KR20180003906A - Inorganic Filler Coated With Ammonium cerium(IV) nitrate, Ion Exchange Membrane and Vanadium Redox Flow Battery Comprising The Same - Google Patents

Abstract

The present invention relates to an inorganic filler coated with ammonium cerium (IV) nitrate (ACN), and to an ion exchange membrane and a vanadium redox flow battery comprising the same. When the surface-modified inorganic filler of the present invention is applied to the ion exchange membrane for a flow battery, it is possible to prevent cerium ions from flowing out to an electrolytic solution even in an environment of the flow battery in which an aqueous solution of sulfuric acid flows, and to improve the ion conductivity by the cerium ions.

Description

[0001] The present invention relates to an inorganic filler coated with ammonium cerium nitrate, an ion exchange membrane containing the same, and a vanadium redox flow battery.

The present invention relates to an inorganic filler coated with ammonium cerium nitrate, an ion exchange membrane containing the same, and a vanadium redox flow battery.

Recently, there is a growing concern about the establishment of a low-carbon society due to global environmental pollution, including global warming caused by fears of exhaustion of fossil energy, rising oil prices, and carbon dioxide emissions from fossil energy use. There is a growing need. For this reason, the need for power supply and demand using renewable energy sources such as wind power and solar power is growing worldwide, and stable and efficient supply of renewable energy is needed to meet modern energy demand. In the case of wind power and solar power generation, which are representative renewable energy sources, there is a variation in power generation and output due to environmental changes. Therefore, a large-capacity, high-efficiency energy storage device is required to solve such problems.

Particularly, Redox flow battery is one of the storage technologies of renewable energy. Among them, vanadium redox flow battery (VRFB) has a long lifetime, fast reaction time, high And the charge / discharge efficiency.

On the other hand, the ion exchange membrane is the core material of the vanadium redox flow battery and plays the most important role in the performance of the battery. Because of the use of strong acid as the electrolyte for the vanadium redox flow battery, the ion exchange membrane should have excellent acid resistance and chemical resistance as well as ion selectivity. Nafion is the most commonly used ion exchange membrane for vanadium redox flow batteries. Nafion has the advantages of high mechanical and chemical stability and high hydrogen ion conductivity.

However, since Nafion has a low selective permeability of ions, the energy efficiency of the battery is deteriorated due to the vanadium cross-over phenomenon in which the vanadium ions in the anode and the cathode electrolyte are mixed with each other while passing through the opposite electrode. The life span can be reduced accordingly. In addition, Nafion is so expensive that it accounts for 41% of the manufacturing cost of vanadium redox flow battery cells.

Therefore, in order to develop an ion exchange membrane capable of replacing such Nafion, various attempts have been made in recent years. Especially, under the condition of vanadium and sulfuric acid, since the cell performance may be reduced due to the damage of the ion exchange membrane by the electrolyte, There is a demand for an ion exchange membrane which maintains conductivity, mechanical strength and durability and improves the performance of the battery.

Partial fluorine-based polymers applicable to such ion exchange membranes are chemically stable due to strong binding force between carbon-fluorine (CF) and shielding effect of fluorine atoms, and have excellent mechanical properties. Therefore, It is possible to provide an ion exchange membrane to which the above characteristics are added. In addition, it is expected that the partial fluorinated polymer chain has an effect of keeping the swelling of the non-fluorinated proton conductive polymer to a certain extent, thereby increasing the dimensional stability.

In addition, it is necessary to develop an additive capable of preventing the damage of the polymer constituting the ion exchange membrane. For example, a technique of introducing cerium into the fuel cell ion exchange membrane to improve the durability thereof is known, and this is to prevent the attack of oxidative radicals generated during driving. However, these prior art techniques mainly impregnate cerium into the ion exchange membrane in the form of a cerium salt. When this is applied to a redox flow cell, the cerium ion of the polymer constituting the ion exchange membrane Ion exchange is performed in the form of a sulfonic acid again, which causes a problem that the added cerium ions are eluted into the electrolyte solution.

U.S. Published Patent Application No. 2008-0160380 entitled " METHOD OF MAKING DURABLE POLYMER ELECTROLYTE MEMBRANES " United States Patent Publication No. 2014-0093808 "High Durability Fuel Cell Components with Cerium Salt Additives"

PNAS, 2012, 109 (4), 1029

Accordingly, the inventors of the present invention have conducted various studies. As a result, the vanadium redox flow battery was also introduced with cerium in order to prevent attack of oxidative radicals generated during driving, and the form of cerium ion (Ce ^{4 +} ) It is possible to prevent ion exchange in the form of sulfonic acid when the cerium salt is introduced as described above and to solve the problem that the cerium ions are eluted into the electrolyte solution.

