KR102287067B1 - High stability pore-filled ion-exchange membranes for redox flow battery and method for preparing the same - Google Patents

Abstract

The present invention relates to an anion exchange membrane for a redox flow battery manufactured by a pore filling technique and a manufacturing method thereof. More specifically, an anion for a redox flow battery that has high mechanical strength, excellent oxidation stability, low electrical resistance and high ion selectivity by impregnating a porous support with a polyphenylene oxide-based polymer and a crosslinking agent to provide an anion exchange membrane forming a crosslinked structure To provide an exchange membrane and a method for manufacturing the same.

Description

Pore-filled anion exchange membrane for high stability redox flow battery and manufacturing method thereof

The present invention relates to an anion exchange membrane for a redox flow battery manufactured by a pore filling technique and a manufacturing method thereof. More specifically, to provide an anion exchange membrane crosslinked by impregnating a resin on a porous support film to have high mechanical strength, excellent oxidation stability, low electrical resistance, and high ion selectivity for a redox flow battery, and a method for manufacturing the same will do

As an ion exchange membrane for a redox flow battery, cation and anion exchange membranes are generally used. Among them, the anion exchange membrane is preferred because it can lower the permeability of vanadium ions, and many studies are in progress. ^{Accordingly, AMX (NEOSEPTA ⓡ} , ASTOM, Japan), one of the commercial anion exchange membranes for redox flow batteries, has the advantages of excellent mechanical and chemical stability, low electrical resistance and excellent ion selectivity, but manufacturing cost is complicated due to the complicated manufacturing process. It has the disadvantage of being high. In order for such an ion exchange membrane to be applied to a redox flow battery that operates for a long time, it is necessary to significantly lower the membrane manufacturing cost compared to the currently used commercial membrane and to further improve the electrochemical performance. That is, it is necessary to develop an anion exchange membrane for a redox flow battery having excellent mechanical strength, chemical stability and electrochemical performance that can replace the AMX commercial membrane.

Republic of Korea Patent Publication No. 10-2022676 (2019.09.10)

The present inventors prepared a crosslinked anion exchange membrane for a redox flow battery using a pore filling technique in which a polymer resin and a crosslinking agent are impregnated on a porous support film, thereby significantly increasing the mechanical and chemical properties, ion selectivity and electrochemical performance of the anion exchange membrane. It was found that the present invention was completed.

That is, in the present invention, in the preparation of an anion exchange membrane applicable to a redox flow battery, the polymer resin is brominated and substituted to have a quaternary ammonium base to create a place where anion can be exchanged, and the porous support is impregnated with a crosslinking agent. A cross-linked anion exchange membrane was prepared. Furthermore, by preparing an anion exchange membrane according to the chain length of the crosslinking agent or the porosity of the porous support, mechanical, chemical properties and electrochemical performance were evaluated to develop an anion exchange membrane having the best performance.

One aspect of the present invention for achieving the above object is to provide an anion exchange membrane for a redox flow battery coated with a cross-linked anion exchange resin produced by coating the surface and the inside of the pores of a porous support.

In one aspect of the present invention, in the case of an anion exchange membrane prepared by impregnating a polyphenylene oxide polymer in a porous support together with a crosslinking agent, the tensile strength increase rate is significantly higher than that of AMX, which is a commercial membrane, by 400% or more, preferably by 500% or more. have increased properties. In addition, the tensile elongation increase rate was significantly increased in an unexpected range to 300% or more, preferably 800% or more, and more preferably 1000% or more.

In addition, in the case of an anion exchange membrane prepared by impregnating a polyphenylene oxide polymer in a porous support with divinylbenzene, as a result of charging and discharging experiments in a redox flow battery, the voltage efficiency was increased by about 3% compared to the commercial membrane, AMX. .

In addition, when the anion exchange membrane was prepared by the above method, the weight fraction of the membrane remaining in the Fenton oxidation experiment was 95% or more, which was higher than that of the commercial membrane, AMX.

