TWI421289B - Preparation and Application of Porous Polyvinyl Alcohol / Polyoxyethylene Polymer Electrolyte Membrane - Google Patents

Preparation and Application of Porous Polyvinyl Alcohol / Polyoxyethylene Polymer Electrolyte Membrane Download PDF

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TWI421289B
TWI421289B TW099101177A TW99101177A TWI421289B TW I421289 B TWI421289 B TW I421289B TW 099101177 A TW099101177 A TW 099101177A TW 99101177 A TW99101177 A TW 99101177A TW I421289 B TWI421289 B TW I421289B
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polyvinyl alcohol
polyethylene oxide
electrode
polymer
porous
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TW201125906A (en
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Chun Chen Yang
Po Wei Chen
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Chun Chen Yang
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Description

多孔性聚乙烯醇/聚氧化乙烯高分子電解質膜的製法及其應用Method for preparing porous polyvinyl alcohol/polyoxyethylene polymer electrolyte membrane and application thereof

本發明係有關一種高分子電解質膜的製法，尤指一種使用非溶劑法及部份溶解法製備具有多孔性的聚乙烯醇/聚氧化乙烯(PVA/PEO)高分子電解質膜的方法，該多孔性固態複合式高分子膜主要是由聚乙烯醇(PVA)和聚氧化乙烯(PEO)兩種高分子共同摻合所組成。The present invention relates to a method for producing a polymer electrolyte membrane, and more particularly to a method for preparing a porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) polymer electrolyte membrane using a non-solvent method and a partial dissolution method. The solid solid polymer membrane is mainly composed of a blend of polyvinyl alcohol (PVA) and polyethylene oxide (PEO).

目前3C電子產品均有朝向輕薄短小發展的趨勢，但其發展條件，主要受制於電力之來源-電池，如能開發出既薄、電容量大、且不佔空間的電池，將來在市場上定會具有一定的競爭力，開發高導電度之固態薄型高分子電解質不但可解決漏液，以及減少所佔電池之空間，且可使電池用途能更加的廣泛。At present, 3C electronic products are trending towards light, thin and short development, but their development conditions are mainly controlled by the source of electricity - batteries. If you can develop batteries that are thin, have large capacity, and do not take up space, they will be set in the market in the future. It will be competitive, and the development of high-conductivity solid-state thin polymer electrolyte can not only solve the leakage, but also reduce the space occupied by the battery, and can make the battery more widely used.

電池係利用化學活性物質產生電化學反應的系統，其性能受到材料而左右。高分子材料原係為絕緣體，但經適當的處理後，高分子可變成導電性材料，係近年來高分子材料科技上的突破性發展。導電性高分子材料具有化學構造上的特徵，例如導電性高分子均具局部化的π-電子密度，基於雙鍵之共振效果，可呈現載體之作用，再因局部化的結果而產生游離基離子。加上，π-軌道之幾何形態將容許軌道之重疊，更促進分子間的載體輸送。由於分子鏈長遠較實際材料試片尺寸短，故試片之導電主要須靠分子間的輸送。A battery is a system in which an electrochemical reaction is generated using a chemically active substance, and its performance is influenced by a material. The polymer material is originally an insulator, but after proper treatment, the polymer can become a conductive material, which is a breakthrough in the technological development of polymer materials in recent years. The conductive polymer material has chemical structural characteristics. For example, the conductive polymer has a localized π-electron density. Based on the resonance effect of the double bond, the carrier can function as a carrier, and a radical is generated due to localization. ion. In addition, the geometry of the π-orbital will allow for the overlap of the orbitals and promote the transport of carriers between the molecules. Since the molecular chain is much shorter than the actual material test piece, the conduction of the test piece mainly depends on the intermolecular transport.

在1953年，M. B. Armand等人提出以聚環氧化乙烯(PEO,polyethylene oxide)與鹼金屬鹽之錯合物可應用於電池當作固態高分子電解質之後，發展出既薄且導電度高的高分子電解質，即成為一個相當熱門的研究與發展主題；經過國內、外長期之研究與發展，發現傳統的聚環氧乙烷系高分子電解質，在常溫的離子導電度介於10-7 ~10-5 S/cm之間，如此低的離子導電度常被限制它的發展，電池無法承受較大電流之負載，而降低固態高分子電解質在電池上的實用性與發展；因此，欲提昇高分子電解質在常溫下的離子導電度，已經成為此領域最重要的課題。通常，一般能應用於電池之固態高分子電解質應滿足符合以下各項條件：In 1953, MB Armand et al. proposed that a complex of poly(ethylene oxide) (PEO) and an alkali metal salt can be applied to a battery as a solid polymer electrolyte to develop a thin and highly conductive high. Molecular electrolytes have become a very popular research and development theme. After long-term research and development at home and abroad, it has been found that traditional polyethylene oxide polymer electrolytes have an ionic conductivity of 10 -7 ~ 10 at room temperature. Between -5 S/cm, such low ionic conductivity is often limited by its development, the battery can not withstand the load of large current, and reduce the practicality and development of solid polymer electrolyte on the battery; therefore, want to increase The ion conductivity of molecular electrolytes at normal temperature has become the most important issue in this field. Generally, solid polymer electrolytes that can generally be applied to batteries should meet the following conditions:

1.常溫下離子導電度在10-3 S/cm以上，導電度愈高，則增加電池所能承受的大電流放電，有助於應用在附加多功能的電子產品。1. The ion conductivity is above 10 -3 S/cm at normal temperature, and the higher the conductivity, the higher the current discharge that the battery can withstand, which is helpful for the application of additional multifunctional electronic products.

2.較寬的電化學穩定範圍(windows of electrochemical stability)，可增加電極與電解質介面間之穩定性，提昇電池之電化學特性。2. The wide window of electrochemical stability can increase the stability between the electrode and the electrolyte interface and improve the electrochemical characteristics of the battery.

3.較低的反應活化能(Ea,activation energy)，可降低電池對溫度之敏感度。3. Lower activation energy (Ea), which can reduce the sensitivity of the battery to temperature.

近來，雖然有人提出將不同種類之高分子以共聚合方式製造出結構較強的固態高分子電解質，但實際的成本及反應機制過於複雜，以致應用於電池之生產成本過高，而不合乎經濟成本，實有待改善。Recently, although it has been proposed to produce different types of solid polymer electrolytes by copolymerization of different types of polymers, the actual cost and reaction mechanism are too complicated, so that the production cost of the battery is too high, and it is not economical. The cost has to be improved.

本發明主要目的係提供一種新穎的複合式高分子電解質膜，該高分子電解質膜的導電度在常溫下可達10-1 S/cm-1 ，逼近於液態鹼性電解液離子導電度，可大大提升常溫型高分子電解質膜在電池上應用之實用性。The main object of the present invention is to provide a novel composite polymer electrolyte membrane having a conductivity of 10 -1 S/cm -1 at room temperature, which is close to the ionic conductivity of the liquid alkaline electrolyte. The utility of the room temperature type polymer electrolyte membrane on the battery is greatly improved.

