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

Description

Method for preparing porous polyvinyl alcohol/polyoxyethylene polymer electrolyte membrane and application thereof

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).

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.

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.

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. 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. 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. Lower activation energy (Ea), which can reduce the sensitivity of the battery to temperature.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

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.

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.

Description of the embodiments: Example 1:

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.

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.

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.

Example 2:

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.

Formula for calculating the ionic conductivity (σ) of the electrolyte membrane

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 ).

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.

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.

Example 3:

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.

Example 4:

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.

Example 5:

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.

Example 6

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.

Example 7

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.

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.

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.

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.

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.

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.

1 is a flow chart showing the preparation of a porous polyvinyl alcohol/polyethylene oxide blended polymer film of the present invention.

2 is a Nyquist analysis diagram of a PVA/5wt.% GA polymer film of the present invention.

3 is an Arrhenius analysis diagram of a PVA/5wt.% GA polymer film of the present invention.

4 is a Nyquist analysis diagram of a PVA/10 wt.% PEO/5 wt.% GA blended polymer film of the present invention.

Figure 5 is an Arrhenius analysis diagram of a PVA/10 wt.% PEO/5 wt.% GA blended polymer film of the present invention.

6a and 6b are SEM analysis diagrams of a PVA/5wt.% PEO/5wt.% GA blended polymer film of the present invention.

Fig. 7 is a micro-Raman analysis diagram of a PVA/PEO blended polymer electrolyte membrane of the present invention.

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.

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)

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. 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. The method of claim 1, wherein the polyvinyl alcohol (PVA) polymer has a degree of saponification of 80% or more. 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. The method of claim 1, wherein the crosslinking reaction temperature is 40 to 50 °C. 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. 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. 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. 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. 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. 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. 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. 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.