In addition, when an anion exchange membrane was prepared by the above method, in the vanadium oxidation experiment, the concentration of vanadium ions passing through the membrane was 0.005 mg/L or less, and showed much more stable oxidation stability than the commercial membrane AMX that was 0.16 mg/L or more.

1 is a graph showing the results when applied to the Fenton oxidation experiment of a 25 μm thick anion exchange membrane prepared for each crosslinking agent in Comparative Examples and Examples of the present invention.
FIG. 2 is a graph showing results when an anion exchange membrane having a thickness of 25 μm prepared for each crosslinking agent in Comparative Examples and Examples of the present invention was applied to a vanadium oxidation experiment.

Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only, and is not intended to limit the invention.

In the present invention, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

One aspect of the present invention is to provide an anion exchange membrane for a redox flow battery coated with a phenylene oxide-based cross-linked anion exchange resin produced by coating the surface and the inside of the pores of a porous support, and a method for manufacturing the same.

Briefly describing the manufacturing method of the anion exchange membrane for a redox flow battery of the present invention, the cross-linked anion exchange membrane is manufactured by a pore filling method, rather than by a conventional casting method. This synthesizes a PPO polymer containing a quaternary ammonium group by reacting with an amine compound having a vinyl group through a process of bromination using a polyphenylene oxide-based (PPO) polymer as a main chain. Thereafter, the porous support is impregnated with a crosslinking agent and photocrosslinked to prepare an anion exchange membrane. The polyphenylene oxide-based polymer of the present invention is not particularly limited as long as it has a substituent capable of halogenation on the benzene ring, but for example, polyphenylene oxide (Poly (2,6-dimethyl-1,4-phenylene oxide) ) may include a polymer, and in this specification, it has been described as using polyphenylene oxide having the same structure as above. In addition, the porous support used in the present invention is not particularly limited, but a porous support made of polyethylene was used, and had a thickness of 9, 25 and 50 μm and had a porosity of 54%, 40%, and 78%, respectively. However, the thickness and porosity of the porous support are not proportional.

In one aspect, the thickness of the porous support may be 1 to 300 ㎛.

In one aspect, the porosity of the porous support may be 10 to 80%.

In one embodiment, the porous support is polyolefin, polyester, polytetrafluoroethylene, polyvinyl chloride, polymethyl acrylate, polymethyl methacrylate, polyurea, polyether, polyurethane, polyisocyanurate, and combinations thereof. It may be selected from the group consisting of.

In one embodiment, the cross-linked anion exchange resin includes a halogenated polyphenylene oxide-based polymer and a reactive monomer having an amine group, the cross-linked anion exchange resin is prepared by crosslinking the quaternary aminated polyphenylene oxide-based polymer may have been

The crosslinked anion exchange resin may further include a crosslinking agent and be formed by photocrosslinking.

The crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol di Methacrylate, neopentyl glycol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane trimethacrylate and It may be any one or more selected from the group consisting of trimethylol triacrylate.

The reactive compound may be prepared by reacting a polyphenylene oxide-based polymer with any one or more selected from primary, secondary, and tertiary amine compounds.

The reactive monomer may include at least one selected from reactive monomer compounds having primary, secondary and tertiary amine groups.

In addition, the cross-linked anion exchange resin may have a molar ratio of the halogenated phenylene oxide-based polymer and the reactive monomer of 1.5:1 to 2.5:1.

Hereinafter, each configuration of the present invention will be described in more detail.