為達成前述之目的，本案所採取之技術手段係提供一種多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜之製法，其包括：(a)選取分子量介於2,000~120,000的聚乙烯醇(PVA)，使用量為30~95wt.%，在常溫下及密閉環境下與重量比50~60wt.%的第一溶劑之水攪拌混合反應；(b)將重量比為1~40wt.%之聚氧化乙烯(PEO)粉末，在常溫 及連續攪拌下與第一溶劑的水攪拌混合反應；(c)將聚乙烯醇/聚氧化乙烯高分子混合溶液中加入5~20wt.%的第二非溶劑均勻混合，再加入1wt.%~75wt.%的交聯劑，攪拌約5~60分鐘後，另加入0.1wt.%~20wt.%的觸媒，攪拌2~10分鐘，並在20~70℃進行交聯反應；(d)將步驟c所得之高分子黏液依照所需的膜厚去控制塗佈於承載盤上，於溫度在80℃下，真空度在0.06MPa，放置約10~24小時，以成為固態聚乙烯醇/聚氧化乙烯摻合高分子電解質膜，取出承載盤置於常溫下熱平衡，即可將薄膜取下；以及(e)取適當大小之固態聚乙烯醇/聚氧化乙烯摻合高分子電解質膜置入四氫呋喃(THF)有機溶劑中，以進行選擇性的溶解聚氧化乙烯，於20~65℃下，放置約1~24小時，使聚氧化乙烯形成許多微孔。In order to achieve the foregoing objectives, the technical means adopted in the present invention is to provide a porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) blended polymer electrolyte membrane, which comprises: (a) selecting a molecular weight of 2,000~ 120,000 polyvinyl alcohol (PVA), used in an amount of 30 to 95 wt.%, stirred and mixed with water of a first solvent having a weight ratio of 50 to 60 wt.% at room temperature and in a closed environment; (b) the weight ratio is 1~40wt.% of polyethylene oxide (PEO) powder at room temperature And stirring and mixing with water of the first solvent under continuous stirring; (c) uniformly adding 5~20 wt.% of the second non-solvent to the polyvinyl alcohol/polyethylene oxide polymer mixed solution, and adding 1 wt.%~ 75 wt.% of the crosslinking agent, after stirring for about 5 to 60 minutes, another 0.1 wt.% to 20 wt.% of the catalyst is added, stirred for 2 to 10 minutes, and cross-linked at 20 to 70 ° C; (d) The polymer mucilage obtained in the step c is controlled to be applied to the carrier tray according to the required film thickness, and the vacuum is at 0.06 MPa at a temperature of 80 ° C for about 10 to 24 hours to become a solid polyvinyl alcohol / Polyethylene oxide is blended with a polymer electrolyte membrane, the carrier tray is taken out to be thermally equilibrated at room temperature, and the film can be removed; and (e) an appropriate size solid polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane is placed. In a tetrahydrofuran (THF) organic solvent, a selective dissolution of polyethylene oxide is carried out at 20 to 65 ° C for about 1 to 24 hours to form a plurality of micropores in the polyethylene oxide.

本發明另一目的係提供一種使用鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜的應用，該膜可搭配多孔性二次電極，例如Zn電極、Cd電極、Fe電極、MnO2 電極、Ni(OH)2 電極、碳電極，以進行充/放電。Another object of the present invention is to provide an application of a polymer electrolyte membrane using an alkaline porous polyvinyl alcohol/polyethylene oxide (PVA/PEO), which can be combined with a porous secondary electrode such as a Zn electrode or a Cd electrode. The Fe electrode, the MnO 2 electrode, the Ni(OH) 2 electrode, and the carbon electrode are charged/discharged.

本發明又一目的係提供一種使用鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜的應用，該膜可搭配多孔性碳電極，以組成一電容器(capacitors)，該電容器可進行充/放電。Still another object of the present invention is to provide an application of a polymer electrolyte membrane using an alkaline porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) which can be combined with a porous carbon electrode to form a capacitor. The capacitor can be charged/discharged.

本發明再一目的係提供一種使用鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜的應用，該膜可搭配PtRu/C或PtRu黑(含量1~10mg/cm2 )陽電極，Pt/C、Pt黑(含量1~10mg/cm2)陰電極，以組成一種直接甲醇燃料電池(Alkaline DMFC)，該直接甲醇燃料電池可進行放電。Still another object of the present invention is to provide an application of a polymer electrolyte membrane blended with an alkali porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) which can be used with PtRu/C or PtRu black (content 1 to 10 mg/ Cm 2 ) A positive electrode, Pt/C, Pt black (content 1~10mg/cm2) cathode electrode to form a direct methanol fuel cell (Alkaline DMFC), which can be discharged.

本發明另一目的係提供一種使用鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜的應用，該膜可搭配Pt/C、Pt黑(含量1~10mg/cm2 )電極，以組成一種氫-氧燃料電池(Alkaline PEMFC)，該氫-氧燃料電池可進行放電的應用。Another object of the present invention is to provide an application of a polymer electrolyte membrane using an alkaline porous polyvinyl alcohol/polyethylene oxide (PVA/PEO), which can be combined with Pt/C and Pt black (content 1 to 10 mg/ Cm 2 ) electrodes to form a hydrogen-oxygen fuel cell (Alkaline PEMFC), which can be used for discharge applications.

其中，聚乙烯醇(PVA,poly(vinyl alcohol))，係一種以共價鍵及氫鍵所結合的高分子，屬於一種無定型具低結晶性的高分子，且為具旋轉結構之高分子鏈，可阻隔電子之傳導，並為一種柔軟性相當高的高分子材料。由於聚乙烯醇具有氫氧基(-OH)，為一種親水性相當高的高分子，與同樣具有氫氧基之水及氫氧化鉀，具有相當好的相容性；金屬離子在聚乙烯醇高分子內之傳導，係利用金屬離子與高分子鏈骨幹之強偶合作用力產生暫時性的配位結合，再利用高分子鏈之柔軟性將金屬離子傳輸出。聚乙烯醇係一種用途相當的普遍、價位低廉且無任何環保問題之高分子材料，將其應用於鋅空氣電池、鹼性電池、燃料電池、鎳氫電池，取代現有市售的PP/PE或纖維素之隔離膜，將成為未來的新趨勢。Among them, polyvinyl alcohol (PVA, poly(vinyl alcohol)) is a polymer which is bonded by a covalent bond and a hydrogen bond, and belongs to an amorphous polymer having a low crystallinity and a polymer having a rotating structure. The chain blocks the conduction of electrons and is a highly flexible polymer material. Since polyvinyl alcohol has a hydroxyl group (-OH), it is a relatively hydrophilic polymer, and has a relatively good compatibility with water and potassium hydroxide which also have a hydroxyl group; metal ions in polyvinyl alcohol The conduction in the polymer is to use a strong coupling force between the metal ion and the polymer backbone to generate a temporary coordination bond, and then use the flexibility of the polymer chain to transport the metal ion. Polyvinyl alcohol is a kind of polymer material with similar application, low price and no environmental protection problem. It is applied to zinc air battery, alkaline battery, fuel cell and nickel hydrogen battery to replace the existing commercially available PP/PE or The cellulose separator will become a new trend in the future.