Accordingly, an object of the present invention is to provide an ion exchange membrane for a vanadium redox flow battery in which cerium ions are stably introduced.

Another object of the present invention is to provide a vanadium redox flow battery including the ion exchange membrane.

In order to achieve the above object, the present invention provides an inorganic filler whose inorganic particle surface is modified with ammonium cerium (IV) nitrate (ACN).

Also provided is an ion exchange membrane comprising the ionic conductor and the inorganic filler impregnated in the ionic conductor.

Also disclosed is an ion exchange membrane comprising a porous substrate, an ion conductor provided in the pores of the porous substrate, and the inorganic filler impregnated in the ion conductor.

And a vanadium redox flow battery to which an ion exchange membrane including the inorganic filler is applied.

When the surface-modified inorganic filler of the present invention is applied to an ion exchange membrane for a flow battery, cerium ions can be prevented from flowing out to the electrolyte even in an environment of a flow battery in which an aqueous solution of sulfuric acid flows, and the ion conductivity of cerium ions can be improved Do.

1 is a schematic view showing an inorganic filler according to the present invention introduced into an ion exchange membrane.
2 shows the EDAX analysis results of the inorganic filler produced according to Example 1 of the present invention.
3 is an experimental schematic diagram for measuring the vanadium ion permeability of the ion exchange membranes of Example 1 and Comparative Example 2 of the present invention.
4 is data of vanadium ion permeability data of the ion exchange membranes of Example 1 and Comparative Example 2 of the invention.
5 is current efficiency data of VRFB having ion exchange membranes of Example 1 and Comparative Examples 1 and 2 of the present invention.
6 is voltage efficiency data of VRFB having ion exchange membranes of Example 1 and Comparative Examples 1 and 2 of the present invention.
7 is energy efficiency data of VRFB including the ion exchange membrane of Example 1 and Comparative Examples 1 and 2 of the present invention.
8 is current, voltage and energy efficiency data of VRFB including the ion exchange membrane of Example 1 and Comparative Example 3 of the present invention.

The present invention discloses an inorganic filler whose inorganic particle surface is modified with ammonium cerium (IV) nitrate (ACN) and an ion exchange membrane comprising the inorganic filler. The details will be described below.

Surface modified Inorganic filler

The vanadium redox flow battery has an ion exchange membrane composed of an ion conductive polymer and has an inorganic filler impregnated in pores of the ion exchange membrane. The vanadium redox flow battery is operated under an aqueous sulfuric acid solution, which generates oxidative radicals during operation. The oxidation radical may lower the activity through the introduction of cerium. However, when the sulfone group substituted with cerium in the ion exchange membrane is again ion-exchanged in the form of sulfonic acid, the added cerium ion simultaneously dissolves into the electrolyte solution.

In the present invention, the cerium ion is introduced into the ion exchange membrane, and is introduced into the inorganic filler in a state where it is not simply mixed but is inhibited from leaching. Preferably, the inorganic filler according to the present invention is obtained by coating the surface of the inorganic particles with ammonium cerium (IV) nitrate (ACN, (NH ₄ ) ₂ Ce (NO ₃ ) ₆ ). The ammonium cerium nitrate is hydrophilic and is coated on the surface of inorganic particles and then converted into cerium ions by an aqueous solution of sulfuric acid introduced into the ion exchange membrane. By fixing the cerium ions to the surface of the inorganic particles in this manner, it is possible to prevent the cerium ions from flowing out to the electrolytic solution even in the environment of the flow battery in which the aqueous sulfuric acid solution flows.

1 is a schematic view showing an inorganic filler according to the present invention introduced into an ion exchange membrane. 1, ammonium cerium nitrate coated on the inorganic filler is present in a hydrophilic region composed of sulfone groups in the ion exchange membrane, and the sulfone group and cerium ion are ionically bonded to each other and stably fixed. Prevent escape of cerium ions.

The inorganic particles constituting the inorganic filler may contain at least one of TiO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , MnO ₂ , BaTiO ₃ , CaCO ₃ , Montmorillonite and Mordenite .