The present invention relates to an anion exchange membrane manufactured by a pore filling technique and a method for manufacturing the same, and the mechanical and chemical properties and electrochemical performance of the manufactured anion exchange membrane were evaluated to compare their performance with AMX, a commercial membrane. The anion exchange membrane prepared by the pore filling technique was manufactured through the following process. First, polyphenylene oxide (Poly(2,6-dimethyl-1,4-phenylene oxide), PPO) is brominated to synthesize PPO containing a quaternary ammonium group, and this is impregnated into a porous support together with a crosslinking agent. An anion exchange membrane was prepared by a pore filling technique of photocrosslinking. It was confirmed that the prepared anion exchange membrane performed better than the commercial membrane AMX through tensile strength and tensile elongation, Fenton and vanadium oxidation tests, and electrochemical evaluation. In particular, in the case of an anion exchange membrane prepared by impregnating the polyphenylene oxide polymer of Example 1 in a porous support together with a crosslinking agent (divinylbenzene, DVB), the tensile strength increase rate is 400% or more, preferably 500% compared to AMX, a commercial membrane. % or more, which has significantly increased properties. In addition, the tensile elongation increase rate was significantly increased in an unexpected range to 300% or more, preferably 800% or more, and more preferably 1000% or more.

In addition, in the case of an anion exchange membrane prepared by impregnating the polyphenylene oxide polymer resin of Example 1 in a porous support together with divinylbenzene, as a result of charging and discharging experiments in a redox flow battery, the voltage efficiency was higher than that of AMX, a commercial membrane. increased by about 3%.

In addition, in the case of Example 1, which is an anion exchange membrane prepared by the above method, the weight fraction of the remaining membrane in the Fenton oxidation experiment was 95% or more, which was higher than that of AMX, a commercial membrane.

In addition, in the case of Example 1, which is an anion exchange membrane prepared by the above method, in the vanadium oxidation experiment, the concentration of vanadium ions passing through the membrane is 0.005 mg/L or less, which is much more stable than the commercial membrane AMX that is 0.16 mg/L or more. showed

The present invention also prepared an anion exchange membrane using a pore filling technique for each chain length (molecular weight) of the crosslinking agent, which also outperformed AMX, a commercial membrane, and produced using DVB with the shortest chain length of the crosslinking agent It was found that the tensile strength and tensile elongation, Fenton and vanadium oxidation degrees, and electrochemical properties of the anion exchange membrane were the best.

Moreover, in the present invention, anion exchange membranes were prepared using porous supports having various thicknesses and porosities, and it was confirmed that the membrane resistance was lowered as the porosity was higher due to the influence of the porosity rather than the tendency to the thickness of the membrane.

The porous support used in one aspect of the present invention may be a film, a sheet, a nonwoven fabric, etc., and the thickness is not particularly limited, but as long as it has a thickness of a degree to facilitate the passage of ions, it may be used without limitation. 1 to 300 μm, preferably 10 to 100 μm, more preferably 5 to 100 μm, even more preferably 10 to 50 μm. When an anion exchange membrane is prepared using the porous support in the above range, it is particularly preferable because of low membrane resistance and excellent electrochemical properties and energy efficiency.

In addition, the porosity of the porous support used in one aspect of the present invention is not necessarily limited thereto, but may be 10 to 80%, preferably 20 to 80%, more preferably 40 to 60%. When an anion exchange membrane is prepared using a porous support having a porosity in the above range, it has excellent tensile strength and tensile elongation, and reduces the increase in membrane resistance with increase in thickness, resulting in better energy due to increased electrochemical properties, particularly ion exchange capacity It is preferable because it can have efficiency.

In one aspect of the present invention, the porous support can be used without limitation as long as it includes pores so that polymerization can be performed after the anion exchange resin mixture is filled, and if it is a material capable of supporting the anion exchange membrane, it is particularly limited but selected from the group consisting of polyolefin, polyester, polytetrafluoroethylene, polyvinyl chloride, polymethyl acrylate, polymethyl methacrylate, polyurea, polyether, polyurethane, polyisocyanurate, and combinations thereof can