而聚乙烯醇(PVA)具有高氧氣阻斷性，若將其應用於一次鋅空氣電池上時，可隔絕空氣中的氧氣透過隔離膜進入至負極與鋅反應產生氧化，增加電池壽命；由於電解液含於高分子膜中保持凝膠狀態，可解決電解液於一般隔離膜滲出造成電池漏液的問題，且置於高溫亦有甚高的導電度及電化學穩定性。但是，應用於二次(secondary)鋅空氣電池(rechargeable Zn/air battery)上時，因為在充/放電過程時會有副反應發生，而產生氫氣或氧氣，反而使得具有氣體阻斷性的聚乙烯醇(PVA)隔絕了氣體之輸出，而令鋅二次電極膨脹，並在鋅二次電極上形成一層氣體膜，反而使得電池循環壽命下降。Polyvinyl alcohol (PVA) has high oxygen barrier property. If it is applied to a zinc-air battery, it can block the oxygen in the air from entering the negative electrode and reacting with the zinc to generate oxidation, which increases the battery life. The liquid is contained in the polymer film to maintain the gel state, which can solve the problem that the electrolyte leaks out due to the leakage of the common separator, and has high conductivity and electrochemical stability at high temperature. However, when applied to a secondary Zn/air battery, hydrogen or oxygen is generated because a side reaction occurs during the charge/discharge process, which in turn causes a gas barrier property. Vinyl alcohol (PVA) isolates the output of the gas, causing the zinc secondary electrode to expand and form a gas film on the zinc secondary electrode, which in turn reduces the cycle life of the battery.

本發明提供一種多孔性聚乙烯醇/聚氧化乙烯摻合高分子電解質膜，其主要是由聚乙烯醇(PVA)和聚氧化乙烯(PEO)兩種高分子摻合所組成的高分子電解質膜，由於聚乙烯醇薄膜具有相當良好親水性、高的離子導電度，以及結構相當緻密性等特殊性，因此相當適合應用在許多鹼性一次電池上。不過，由於純聚乙烯醇的薄膜結構的關係，聚乙烯醇高分子薄膜具有相當良好的氣密性，造成二次鋅電極在充/放電時所產生的氣體(O2 或H2 )無法宣洩排出，因而造成高分子電解質膜膨脹剝離二次鋅電極表面，導致二次鋅電極嚴重的變形，同時也會在二次鋅電極表面形成一層氣體膜，增加了二次鋅電極的膜電阻(film resistance)，大幅增加了二次鋅電極的所需活化時間。The invention provides a porous polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane, which is mainly composed of a polymer electrolyte membrane composed of polyvinyl alcohol (PVA) and polyethylene oxide (PEO) polymer blending. Since the polyvinyl alcohol film has a particularly good hydrophilicity, a high ionic conductivity, and a relatively compact structure, it is quite suitable for use in many alkaline primary batteries. However, due to the film structure of pure polyvinyl alcohol, the polyvinyl alcohol polymer film has a relatively good airtightness, and the gas (O 2 or H 2 ) generated during the charging/discharging of the secondary zinc electrode cannot be vented. Discharge, thus causing the polymer electrolyte membrane to swell and peel off the surface of the secondary zinc electrode, causing severe deformation of the secondary zinc electrode, and also forming a gas film on the surface of the secondary zinc electrode, increasing the membrane resistance of the secondary zinc electrode (film Resistance), which greatly increases the required activation time of the secondary zinc electrode.

因此，將聚氧化乙烯摻合聚乙烯醇中，製備成高分子薄膜，再使用適當的有機溶劑例如四氫呋喃(THF)，可將聚氧化乙烯部份溶解(partial-etch)，藉此在複合式高分子薄膜中形成特殊細微的小孔洞(micro-pores)。所形成的微小孔洞(micro-porous)大小，剛好介於針狀鋅和氣體分子大小之間，如此便能達到一方面能阻止針狀鋅刺穿的高分子膜。Therefore, polyoxyethylene is blended into polyvinyl alcohol to prepare a polymer film, and a suitable organic solvent such as tetrahydrofuran (THF) can be used to partially dissolve the polyethylene oxide, thereby Special fine micro-pores are formed in the polymer film. The size of the micro-porous formed is just between the size of the acicular zinc and the gas molecules, so that a polymer film capable of preventing needle-like zinc puncture can be achieved.

另一方面，此多孔性膜具有適當大小的孔洞，可以讓二次鋅電極在充/放電間所產生的氣體(主要是水分解生成的)宣洩而出，降低電極之極化，而減少電極活化時間。因為高分子膜緊密貼在二次鋅電極表面，可有效的抑制鋅電極變形及針狀鋅形成的問題。一般市售之PE/PP隔離膜孔洞夠大(約10~20μm)，是可以使氣體(H2 )宣洩而出，但是卻會造成非常嚴重的針狀鋅刺穿隔離膜及鋅電極變形的問題，根本無法使用。On the other hand, the porous membrane has pores of appropriate size, which allows the gas generated by the secondary zinc electrode between charge and discharge (mainly formed by water decomposition) to vent, lowering the polarization of the electrode, and reducing the electrode. Activation time. Since the polymer film is closely attached to the surface of the secondary zinc electrode, the deformation of the zinc electrode and the formation of acicular zinc can be effectively suppressed. The commercially available PE/PP separator has a large hole (about 10~20μm), which can make the gas (H 2 ) vent out, but it will cause very serious needle-like zinc piercing separator and zinc electrode deformation. The problem is simply not available.

而本發明使用聚氧化乙烯(PEO)當做媒介可以均勻而有效的控制微小孔洞大小，主要的控制方法是加入非溶劑DMF的量及第二高分子，例如聚氧化乙烯(PEO)的添加量，形成大小均一的微小孔洞，可以協助電極界面間氣體之排出，且不會造成針狀鋅刺穿高分子隔離膜，以及電極變形等問題。本發明之多孔性聚乙烯醇/聚氧化乙烯摻合高分子電解質膜製備方法簡單，且成本非常低，可以應用在許多二次電池上。However, the present invention uses polyethylene oxide (PEO) as a medium to uniformly and effectively control the size of small pores. The main control method is to add the amount of non-solvent DMF and the amount of second polymer, such as polyethylene oxide (PEO). The formation of small pores of uniform size can assist the gas discharge between the electrode interfaces without causing problems such as needle-like zinc piercing of the polymer separator and electrode deformation. The porous polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane of the present invention is simple in preparation method and low in cost, and can be applied to many secondary batteries.