The average particle diameter of the inorganic particles may be 1 to 1000 nm, preferably 1 to 100 nm. The inorganic filler having such a particle diameter is preferable for securing an effect of not only lowering the ion conductivity while increasing the mechanical strength of the ion exchange membrane as well as being easy to penetrate into the ion channel inside the hydrophilic region constituted by the sulfone group in the ion exchange membrane Do.

At this time, it is preferable that the inorganic filler is coated with ammonium cerium nitrate in an amount of 5 to 20 wt% on the surface of 80 to 95 wt% of inorganic particles. Such a range of the content of ammonium cerium nitrate is a preferable range for improving the ionic conductivity while securing the mechanical strength of the ion exchange membrane due to the inorganic particles and ensuring the fixing effect of cerium ion due to ionic bonding with the ion exchange membrane.

The present invention can surface-modify the inorganic particles with hydrophilic cerium, selectively impregnate the hydrophilic portion of the ion exchange membrane, and can be easily dispersed on the surface of the ion exchange membrane. When such an inorganic particle alone is impregnated into an ion exchange membrane, there is a problem that the ion conductivity of the battery is reduced. However, when an inorganic filler surface-modified with hydrophilic cerium is applied, it is possible to improve ionic conductivity by cerium ion.

The inorganic filler surface-modified with ammonium cerium (IV) nitrate (ACN) according to the present invention can be prepared by a conventional method, but the present invention is not limited thereto. For example, after the inorganic particles and the aqueous solution of ammonium cerium nitrate are mixed and stirred, the mixture is depressurized to evaporate the solvent, whereby the surface can fix the cerium nitrate.

Ion exchange membrane

The ion exchange membrane according to the first embodiment of the present invention comprises an ion conductor; And an inorganic filler impregnated in the ion conductor, and can be manufactured in the form of a pure membrane.

At this time, it is preferable that the inorganic filler is applied as an inorganic filler in which the surface of the inorganic particles according to the present invention is modified with ammonium cerium nitrate (ACN). When an ion exchange membrane containing an inorganic filler whose surface is modified with ammonium cerium nitrate (ACN) as described above is prepared, not only the mechanical strength is improved but also the problem of elution of the cerium ions to be washed away by the electrolyte can be reduced .

The ion conductor is not particularly limited as long as it is a polymer capable of ion exchange, and those generally used in the art can be used. For example, the polymer forming the ionic conductor may be a fluorine-based polymer, a partially fluorinated polymer, or a hydrocarbon-based polymer, and more specifically, a perfluorosulfonic acid polymer, a hydrocarbon polymer, an aromatic sulfonic polymer, an aromatic ketone polymer, A polymer, a polystyrene polymer, a polyester polymer, a polyimide polymer, a polyvinylidene fluoride polymer, a polyether sulfone polymer, a polyphenylene sulfide polymer, a polyphenylene oxide polymer, a polyphosphazene polymer, Based polymer, polyethylene naphthalate-based polymer, polyester-based polymer, doped polybenzimidazole-based polymer, polyether ketone-based polymer, polyphenylquinoxaline-based polymer, polysulfone-based polymer, sulfonated polyarylene ether- Ether ketone type polymer, sulfonated polyether ether A group consisting of a sulfonated polyimide polymer, a sulfonated polyimide polymer, a sulfonated polyphosphazene polymer, a sulfonated polystyrene polymer, and a radiation-polymerized sulfonated low density polyethylene-g-polystyrene polymer A homopolymer, an alternating copolymer, a random copolymer, a block copolymer, a multiblock copolymer, or a graft copolymer of one or more selected polymers may be used. Or a graft copolymer.

The partially fluorinated polymer used in the present invention is preferably a partially fluorinated polymer having a functional group that exhibits ionic conductivity like a sulfonic acid group and contains a fluorine component and is more economical than a fluorinated ion conductive polymer such as Nafion The ion permeability can be reduced to prevent the performance degradation of the flow battery. However, the partial fluorine-based ion exchange membrane has a lower current efficiency due to a low cross-over of vanadium ion as compared with the fluorine-based ion exchange membrane, but has a disadvantage in that the voltage efficiency is low due to low ion conductivity. Therefore, the addition of the surface-modified inorganic filler with the ammonium cerium nitrate (ACN) of the present invention to the fluorine-based ion exchange membrane can improve the current efficiency, the voltage efficiency and the energy efficiency.

The ion exchange membrane according to the second embodiment of the present invention may be made of a reinforced composite membrane including a porous substrate, an ion conductor provided in the pores of the porous substrate, and an inorganic filler impregnated in the ion conductor.