In one aspect of the present invention, the cross-linked anion exchange resin includes a halogenated polyphenylene oxide-based polymer and a reactive monomer having an amine group, and is prepared by crosslinking after preparing a quaternary aminated polyphenylene oxide-based polymer. can The halogenated polyphenylene oxide-based polymer is intended to introduce an anion exchange group using the introduced halogen functional group, and the halogen element used is not particularly limited, but may be adjusted according to the size, performance, etc. of the membrane to be manufactured. The halogen element may include, but is not limited to, fluorine, chlorine, bromine, and iodine, for example. As a specific example, the present specification may be a brominated polyphenylene oxide, but is not necessarily limited thereto. In addition, the reactive monomer having an amine group must have a functional group capable of performing anion exchange after reaction with the polymer resin, which includes at least one selected from reactive monomer compounds having primary, secondary and tertiary amine groups. can In addition, the reactive monomer may be used without limitation as long as it has a reactive group that can be photocrosslinked later. As a non-limiting example, the quaternary ammonium salt may be substituted vinylbenzene, and specifically 2-dimethylaminoethyl acrylate (2-(Dimethylamino)ethyl methacrylate (DMAEMA)), but is not necessarily limited thereto.

In one aspect of the present invention, the crosslinked anion exchange resin may further include a crosslinking agent and be formed by photocrosslinking, and the crosslinking agent may be divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, tri It may be at least one selected from the group consisting of ethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane trimethacrylate, and trimethylol triacrylate. In addition, since the conditions of photocrosslinking can be carried out by a conventional method within a range that does not impair the purpose of the present invention, detailed methods are omitted.

In one aspect of the present invention, the cross-linked anion exchange resin may have a molar ratio of the halogenated phenylene oxide-based polymer and the reactive monomer of 1.5:1 to 2.5:1, and the molar ratio is not particularly limited, but preferably 1.8:1 to 2.3. It may be 1:1. The anion exchange membrane prepared in the above range has excellent ion exchange capacity, moisture content and electrochemical properties, but this is only a non-limiting example, and is not limited by the numerical range.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Method of measuring physical properties]

1. Electrochemical evaluation of anion exchange membranes

(1) Electrical resistance (ER): The electrical resistance of the membrane was measured using electrical impedance spectroscopy using a clip cell. The aqueous solution was 0.5 M NaCl and 0.5 MH ₂ SO ₄ . The impedance (│Z│) and the phase angle of the impedance (θ) of the membrane were measured and ^{converted into area resistance (Ω·cm 2} ) values using the equation below.

(2) Water uptake (WU): The moisture content of the membrane was determined by the following equation by measuring the weight of the membrane in wet and dry conditions, respectively.

(3) Ion exchange capacity (IEC): For the ion exchange capacity, a ^{membrane cut to a size of 2×2 cm 2} is immersed in 0.5 M NaCl for more than 6 hours to maintain a neutral state with Cl- attached to the anion exchanger. . After washing the NaCl attached to the membrane with distilled water, _{soak it in 0.25 M Na 2} SO ₄ for 3 hours or more so that the SO ₄ ^2- ions are replaced with Cl- attached to the anion exchanger of the membrane. The membrane is taken out, dried, and then weighed. The amount of Cl- substituted from the membrane _{was found by titration with 0.01 N AgNO 3} solution until a red precipitate was formed, and the volume at this time was applied to the following equation to indicate the ion exchange capacity. In this case, 1 wt% K ₂ CrO ₄ was used as the indicator.

(4) Transport number (TN): After filling the 2-compartment cell with about 150 ml each of 0.001 and 0.005 M NaCl, the transport number of ions (TN): Using a pair of Ag/AgCl wire electrodes, use a digital voltmeter connected to and measured.

Here, Em is the measured cell potential, R is the gas constant, T is the absolute temperature, F is the Faraday constant, and C _L and _CH are the concentrations of NaCl solution, respectively, 1 mM and 5 mM.