茲將本發明之製備具有多孔性的聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜方法詳敘述如下：首先，取聚乙烯醇(PVA)和10wt.%之聚氧化乙烯(PEO)分別溶解於第一溶劑，例如水中，將反應器以水浴或其他加熱方式控制80~90℃溫度下，使聚乙烯醇及聚氧化乙烯完全溶解，時間約60~100分鐘內，將此溶解後的兩高分子黏液攪拌混合，接著在PVA/PEO高分子混合溶液中加入使用量為1~100wt.%之間的第二非溶劑，例如二甲基甲醯胺(DMF,dimethyl formamide)、伽瑪羥基丁酸(BL,γ-butyrolactone)、二甲基亞碸(DMSO,dimethylsulfoxide)、硫酸二甲酯(DMSI,dimethyl sulfite)、碳酸丙烯酯(PC,propylene carbonate)、碳酸乙烯酯(EC,ethylene carbonate)、環丁碸(sufolane)、N-甲基吡咯烷酮(NMP,N-methylpyrrolidinone)，均勻混合，再加入交聯劑，例如戊二醛(GA,gutaraldehyde)丁二醛、己二醛等，其含量在1wt.%~75wt.%之間，最佳為5~20wt.%，並在20~70℃，最佳在40~50℃溫度之間進行交聯反應，攪拌約10分鐘；最後加入0.1wt.%~20wt.%的觸媒，例如鹽酸、H2 SO4 、HNO3 等，其含量在0.1wt.%~20wt.%之間，最佳為1~5wt.%，攪拌5分鐘後，利用刮刀式塗佈機進行塗佈成膜。The method for preparing a polyvinyl alcohol/polyethylene oxide (PVA/PEO) blended polymer electrolyte membrane having porosity of the present invention is described in detail as follows: First, polyvinyl alcohol (PVA) and 10 wt.% of polyethylene oxide are taken. (PEO) is dissolved in the first solvent, for example, water, and the reactor is controlled by a water bath or other heating method at a temperature of 80 to 90 ° C to completely dissolve the polyvinyl alcohol and the polyethylene oxide, and the time is about 60 to 100 minutes. The dissolved two polymer mucilages are stirred and mixed, and then a second non-solvent is used in the PVA/PEO polymer mixed solution in an amount of 1 to 100 wt.%, such as dimethyl formamide (DMF, dimethyl formamide). ), gamma hydroxybutyric acid (BL, γ-butyrolactone), dimethyl sulfoxide, dimethyl sulfite, propylene carbonate, propylene carbonate, ethylene carbonate (EC, ethylene carbonate), sufolane, N-methylpyrrolidinone, uniformly mixed, and then added a crosslinking agent such as glutaraldehyde (GA, gutaraldehyde) succinaldehyde, Dialdehyde, etc., its content is between 1wt.%~75wt.%, preferably 5~20wt. %, and at 20 ~ 70 ° C, the best cross-linking reaction between 40 ~ 50 ° C temperature, stirring for about 10 minutes; finally adding 0.1wt.% ~ 20wt.% of the catalyst, such as hydrochloric acid, H 2 SO 4 HNO 3 or the like is contained in an amount of 0.1 wt.% to 20 wt.%, preferably 1 to 5 wt.%, and after stirring for 5 minutes, it is coated by a knife coater to form a film.

為避免氣體(air bubbles)的生成，將聚乙烯醇/聚氧化乙烯摻合的水溶液以100~200rpm轉速混合充分攪拌1~12小時，之後混合高分子溶液在100~500rpm轉速下充分攪拌1~3小時，即可去除氣體。In order to avoid the formation of air bubbles, the polyvinyl alcohol/polyethylene oxide blended aqueous solution is mixed at 100-200 rpm for 1 to 12 hours, and then the mixed polymer solution is stirred at 100-500 rpm for 1~. The gas can be removed in 3 hours.

接著，使用塗佈機並控制塗佈摻合高分子黏液的厚度於承載盤，例如玻璃板、聚四氟乙烯(PTFE)盤或不鏽鋼盤中，然後將此玻璃板置於真空烘箱中，烘箱溫度設定80℃，真空壓力設定0.06MPa，烘烤3小時，進行乾燥成膜。Next, using a coater and controlling the thickness of the coated blended polymer mucilage in a carrier tray, such as a glass plate, a polytetrafluoroethylene (PTFE) disk, or a stainless steel pan, and then placing the glass plate in a vacuum oven, oven The temperature was set to 80 ° C, the vacuum pressure was set to 0.06 MPa, and baking was carried out for 3 hours, and drying was carried out to form a film.

最後，將成膜之高分子薄膜取下，將聚乙烯醇/聚氧化乙烯摻合高分子薄膜置入四氫呋喃(THF)溶劑中，THF部份溶解聚氧化乙烯(PEO)高分子，而聚乙烯醇(PVA)不會溶解，即形成具有多孔性之PVA/PEO摻合高分子電解質薄膜，其詳細製備流程如圖1所示。Finally, the film-forming polymer film is removed, and the polyvinyl alcohol/polyethylene oxide blended polymer film is placed in a tetrahydrofuran (THF) solvent, and the THF partially dissolves the polyethylene oxide (PEO) polymer, and the polyethylene. The alcohol (PVA) does not dissolve, that is, a porous PVA/PEO blended polymer electrolyte membrane is formed, and the detailed preparation process is shown in FIG.

取一適當大小(A=1cm2 )之PVA/PEO摻合高分子電解質薄膜以不鏽鋼夾具，並以Autolab FRA之系統對此固態摻合高分子電解質膜進行離子導電度之量測，並由變化不同溫度所測得之離子導電度值，可以進一步的計算出摻合高分子電解質膜之活化能(Ea)。另外，對於固態摻合高分子電解質薄膜之進行含水率測試，表面形態以SEM(Hitachi 2600S)觀察，以顯微拉曼光譜儀(micro-Raman spectroscopy,Ranishaw)分析薄膜之化學組成分析。Take a PVA/PEO blended polymer electrolyte film of appropriate size (A=1cm 2 ) into a stainless steel fixture, and measure the ionic conductivity of the solid-state polymer electrolyte membrane by Autolab FRA system. The activation energy (Ea) of the polymer electrolyte membrane can be further calculated by measuring the ionic conductivity values at different temperatures. In addition, the moisture content of the solid-state polymer electrolyte membrane was tested, and the surface morphology was observed by SEM (Hitachi 2600S), and the chemical composition analysis of the film was analyzed by micro-Raman spectroscopy (Ranishaw).

前述該聚乙烯醇(PVA)高分子具有80%以上之皂化度，其有平均分子量(Mw)為50,000~200,000之間。聚氧化乙烯(PEO)高分子具有分子量(MW )為10,000~1,000,000，密度在1.1~1.2之間。The polyvinyl alcohol (PVA) polymer has a degree of saponification of 80% or more and an average molecular weight (Mw) of between 50,000 and 200,000. Polyethylene oxide (PEO) polymers have a molecular weight (M W ) of 10,000 to 1,000,000 and a density of 1.1 to 1.2.

再者，該多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)高分子膜中可添加任何具有多孔性奈米級或微米級陶瓷材料粒子或粉末，其中加入奈米級粒子係為親水性二氧化矽(SiO2 )、二氧化鈦(TiO2 )、二氧化鋯(ZrO2 )、二氧化鈰(CeO2 )、三氧化二鋁(Al2 O3 )陶瓷材料粉末，藉以改善固態PVA/PEO電解質薄膜的離子導電度、電化學穩定度以及機械強度等性質。Furthermore, any porous nano- or micro-scale ceramic material particles or powders may be added to the porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) polymer film, wherein the nano-sized particles are added to be hydrophilic. Antimony (SiO 2 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ) ceramic material powder, thereby improving solid PVA/PEO The properties of the electrolyte membrane such as ionic conductivity, electrochemical stability, and mechanical strength.

