
本實施例測量不同量二氧化矽的高分子纖維薄膜以及聚丙烯薄膜的孔隙度的方法與實施例三相同，各高分子纖維薄膜及聚丙烯的孔隙度的結果如下表九。 The method for measuring the porosity of polymer fiber films and polypropylene films with different amounts of silicon dioxide in this embodiment is the same as that in Example 3. The results of the porosity of each polymer fiber film and polypropylene are shown in Table 9 below.
由表九可知，聚丙烯薄膜的孔隙度為最小為33.70%，而本發明高分子纖維薄膜NPS0、NPS3、NPS6、NPS9、NPS12之孔隙度明顯高於聚丙烯薄膜，其中高分子纖維薄膜NPS6孔隙度最高為91.4%，而高分子纖維薄膜NPS12最小為84.42%。該孔隙度隨著加入二氧化矽增加而升高至二氧化矽6%後下降，高分子纖維薄膜NPS9及NPS12之孔隙度反而降低。 As can be seen from Table 9, the minimum porosity of polypropylene film is 33.70%, and the porosity of the polymer fiber films NPS0, NPS3, NPS6, NPS9, and NPS12 of the present invention is significantly higher than that of polypropylene films, and the polymer fiber film NPS6 has porosity. The highest degree is 91.4%, while the minimum of polymer fiber film NPS12 is 84.42%. The porosity increased with the addition of silicon dioxide and then decreased to 6% of silicon dioxide, and the porosity of the polymer fiber films NPS9 and NPS12 decreased.
再者，本實施例討論不同量二氧化矽的高分子纖維薄膜以及聚丙烯薄膜對電解液攝許率的影響。 Furthermore, this embodiment discusses the effects of polymer fiber films and polypropylene films with different amounts of silicon dioxide on the permittivity of the electrolyte.
本實施例的電解液攝取率是將隔離膜試片剪裁為2cm×2cm之大小，浸泡於電解液中，靜置室溫兩小時後，將試片取出擦去多餘的電解液稱取其重量，再利用式(4)計算，其結果列於下表十。其中Ww為濕式樣之重量，Wd為乾式樣之重量，ρ為液體密度，V為試樣之體積。 The electrolyte uptake rate of this embodiment is to cut a test piece of the separator to a size of 2cm × 2cm, soak it in the electrolyte, and leave it at room temperature for two hours. Then remove the test piece and wipe away the excess electrolyte to weigh it. Then, calculate it with formula (4), and the results are listed in Table 10 below. Where Ww is the weight of the wet pattern, Wd is the weight of the dry pattern, ρ is the density of the liquid, and V is the volume of the sample.
由表十可知，本發明高分子纖維薄膜的電解液攝取率的趨勢 與孔隙度相同，皆是隨著二氧化矽(SiO2)含量增加而先上升後下降。高分子纖維薄膜NPS6的電解液攝取率為最高417.39%，高分子纖維薄膜NPS12的電解液攝取率為最低344.93%。在許多文獻中亦證明出電解液攝取率與隔離膜之電化學性能相關，高電解液攝取率有助於組成鋰電池後之電池性能的提升。 It can be seen from Table 10 that the tendency of the electrolyte uptake rate of the polymer fiber film of the present invention is the same as the porosity, and both increase first and then decrease as the content of silicon dioxide (SiO 2 ) increases. The highest electrolyte uptake rate of polymer fiber film NPS6 is 417.39%, and the lowest electrolyte uptake rate of polymer fiber film NPS12 is 344.93%. It has also been proven in many literatures that the electrolyte uptake rate is related to the electrochemical performance of the separator. A high electrolyte uptake rate contributes to the improvement of battery performance after forming a lithium battery.
以上已將本發明做一詳細說明，惟以上所述者，僅為本發明之一較佳實施例而已，當不能以此限定本發明實施之範圍，即凡依本發明申請專利範圍所作之均等變化與修飾，皆應仍屬本發明之專利涵蓋範圍內。 The present invention has been described in detail above, but the above is only one of the preferred embodiments of the present invention. When the scope of implementation of the present invention cannot be limited by this, that is, the equality made according to the scope of patent application of the present invention Changes and modifications should still be covered by the patent of the present invention.
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