(5) Redox flow battery charge/discharge experiment

In the experiment, a non-flowing method without an electrolyte tank was used. The size of carbon felt (GF20-3, Nippon Graphite) is 2.5×5 cm ² , and after heat treatment at 400 to 500 ℃ for 30 minutes with a hot air blower, 1.6 M V3.5+ dissolved in _{2 MH 2} SO ₄ Soak in the electrolyte for at least 30 minutes and wet thoroughly before use. After the cell is fastened in the order of FIG. 1, the electrolyte of V3.5+ is filled in both the anode and the cathode into the injection hole of the bipolr plate. Redox flow battery charging and discharging experiments were carried out in the range of 0.9 to 1.9 V using a battery cycler (WBCS3000, WonAtech).

2. Evaluation of mechanical and chemical properties of anion exchange membrane

(1) Fenton oxidation experiment

3 wt% of H ₂ O ₂ and 3 ppm of FeSO ₄ are dissolved to prepare a Fenton solution. The sample is prepared in the size of 2×2 cm ^{2 .} Before the experiment, the membrane is weighed. Fill a 20 ml vial with 10 ml of Fenton's solution and ensure that the membrane is completely submerged. The vial bottle is sealed and kept at 80° C. for 8 hours. Membrane weights were measured at 4 hour intervals to observe changes in the membrane under oxidizing conditions. As can be seen in FIG. 1 , it was confirmed that the anion exchange membrane prepared in Example 1 had a greater weight fraction than Comparative Example 1, which remained after 8 hours.

(2) Vanadium oxidation experiment

A 0.1 MV ₂ O ₅ solution is prepared in a 5 MH ₂ SO _{4 solution.} Prepare a membrane with a size of 2×2 cm ² _{, fill a vial with 20 ml of V 2} O ₅ solution, and then completely immerse the membrane, seal it, and maintain 40 ℃. After collecting 1 ml of the solution every set time, it is diluted with _{4 ml of 5 MH 2} SO _{4 .} The concentration of vanadium ions in the collected sample is calculated using a UV-vis spectrophotometer. At the same time, observe the apparent degree of oxidation (V ⁵⁺ is yellow, V ⁴⁺ is blue). As can be seen in FIG. 2 , it was confirmed that the anion exchange membrane prepared in Example 1 was much more stable to oxidation of vanadium ions than in Comparative Example 1.

(3) Tensile strength and elongation

In order to examine the physical properties of the pore filling system and crosslinking, a membrane made by casting without using a support and a membrane without a crosslinking agent are prepared in a dry and wet state, respectively, with a diameter of 9 and 25 μm, respectively. The membrane was cut into a size of 5×2.5 cm ² and tensile strength and elongation were measured using a Model durometer 3343 (Instron, Norwodd, MA, USA). Tensile strength and elongation were calculated by the following formula.

Equation 1) Tensile strength (MPa) = Maximum tensile force / cross sectional area

(Maximum tensile force refers to the greatest force applied to each film until the film is cut.)

Equation 2) Elongation (%) = (ΔL/L) × 100

(L represents the distance (mm) between the initial grips of the universal testing machine, and in this experiment, it was set to 100 mm.)

[Preparation Example 1] BPPO (brominated PPO) synthesis method

Bromine is substituted to introduce a ^{quaternary ammonium group (NR 3+} ) into polyphenylene oxide (Poly (2,6-dimethyl-1,4-phenylene oxide), PPO, Aldrich Co.). In this way, 16 g of 8 wt% of PPO compared to the total weight (200 g) was added to 184 g of chlorobenzene in a four-neck round bottom flask and dissolved while raising the temperature of a hot stirrer to 131 °C. While flowing nitrogen, a solution of 21.31 g of bromine dissolved in 100 g of chlorobenzene as a solvent to the prepared PPO solution was added dropwise for about 30 to 40 minutes, followed by refluxing to react. While maintaining the reaction temperature of 131 ℃, the reaction is continued for 10 hours. After the synthesis is completed, ^{fill a 10×10 cm 2} square glass element with high-purity methanol and pour the synthesized BPPO solution against the wall of the element using a dropper while the stirring magnet is rotating. Only the synthesized BPPO is wound around the stirring magnet and precipitates do. The precipitate is again washed with clean high-purity methanol three or more times, and dried in a vacuum oven at 80° C. for 24 hours.