實施例說明：Description of the embodiments: 實施例1：Example 1:

取20g之聚乙烯醇(PVA)和2g之聚氧化乙烯(PEO,約10wt.%)分別溶解於170g及30g水中，將反應器以水浴或其他加熱方式在80~90℃溫度下，使其完全溶解，時間約60~100分鐘，將此溶解後的高分子黏液中加入10wt.%的第二非溶劑，例如二甲基甲醯胺(DMF)均勻混合，再加入戊二醛交聯劑，攪拌約10分鐘；最後加入1wt.%鹽酸，攪拌5分鐘後，利用刮刀式塗佈機進行塗佈成膜。20 g of polyvinyl alcohol (PVA) and 2 g of polyethylene oxide (PEO, about 10 wt.%) are respectively dissolved in 170 g and 30 g of water, and the reactor is heated at a temperature of 80 to 90 ° C by a water bath or other heating method. Completely dissolved for about 60~100 minutes. Add 10wt.% of the second non-solvent to the dissolved polymer mucilage, such as dimethylformamide (DMF), and then add glutaraldehyde crosslinker. The mixture was stirred for about 10 minutes; finally, 1 wt.% hydrochloric acid was added, and after stirring for 5 minutes, the film was formed by coating with a knife coater.

然後將聚乙烯醇/聚氧化乙烯摻合的水溶液以2,000rpm轉速混合充分攪拌1~12小時，之後混合高分子溶液在100~500rpm轉速下充分攪拌1~3小時，以去除氣體。Then, the polyvinyl alcohol/polyethylene oxide blended aqueous solution is mixed and stirred at 2,000 rpm for 1 to 12 hours, and then the mixed polymer solution is thoroughly stirred at 100 to 500 rpm for 1 to 3 hours to remove the gas.

接著，使用塗佈機並控制塗佈高分子的黏度及厚度，直接塗佈在承載盤，例如玻璃板上。將此玻璃板置於真空烘箱中，烘箱溫度設定80℃，真空壓力設定0.06MPa，進行乾燥成膜，乾燥時間約為3小時。最後，將成膜之高分子薄膜取下，將高分子薄膜浸置在四氫呋喃(THF)有機溶劑中，做選擇性的溶解PVA/PEO摻合高分子薄膜中的聚氧化乙烯(PEO)，再經由清洗及乾燥處理，此即為多孔性固態PVA/PEO摻合高分子薄膜。Next, the viscosity and thickness of the coating polymer are controlled using a coater and applied directly to a carrier tray such as a glass plate. The glass plate was placed in a vacuum oven, the oven temperature was set to 80 ° C, the vacuum pressure was set to 0.06 MPa, and drying was carried out to form a film, and the drying time was about 3 hours. Finally, the film-forming polymer film is removed, and the polymer film is immersed in a tetrahydrofuran (THF) organic solvent to selectively dissolve the polyethylene oxide (PEO) in the PVA/PEO blended polymer film, and then Through the washing and drying treatment, this is a porous solid PVA/PEO blended polymer film.

實施例2：Example 2:

取一適當大小之無孔PVA高分子電解質薄經過5wt.%的戊二醛進行交聯處理。同樣的，取一適當大小之多孔性的PVA/PEO(10wt.%)摻合高分子電解質薄，經過5wt.%的戊二醛進行交聯處理，以不鏽鋼(block electrode)夾具固定，並以Autolab FRA(Eco Chemi,Netherland)之系統對固態摻合高分子電解質薄膜進行離子導電度之測量，頻率在100kHz~10Hz，且振幅為5mV；並由變化不同溫度所測得之離子導電度值，其PVA/5%GA SPE於不同濃度的電解液中的Nyquist圖和Arrhenius plot，其結果如圖2、圖3所示。而PVA/10wt%PEO/5%GA SPE的Nyquist圖和Arrhenius plot，則如圖4、圖5所示。A suitably sized non-porous PVA polymer electrolyte was thinly cross-linked by 5 wt.% glutaraldehyde. Similarly, a suitable size of PVA/PEO (10wt.%) is blended with a thin polymer electrolyte, cross-linked by 5wt.% glutaraldehyde, fixed with a block electrode clamp, and The system of Autolab FRA (Eco Chemi, Netherland) measures the ionic conductivity of the solid-state polymer electrolyte membrane at a frequency of 100 kHz to 10 Hz with an amplitude of 5 mV; and the ionic conductivity value measured by varying the temperature, The Nyquist plot and the Arrhenius plot of the PVA/5% GA SPE in different concentrations of electrolyte are shown in Figures 2 and 3. The Nyquist diagram and Arrhenius plot of PVA/10wt% PEO/5% GA SPE are shown in Figures 4 and 5.

電解質膜的離子導電度(σ)的計算公式Formula for calculating the ionic conductivity (σ) of the electrolyte membrane

其中σ：離子導電度(S cm-1)；L：膜的厚度(cm)；Rb ：電阻(ohm)；A：截面積，夾具截面積為(cm2 )。Wherein σ: ionic conductivity (S cm-1); L: film thickness (cm); R b : resistance (ohm); A: cross-sectional area, jig cross-sectional area (cm 2 ).

在表1中可以知道PVA/5wt.%GA(無孔)摻合高分子薄膜浸置在4M KOH水溶液中的離子導電度，在30℃時，其σ=0.0167(S cm-1 )。但是多孔性之PVA/PEO(10wt.%)/5wt.%GA摻合高分子薄膜離子導電度，在30℃時，其σ=0.0163(S cm-1 )。The ionic conductivity of the PVA/5wt.%GA (non-porous) blended polymer film immersed in a 4 M KOH aqueous solution is known in Table 1, and σ = 0.0167 (S cm -1 ) at 30 °C. However, the porous PVA/PEO (10 wt.%)/5 wt.% GA blended polymer film ionic conductivity, and its σ = 0.0163 (S cm -1 ) at 30 °C.

在表2中無孔的PVA/5wt.%GA摻合高分子薄膜浸置在8M KOH水溶液中的離子導電度，在30℃時，其σ=0.0076(S cm-1 )。但是多孔性之PVA/PEO(10wt.%)/5wt.%GA摻合高分子薄膜離子導電度，在30℃時，其σ=0.0044(S cm-1 )。The ionic conductivity of the non-porous PVA/5wt.%GA blended polymer film immersed in an aqueous solution of 8 M KOH in Table 2 was σ = 0.0076 (S cm -1 ) at 30 °C. However, the porous PVA/PEO (10 wt.%)/5 wt.% GA blended polymer film ionic conductivity, and its σ = 0.0044 (S cm -1 ) at 30 °C.

實施例3：Example 3:

將經過5wt.%的戊二醛交聯處理的微孔性的PVA/PEO(10wt.%)摻合高分子薄膜，以SEM觀察分析其表面形態如圖6所示。由圖6a、圖6b中可看出真空烘箱處理及四氫呋喃(THF)有機溶劑做選擇性的部份溶解掉一些PEO高分子後，讓原本結構相當緻密的PVA/PEO摻合高分子電解質薄膜會產生細微小孔洞(micro-pores)，且所形成微孔洞並非直接貫穿孔洞之薄膜，而是由不同孔洞位置堆疊而成，因此讓多孔性PVA/PEO摻合高分子電解質薄膜具有氣體分子通過的特殊功能，但是又不至於讓針狀鋅(Zn dendritic)或比較大的粒子或氣體分子直接通過高分子膜的功用。The microporous PVA/PEO (10 wt.%) which was crosslinked by 5 wt.% of glutaraldehyde was blended into a polymer film, and its surface morphology was analyzed by SEM observation as shown in FIG. It can be seen from Fig. 6a and Fig. 6b that the vacuum oven treatment and the tetrahydrofuran (THF) organic solvent are used as a selective part to dissolve some PEO polymers, so that the PVA/PEO blended polymer electrolyte film with a relatively dense structure will be Micro-pores are generated, and the micro-holes formed are not directly through the film of the holes, but are stacked by different holes, so that the porous PVA/PEO blended polymer electrolyte film has gas molecules passing through The special function, but not to let the Zn dendritic or relatively large particles or gas molecules directly through the function of the polymer film.