If the porous substrate includes a plurality of pores, the structure and material of the body are not particularly limited, and those generally used in the art can be used. For example, the porous substrate can be made of a material selected from the group consisting of ethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polycarbonate (PC), polyacrylonitrile (PAN), polytetrafluoroethylene (PVDF), polyimide (PI), polyvinylchloride, polyvinylidene chloride, polysulfone, polyethersulfone, polyarylene ether sulfone (PAES) At least one of polyetherketone, polyetheretherketone (PEEK), polyethylene ether nitrile, polyethylene terephthalate (PET), and combinations thereof.

The ion conductor and the inorganic filler are as described in the first embodiment.

1, the cerium ion (Ce ^{4 +} ) present on the surface of the inorganic filler exists in ionic bonding with a sulfone group (SO ₃ ^- ) existing in the ion conductor, In theory, cerium ions can be fixed to the ion exchange membrane even in a flow battery environment in which an aqueous sulfuric acid solution flows through four sulfonic groups bonded to one cerium ion. In addition, the sulfone group forms an ionic bond with the cerium ion and can exhibit some crosslinking effect. This improves the mechanical properties and chemical properties of the ion exchange membrane, thereby increasing durability.

The method for producing the ion exchange membrane according to the present invention has the following non-limiting examples.

First, the surface-modified inorganic filler and the ion conductor polymer are mixed together with a solvent. At this time, the content of the surface-modified inorganic filler is preferably adjusted to be 0.1 to 5 wt% of the ion conductor polymer. When the content of the surface-modified inorganic filler is less than 0.1% by weight, it is difficult to secure the effect expected in the present invention, and when it exceeds 5% by weight, the ion conductivity of the battery is decreased.

In the preparation of the mixed solution, a usable solvent may be a conventional organic solvent, water, or a mixed solution thereof with an organic solvent. Non-limiting examples of the organic solvent include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and alcohols.

Thereafter, the mixed solution is formed on the porous substrate by an ink jet method, a roll printing method, or the like. When the ion exchange membrane of the present invention is produced in the form of a pure membrane according to the first embodiment, the thickness of the coating can be adjusted to 0.005 to 20 mm, preferably 0.001 to 10 mm. When the ion exchange membrane of the present invention is manufactured in the form of a reinforced composite membrane according to the second embodiment, the coating thickness of the ion conductor impregnated with the inorganic filler coated on the entire porous substrate is preferably adjusted to 0.01 to 1 mm.

Redox Flow  battery

One embodiment of the present disclosure includes a cathode; anode; And a partial fluorine-based polymer ion exchange membrane disposed between the cathode and the anode. A negative electrode electrolyte injected into and discharged from the negative electrode side, and a positive electrode electrolyte injected into and discharged from the positive electrode side. The negative electrode electrolytic solution and the positive electrode electrolytic solution may include an electrolyte and a solvent, respectively. The electrolyte and the solvent are not particularly limited, but those generally used in the art can be employed.

According to the present invention, the electrochemical cell may be a fuel cell or a flow battery, preferably a flow battery, more preferably a redox flow battery. In one embodiment of the present invention, the redox flow battery uses a V (IV) / V (V) vanadium redox couple as a positive electrode electrolyte and a V (II) / V (III) vanadium redox Couples can be used.

The flow battery of the present invention comprises a negative electrode tank and a positive electrode tank for respectively storing a negative electrode electrolyte solution or a positive electrode electrolyte solution; A pump connected to the negative electrode tank and the positive electrode tank to supply the electrolyte solution to the negative electrode or the positive electrode; A cathode inlet and a cathode inlet through which the cathode electrolytic solution or the anode electrolytic solution flows respectively from the pump; And a cathode discharge port and a cathode discharge port through which the electrolytic solution is discharged from the cathode or the anode to the cathode tank and the anode tank, respectively.

The flow battery may utilize structures, materials, and methods known in the art, except for the ion exchange membrane described above.

The present invention also provides a battery module including the flow battery as a unit cell. The battery module may be stacked by inserting a bipolar plate between the flow batteries according to one embodiment of the present invention. The battery module may be specifically used as a power source for an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage device.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. These drawings may be embodied in various different forms as an embodiment for explaining the present invention, and are not limited thereto.

[Example 1]

1) Production of inorganic filler coated with ACN on the surface of silica particles

Neutral silica gel with an average particle size of 10 nm was mixed with an aqueous solution of ammonium cerium (IV) nitrate (ACN). At this time, 9.01 g of silica, 1.02 g of ACN and 2.0 ml of water were mixed, and the mixture was stirred for one day.