[Example 1] Manufacturing method of anion exchange membrane

A solution was prepared by dissolving BPPO and 2-(Dimethylamino)ethyl methacrylate (DAMEMA) prepared in Preparation Example 1 in dimethylformamide (DMF) as a solvent. The molar ratio of BPPO:DMAEMA (monomer-based molar ratio) is 2:1, and the amount of solid content is 30 wt%. The solution was dissolved by stirring at 80 ° C. for 3 hours, cooled to room temperature, a crosslinking agent divinyl benzene (DVB, 130.19 g / mol) and a photoinitiator (benzoyl peroxide) were added and stirred for 10 to 15 minutes. do. The crosslinking agent was 10 wt% of the BPPO and 2 wt% of the initiator was added, and the vial was wrapped with aluminum foil. After impregnating the solution with a polyethylene porous support having a porosity of 40% of 25 μm, it was dried in a vacuum oven, taken out, placed between two glass plates, and then photocrosslinked. When the support was impregnated in the solution and cross-linked, it was confirmed that the support, which was opaque, became transparent by the refractive index, thereby producing an anion exchange membrane.

[Example 2] Cross-linked anion exchange membrane

Same as Example 1, but

An anion exchange membrane was prepared using an ethylene glycol dimethacrylate (EGDMA, 198.22 g/mol) crosslinking agent.

[Example 3] Cross-linked anion exchange membrane

Same as Example 1, but

An anion exchange membrane was prepared using a 1,3-butanediol dimethacrylate (1,3-Butanediol dimethacrylate, BDDMA, 226.27 g/mol) crosslinking agent.

[Example 4] Cross-linked anion exchange membrane

Same as Example 1, but

An anion exchange membrane was prepared using a 1,6-hexanediol dimethacrylate (1,6-Hexanediol dimethacrylate, HDDMA, 254.32 g/mol) crosslinking agent.

[Example 5]

The same procedure as in Example 1 was carried out except that a polyethylene porous film having a porosity of 54% and a thickness of 9 μm was used as a support.

[Example 6]

The same procedure as in Example 1 was carried out except that a polyethylene porous film having a porosity of 78% and a thickness of 50 μm was used as a support.

[Comparative Example 1]

Astom's AMX membrane, which is a commercial anion exchange membrane, was used as a control.

Membranes Thickness(㎛) ER(Ω·cm ² ) WU (%) IEC (meq./g) IN(-) In 0.5 M NaCl In 0.5MH ₂ SO ₄ Comparative Example 1 AMX 136 2.47 2.93 21.7 1.51 0.980 Example 1 DVB 20wt% 22 3.14 1.11 20.60 1.59 0.981 Example 2 EGDMA 20wt% 22 2.99 0.97 20.50 1.22 0.980 Example 3 BDDMA 20wt% 22 2.40 0.76 15.02 1.11 0.978 Example 4 HDDA 20wt% 22 2.16 0.56 14.51 1.05 0.975

As can be seen in Table 1, Examples according to the present invention exhibited significantly lower membrane resistance than Comparative Example 1 in _{0.5 MH 2} SO _{4 aqueous solution.} Moreover, as the molecular weight of the crosslinking agent is small and has a relatively short molecular structure, the membrane resistance value tends to increase, confirming that the membrane resistance of Example 1 is the highest. This suggests that as the molecular weight of the crosslinking agent decreases, the interchain distance of the polymer becomes shorter and the free volume inside the membrane decreases.

Membranes Thickness(㎛) ER(Ω·cm ² ) WU (%) IEC (meq./g) IN(-) Comparative Example 1 AMX 136 2.47 21.7 1.51 0.980 Example 5 DVB 20 wt% (54 %) 8 0.81 24.3 2.24 0.985 Example 6 DVB 20 wt% (78 %) 47 1.09 56.7 1.52 0.982

Table 2 is a table showing the evaluation results of the electrochemical properties of the anion exchange membrane prepared by fixing and using DVB with the smallest molecular weight among the crosslinking agents and varying the thickness and porosity of the porous support. As can be seen in Table 2, it can be seen that the film resistance of all Examples is much lower than that of Comparative Example 1. In addition, the water content, ion exchange capacity, and ion migration number are higher than those of Comparative Example 1.