實施例4：Example 4:

比較經過5wt.%的戊二醛交聯處理的具有多孔性PVA/PEO摻合高分子電解質薄膜的液體吸收率(absorption ratio)和膨脹率(swelling ratio)。由表中發現在純水中吸收率在49.3%和膨脹率在74.1%之間，隨著聚氧化乙烯高分子量之增加，吸收率和膨脹率在下降。The liquid absorption ratio and the swelling ratio of the porous PVA/PEO blended polymer electrolyte membrane treated by 5 wt.% of glutaraldehyde cross-linking were compared. It is found from the table that the absorption rate in pure water is 49.3% and the expansion ratio is between 74.1%. As the high molecular weight of polyethylene oxide increases, the absorption rate and expansion ratio decrease.

實施例5：Example 5:

圖7為複合式聚乙烯醇/聚氧化乙烯(PVA/PEO)高分子膜沒有經過THF溶劑處理的Micro-Raman的分析比較圖，由圖中可得知PEO的拉曼特性峰為1230cm-1 及1279cm-1 ，其中複合式PVA/PEO高分子膜經四氫呋喃(THF)處理後，它在拉曼圖譜並無任何的改變，顯示聚氧化乙烯高分子在此複合式高分子膜上除幫助造孔的作用外，對複合式PVA/PEO膜不會造成任何影響。Fig. 7 is a comparative comparison diagram of a composite polyvinyl alcohol/polyethylene oxide (PVA/PEO) polymer film without Micro-Raman treated with THF solvent. It can be seen from the figure that the Raman characteristic peak of PEO is 1230 cm -1 . And 1279cm -1 , wherein the composite PVA/PEO polymer film treated with tetrahydrofuran (THF) has no change in the Raman spectrum, indicating that the polyoxyethylene polymer is assisted on the composite polymer film. In addition to the role of the pores, there is no effect on the composite PVA/PEO film.

實施例6：Example 6

複合式多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)高分子電解質膜的界面穩定度分析，利用循環伏安法分析複合式高分子膜，將製備完成之高分子隔離膜剪裁適當大小0.5cm×0.5cm浸置於4M KOH溶液中至少12小時，取出後夾於2片相同大小之鋅金屬片電極，再置於兩極式玻璃夾具中，設定掃瞄速度為10mV s-1 、掃描範圍為-0.5V~0.5V進行掃描，實驗數據如圖8a~圖8e所示，由圖中可明顯比較出複合式多孔性PVA/PEO高分子膜，其I-V曲線所積分出之氧化還原面積(面積電量)較其他複合高分子隔離膜大，表示此複合膜較具有較佳充/放電可逆性，並且氧化和還原峰之間的對稱性也較其他高分子隔離膜佳，此舉將有助於二次鋅電池其充/放電性能的提昇改善。Interfacial stability analysis of composite porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) polymer electrolyte membrane. The composite polymer membrane was analyzed by cyclic voltammetry, and the prepared polymer separator was cut to an appropriate size of 0.5. Cm×0.5cm was immersed in 4M KOH solution for at least 12 hours, taken out and clamped on two pieces of zinc metal plate electrode of the same size, and placed in a two-pole glass fixture, setting the scanning speed to 10mV s -1 , scanning range Scanning for -0.5V~0.5V, the experimental data is shown in Figure 8a~8e. From the figure, the composite porous PVA/PEO polymer film can be compared, and the redox area integrated by the IV curve ( area The amount of electricity is larger than that of other composite polymer separators, indicating that the composite membrane has better charge/discharge reversibility, and the symmetry between the oxidation and reduction peaks is better than other polymer separators. The improvement of the charge/discharge performance of the secondary zinc battery is improved.

實施例7：Example 7

取實施例3製備完成的一片多孔性聚乙烯醇/聚氧化乙烯高分子摻合電解質膜，將此多孔性摻合高分子電解質薄膜搭配多孔性二次電極，例如鋅電極進行充/放電測試，發現二次鋅電極在充電過程中所產生的氣體(H2 )，一般是無法穿透無孔固態PVA高分子電解質膜，由於固態PVA高分子電解質膜為層狀堆疊結構，所以產生的氣體無法宣洩，進而堆積在二次鋅電極表面而形成一層氣體膜，此將造成二次鋅電極在充電時極化情形更為嚴重。但是，如使用多孔性固態PVA/PEO摻合高分子電解質膜，搭配二次鋅電極進行充放電測試，經由比較圖9的鋅二次電極的充/放電曲線圖，結果發現搭配固態PVA/PEO摻合高分子電解質薄膜的二次鋅電極在充電時，有明顯減緩二次鋅電極極化情形，因為氣體可以經由微孔排出，而且針狀鋅也不易刺穿。因此，固態聚乙烯醇/聚氧化乙烯摻合高分子電解質膜可以有效的提高二次鋅電極的庫倫效率、能量效率和延長二次鋅電極充/放循環次數。Taking a porous polyvinyl alcohol/polyoxyethylene polymer blended electrolyte membrane prepared in Example 3, the porous blended polymer electrolyte membrane was mixed with a porous secondary electrode, for example, a zinc electrode for charge/discharge test. It is found that the gas (H 2 ) generated during the charging process of the secondary zinc electrode is generally unable to penetrate the non-porous solid PVA polymer electrolyte membrane. Since the solid PVA polymer electrolyte membrane has a layered stacked structure, the generated gas cannot be produced. The catharsis is deposited on the surface of the secondary zinc electrode to form a gas film, which will cause the secondary zinc electrode to be more polarized during charging. However, if a porous solid PVA/PEO blended polymer electrolyte membrane is used, and a secondary zinc electrode is used for charge and discharge test, the charge/discharge curve of the zinc secondary electrode of FIG. 9 is compared, and it is found that the solid state PVA/PEO is used. When the secondary zinc electrode blended with the polymer electrolyte film is charged, the polarization of the secondary zinc electrode is significantly slowed down, because the gas can be discharged through the micropores, and the acicular zinc is also not easily pierced. Therefore, the solid polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane can effectively improve the coulombic efficiency, energy efficiency of the secondary zinc electrode and prolong the number of secondary zinc electrode charge/discharge cycles.

其中，前述多孔性二次電極並不侷限於鋅電極，其亦可選自Cd電極、Fe電極、MnO2 電極、Ni(OH)2 電極、碳電極。The porous secondary electrode is not limited to a zinc electrode, and may be selected from a Cd electrode, an Fe electrode, a MnO 2 electrode, a Ni(OH) 2 electrode, and a carbon electrode.

因此，本發明所製備的鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜，該膜可搭配多孔性碳電極，以組成一電容器(capacitors)，該電容器可進行充/放電。Therefore, the basic porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) prepared by the present invention is blended with a polymer electrolyte membrane, and the membrane can be combined with a porous carbon electrode to form a capacitor, which can be used. Charge/discharge.