Membranes Columbic efficiency(CE)(%) Voltage efficiency(VE)(%) Energy efficiency (EE) (%) Comparative Example 1 AMX 95.9 88.4 84.8 Example 1 DVB 94.5 92.5 87.3 Example 2 EGDMA 93.9 92.4 87.2 Example 3 BDDMA 91.8 93.7 85.9 Example 4 HDDA 85.6 94.5 80.9

Table 3 shows the results of charging and discharging experiments by applying an anion exchange membrane prepared using a support having a porosity of 40% to a redox flow battery. As can be seen from the Examples, as the molecular weight of the crosslinking agent increased, the coulombic efficiency and energy efficiency tended to decrease, and the energy efficiency was 87.3% in Example 1 when the DVB crosslinking agent was used. was shown.

Tensile strength (Mpa) Membranes Tensile strength (Mpa) Tensile Elongation (%) Comparative Example 1 AMX 31.8 10.6 Example 1 DVB 20 wt% 54% 171.9 52.9 Example 2 DVB 20 wt% 78% 192.6 156.1

As shown in Table 4, it can be confirmed that the tensile strength and tensile elongation of Example 1 according to the present invention were significantly increased in an unexpected range by up to 1000% or more than Comparative Example 1.

Moreover, as can be seen in Table 4 above, Example 2, an anion exchange membrane prepared with a support having a porosity of 78%, has tensile strength and tensile elongation compared to Example 1, which is an anion exchange membrane prepared with a support having a porosity of 54%. higher can be seen.

The present invention described above is merely exemplary, and those of ordinary skill in the art to which the present invention pertains will appreciate that various modifications and equivalent other embodiments are possible therefrom. Therefore, it will be well understood that the present invention is not limited to the forms recited in the above detailed description. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (9)

porous support,
A polyphenylene oxide-based cross-linked anion exchange resin is filled on the surface and inside the pores of the porous support,
The polyphenylene oxide-based crosslinked anion exchange resin is reacted with a reactive group of the reactive monomer after preparing a quaternary aminated polyphenylene oxide-based polymer by reacting a halogenated polyphenylene oxide-based polymer with a reactive monomer having an amine group An anion exchange membrane for a redox flow battery that is produced by crosslinking by reacting a crosslinking agent that can be used. The method of claim 1,
The thickness of the porous support is an anion exchange membrane for a redox flow battery of 1 to 300 ㎛. The method of claim 1,
The porosity of the porous support is 10 to 80% anion exchange membrane for a redox flow battery. The method of claim 1,
The porous support is from the group consisting of polyolefin, polyester, polytetrafluoroethylene, polyvinyl chloride, polymethyl acrylate, polymethyl methacrylate, polyurea, polyether, polyurethane, polyisocyanurate, and combinations thereof. An anion exchange membrane for a redox flow battery of choice. delete The method of claim 1,
The crosslinked anion exchange resin further comprises a crosslinking agent and is formed by photocrosslinking an anion exchange membrane for a redox flow battery. 7. The method of claim 6,
The crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , neopentyl glycol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylol propane trimethacrylate and trimethylol tri An anion exchange membrane for a redox flow battery at least one selected from the group consisting of acrylates. 7. The method of claim 6,
The reactive monomer is an anion exchange membrane for a redox flow battery comprising at least one selected from reactive monomer compounds having primary, secondary and tertiary amine groups. The method of claim 1,
The crosslinked anion exchange resin is an anion exchange membrane for a redox flow battery having a molar ratio of a halogenated phenylene oxide-based polymer and a reactive monomer of 1.5:1 to 2.5:1.

Images