同理，該鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜可搭配PtRu/C或PtRu黑(含量1~10mg/cm2 )陽電極，Pt/C、Pt黑(含量1~10mg/cm2)陰電極，以組成一種直接甲醇燃料電池(Alkaline DMFC)，該直接甲醇燃料電池可進行放電。Similarly, the alkaline porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) blended polymer electrolyte membrane can be combined with PtRu/C or PtRu black (content 1~10mg/cm 2 ) anode electrode, Pt/C, Pt black (content 1~10mg/cm2) cathode electrode to form a direct methanol fuel cell (Alkaline DMFC), which can be discharged.

尤有進者，該鹼性多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜可搭配Pt/C、Pt黑(含量1~10mg/cm2 )電極，以組成一種氫-氧燃料電池(Alkaline PEMFC)，該氫-氧燃料電池可進行放電的應用。In particular, the alkaline porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) blended polymer electrolyte membrane can be combined with Pt/C, Pt black (content 1~10mg/cm 2 ) electrodes to form a kind of Hydrogen-oxygen fuel cell (Alkaline PEMFC), which can be used for discharge.

本案所揭示者，乃較佳實施例之一種，舉凡局部之變更或修飾而源於本案之技術思想而為熟習該項技藝之人所易於推知者，俱不脫本案之專利權範疇。The disclosure of the present invention is a preferred embodiment. Any change or modification of the present invention originating from the technical idea of the present invention and being easily inferred by those skilled in the art will not deviate from the scope of patent rights of the present invention.

圖1為本發明多孔性聚乙烯醇/聚氧化乙烯摻合高分子薄膜製備流程圖。1 is a flow chart showing the preparation of a porous polyvinyl alcohol/polyethylene oxide blended polymer film of the present invention.

圖2為本發明PVA/5wt.% GA高分子薄膜的Nyquist分析圖。2 is a Nyquist analysis diagram of a PVA/5wt.% GA polymer film of the present invention.

圖3為本發明PVA/5wt.% GA高分子薄膜的Arrhenius分析圖。3 is an Arrhenius analysis diagram of a PVA/5wt.% GA polymer film of the present invention.

圖4為本發明PVA/10wt.% PEO/5wt.% GA摻合高分子薄膜的Nyquist分析圖。4 is a Nyquist analysis diagram of a PVA/10 wt.% PEO/5 wt.% GA blended polymer film of the present invention.

圖5為本發明PVA/10wt.% PEO/5wt.% GA摻合高分子薄膜的Arrhenius分析圖。Figure 5 is an Arrhenius analysis diagram of a PVA/10 wt.% PEO/5 wt.% GA blended polymer film of the present invention.

圖6a及圖6b為本發明PVA/5wt.% PEO/5wt.% GA摻合高分子薄膜SEM分析圖。6a and 6b are SEM analysis diagrams of a PVA/5wt.% PEO/5wt.% GA blended polymer film of the present invention.

圖7為本發明PVA/PEO摻合高分子電解質薄膜的micro-Raman分析圖。Fig. 7 is a micro-Raman analysis diagram of a PVA/PEO blended polymer electrolyte membrane of the present invention.

圖8a至圖8e為本發明不同摻合高分子電解質膜界面穩定度各週期(cycle)分析圖，其中圖8a在第一週期、圖8b在第三週期、圖8c在第五週期、圖8d在第七週期、圖8e在第十週期。8a to 8e are diagrams showing cycle analysis of interface stability of different polymer electrolyte membranes according to the present invention, wherein FIG. 8a is in the first period, FIG. 8b is in the third period, FIG. 8c is in the fifth period, and FIG. 8d is in FIG. In the seventh cycle, Figure 8e is in the tenth cycle.

圖9為本發明多孔性PVA/PVC摻合高分子電解質薄膜搭配二次鋅電極的充/放電曲線圖。Fig. 9 is a graph showing the charge/discharge curve of a porous PVA/PVC blended polymer electrolyte membrane with a secondary zinc electrode according to the present invention.

Claims (13)

一種多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)摻合高分子電解質膜之製法，其包括：(a)選取分子量介於2,000~120,000的聚乙烯醇(PVA)，使用量為30~95wt.%，在常溫下及密閉環境下與重量比50~60wt.%的第一溶劑之水攪拌混合反應；(b)將重量比為1~40wt.%之聚氧化乙烯(PEO)粉末，在常溫及連續攪拌下與第一溶劑的水攪拌混合反應；(c)將聚乙烯醇/聚氧化乙烯高分子混合溶液中加入5~20wt.%的第二非溶劑均勻混合，再加入1wt.%~75wt.%的交聯劑，攪拌約5~60分鐘後，另加入0.1wt.%~20wt.%的觸媒，攪拌2~10分鐘，並在20~70℃進行交聯反應，其中，該第二非溶劑係選自二甲基甲醯胺(DMF,dimethyl formamide)、伽瑪羥基丁酸(BL,γ-butyrolactone)、二甲基亞碸(DMSO,dimethylsulfoxide)、硫酸二甲酯(DMSI,dimethyl sulfite)、碳酸丙烯酯(PC,propylene carbonate)、碳酸乙烯酯(EC,ethylene carbonate)、環丁碸(Sufolane)、N-甲基吡咯烷酮(NMP,N-methylpyrrolidinone)等有機溶劑，使用量為1~100wt.%之間，該交聯劑係選自戊二醛、丁二醛、己二醛，該觸媒係選自HCl、H2 SO4 、HNO3 ；(d)將所得之高分子黏液依照所需的膜厚去控制塗佈於承載盤上，於溫度在80℃下，真空度在0.06MPa，放置約10~24小時，以成為固態聚乙烯醇/聚氧化乙烯摻合高分子電解質膜，取出承載盤置於常溫下熱平衡，即可將薄膜取下；以及(e)取適當大小之固態聚乙烯醇/聚氧化乙烯摻合高分子電解質膜置入四氫呋喃(THF)有機溶劑中，以進行選擇性的溶解聚氧化乙烯，於20~65℃下，放置約1~24小時，使聚氧化乙烯形成許多微孔。A method for preparing a porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) blended polymer electrolyte membrane, comprising: (a) selecting a polyvinyl alcohol (PVA) having a molecular weight of 2,000 to 120,000, and the amount of use is 30~ 95wt.%, mixed with a water of a first solvent having a weight ratio of 50 to 60 wt.% at a normal temperature and a closed environment; (b) a polyethylene oxide (PEO) powder having a weight ratio of 1 to 40 wt.%, The mixture is stirred and mixed with water of the first solvent at normal temperature and continuous stirring; (c) the polyvinyl alcohol/polyethylene oxide polymer mixed solution is uniformly mixed with 5-20 wt.% of the second non-solvent, and then 1 wt. %~75wt.% of the crosslinking agent, after stirring for about 5~60 minutes, another 0.1wt.%~20wt.% of the catalyst is added, stirred for 2~10 minutes, and the crosslinking reaction is carried out at 20~70 °C, wherein The second non-solvent is selected from the group consisting of dimethyl formamide (DMF), gamma hydroxybutyric acid (BL, γ-butyrolactone), dimethyl sulfoxide (dimethylsulfoxide), and dimethyl sulfate. (DMSI, dimethyl sulfite), propylene carbonate (PC, propylene carbonate), ethylene carbonate (EC, ethylene carbonate), succinol (Sufolane), N-methylpyrrolidone (NMP, N- An organic solvent such as methylpyrrolidinone) is used in an amount of from 1 to 100 wt.%, and the crosslinking agent is selected from the group consisting of glutaraldehyde, succinaldehyde, and adipaldehyde, and the catalyst is selected from the group consisting of HCl, H 2 SO 4 , and HNO. 3 ; (d) The obtained polymer mucilage is controlled to be applied to the carrier plate according to the required film thickness, and the vacuum is at 0.06 MPa at a temperature of 80 ° C, and left for about 10 to 24 hours to become a solid polymer. Vinyl alcohol/polyethylene oxide blended with a polymer electrolyte membrane, the carrier tray is taken out to be thermally equilibrated at room temperature, and the film can be removed; and (e) an appropriate size solid polyvinyl alcohol/polyethylene oxide blended polymer electrolyte is taken. The membrane is placed in a tetrahydrofuran (THF) organic solvent to selectively dissolve the polyethylene oxide, and is allowed to stand at 20 to 65 ° C for about 1 to 24 hours to form a plurality of micropores of the polyethylene oxide. 如申請專利範圍第1項所述之製法，其於步驟c與步驟d 之間進一步包括：(c’)將聚乙烯醇/聚氧化乙烯摻合的水溶液以200~1000rpm轉速混合充分攪拌1~12小時，之後混合高分子溶液在100~500rpm轉速下充分攪拌1~3小時，以去除氣體(air bubbles)。 For example, the method described in claim 1 is in steps c and d Further comprising: (c') mixing the polyvinyl alcohol/polyethylene oxide blended aqueous solution at 200-1000 rpm for 1 to 12 hours, and then mixing the polymer solution at 100-500 rpm for 1 to 3 times. Hours to remove air bubbles. 如申請專利範圍第1項所述之製法，其中該聚乙烯醇(PVA)高分子具有80%以上之皂化度。 The method of claim 1, wherein the polyvinyl alcohol (PVA) polymer has a degree of saponification of 80% or more. 如申請專利範圍第1項所述之製法，其中該聚氧化乙烯(PEO)高分子具有分子量(MW )為10,000~100,000，密度在1.1~1.2之間。The method of claim 1, wherein the polyoxyethylene (PEO) polymer has a molecular weight (M W ) of 10,000 to 100,000 and a density of 1.1 to 1.2. 如申請專利範圍第1項所述之製法，其中該交聯反應溫度在40~50℃。 The method of claim 1, wherein the crosslinking reaction temperature is 40 to 50 °C. 如申請專利範圍第1項所述之製法，其中該承載盤係選自玻璃片、聚四氟乙烯(PTFE)盤或不鏽鋼盤。 The method of claim 1, wherein the carrier tray is selected from the group consisting of a glass sheet, a polytetrafluoroethylene (PTFE) disk, or a stainless steel disk. 如申請專利範圍第1項所述之製法，其中該多孔性聚乙烯醇/聚氧化乙烯(PVA/PEO)高分子膜中可添加任何具有多孔性奈米級或微米級陶瓷材料粒子或粉末，其中加入奈米級粒子係為親水性二氧化矽(SiO2 )、二氧化鈦(TiO2 )、二氧化鋯(ZrO2 )、二氧化鈰(CeO2 )、三氧化二鋁(Al2 O3 )陶瓷材料粉末。The method of claim 1, wherein the porous polyvinyl alcohol/polyethylene oxide (PVA/PEO) polymer film may be added with any porous nano or micron ceramic material particles or powder. The nano-sized particles are added as hydrophilic cerium oxide (SiO 2 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), cerium oxide (CeO 2 ), and aluminum oxide (Al 2 O 3 ). Ceramic material powder. 如申請專利範圍第1項所述之製法，其中該聚乙烯醇/聚氧化乙烯高分子電解質膜的離子導電度，在25℃下，至少為10-2 S/cm以上。The method of claim 1, wherein the polyvinyl alcohol/polyoxyethylene polymer electrolyte membrane has an ionic conductivity of at least 10 -2 S/cm at 25 °C. 一種使用如申請專利範圍第1項所述之鹼性多孔性聚乙烯醇/聚氧化乙烯摻合高分子電解質膜之應用，其可搭配多孔性二次電極，以進行充/放電的應用。 An application using the alkaline porous polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane according to the first aspect of the patent application, which can be used with a porous secondary electrode for charging/discharging applications. 如申請專利範圍第9項所述之應用，其中該多孔性二次電極係選自Zn電極、Cd電極、Fe電極、MnO2 電極、Ni(OH)2 電極、碳電極。The application according to claim 9, wherein the porous secondary electrode is selected from the group consisting of a Zn electrode, a Cd electrode, an Fe electrode, a MnO 2 electrode, a Ni(OH) 2 electrode, and a carbon electrode. 一種使用如申請專利範圍第1項所述之鹼性多孔性聚乙烯 醇/聚氧化乙烯摻合高分子電解質膜之應用，其可搭配多孔性碳電極，以組成一電容器(capacitors)，該電容器可進行充/放電的應用。 An alkaline porous polyethylene as described in claim 1 of the patent application The use of an alcohol/polyethylene oxide blended polymer electrolyte membrane can be combined with a porous carbon electrode to form a capacitor, which can be used for charge/discharge applications. 一種使用如申請專利範圍第1項所述之鹼性多孔性聚乙烯醇/聚氧化乙烯摻合高分子電解質膜之應用，其可搭配PtRu/C或PtRu黑(含量1~10mg/cm2 )陽電極，Pt/C、Pt黑(含量1~10mg/cm2 )陰電極，以組成一種直接甲醇燃料電池(Alkaline DMFC)，該直接甲醇燃料電池可進行放電的應用。An application using an alkaline porous polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane as described in claim 1 of the patent application, which can be used with PtRu/C or PtRu black (content 1 to 10 mg/cm 2 ) A positive electrode, Pt/C, Pt black (content 1~10mg/cm 2 ) cathode electrode to form a direct methanol fuel cell (Alkaline DMFC), which can be used for discharge. 一種使用如申請專利範圍第1項所述之鹼性多孔性聚乙烯醇/聚氧化乙烯摻合高分子電解質膜之應用，其可搭配Pt/C、Pt黑(含量1~10mg/cm2 )電極，以組成一種氫-氧燃料電池(Alkaline PEMFC)，該氫-氧燃料電池可進行放電的應用。An application using an alkaline porous polyvinyl alcohol/polyethylene oxide blended polymer electrolyte membrane as described in claim 1 of the patent application, which can be combined with Pt/C and Pt black (content 1 to 10 mg/cm 2 ) Electrodes to form a hydrogen-oxygen fuel cell (Alkaline PEMFC), which can be used for discharge applications.
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* Cited by examiner, † Cited by third party
Title
陳柏瑋，製備鋅鈣化合物應用在鎳鋅(Ni/Zn)電池之研究，碩士論文，明志科技大學化工與材料工程研究所，2009。 *

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