Thereafter, the mixture was evaporated under a reduced pressure of 0.1 Torr for 4 hours to obtain a yellow powder containing about 10% by weight of ACN relative to silica. The powder was washed several times with water to remove the remaining ACN, and the remaining solvent (water) was removed from the vacuum oven at room temperature to prepare an inorganic filler.

2) Preparation of ion exchange membrane

100 parts by weight of perfluorinated polyether ketone with CF ₃ group and 0.5 part by weight of the inorganic filler prepared above were dissolved in dimethylacetamide (DMAc) and stirred. For uniform dispersion, the solution was stirred for one day, and a uniform solution was prepared by applying ultrasonic waves. The mixed solution was formed into a film having a thickness of 50 탆 by using a coater, followed by drying at room temperature for 2 hours, drying at 80 캜 for 2 days, hot air drying at 120 캜 for 1 day to remove remaining solvent, Respectively.

[Comparative Example 1]

A commercially available ion exchange membrane Nafion 115 (DuPont) was used.

[Comparative Example 2]

Perfluorinated polyether ketone with CF 3 group was formed by the method of Example 1 and dried to prepare an ion exchange membrane.

[Comparative Example 3]

100 parts by weight of polyetherketone (CF ₃ group) and 0.5 part by weight of ammonium cerium (IV) nitrate (ACN) were dissolved in DMAc, followed by stirring for 1 day. This mixed solution was formed into a film by the method of Example 1 and then dried to prepare an ion exchange membrane.

[Experimental Example 1] EDAX element analysis

The content and distribution of cerium coated on the surface of the silica prepared in Example 1 were measured by EDAX (Energy Dispersive X-ray Fluorescence (Spectroscopy)). The results are shown in FIG. FIG. 2 (a) is a graph showing the shape of cerium coated on the silica surface using a scanning electron microscope (SEM) ) The distribution of cerium (Ce) was expressed in color. As a result, it was confirmed that the Ce element was contained in an amount of 1.24% by weight based on 11.15% by weight of the Si element and the weight ratio thereof was about 9: 1, and it was confirmed that the Ce element was evenly distributed in each silica particle.

[Experimental Example 2] Vapor permeability

As shown in Fig. 3, a water tank containing 2M of H ₂ SO ₄ solution in which 1M of VOSO ₄ was dissolved and 2M of H ₂ SO ₄ solution in which 1M of MgSO ₄ was dissolved was added to the relaxation exchange membrane prepared in Example 1 and Comparative Example 2 The permeability of the vanadium ion was calculated using the following equation (1). The results are shown in FIG.

&Quot; (1) "

(Where in the equation 1 V _B is the volume (L) of MgSO ₄ solution, C _A is the concentration (concentration of vanadium ions in enrichment side, mol / L) of the increased vanadium ion after a period of time of MgSO ₄ solution and , C _B is the concentration of vanadium ions in the MgSO ₄ solution, L is the thickness of the used ion exchange membrane (m), A is the active area of the ion exchange membrane used (m ² ), and D is the diffusion coefficient of vanadium ions (m ² / s)

Referring to FIG. 4, the results are summarized in Table 1 below. In Table 1, L is the thickness (cm) of the used ion exchange membrane, A is the active area (cm ² ) of the used ion exchange membrane, V _Mg is the volume (cm ³ ) of one solution, P is the vanadium (Cm < ² > / min) of the ion.

Slope L A V _Mg P cm cm ² cm ³ cm ² / min Example 1 4.09E-06 0.0055 7.69 190 5.56E-07 Comparative Example 2 1.49E-05 0.0052 7.69 200 2.02E-06

As can be seen from Fig. 4 and Table 1, it can be seen that the permeability of vanadium in the case of the ion exchange membrane of Example 1 was reduced to 25% level as compared with that of the ion exchange membrane of Comparative Example 2. Therefore, It is expected that the performance will be improved by reducing the cross-over phenomenon.

[Experimental Example 3] Current / voltage / energy efficiency

A vanadium redox flow battery (VRFB) containing the ion exchange membranes of Example 1 and Comparative Examples 1 to 3 thus prepared was tested for the following items.

1) The current efficiency, the voltage efficiency and the energy efficiency of the vanadium redox flow battery (VRFB) including the ion exchange membranes of Example 1 and Comparative Examples 1 and 2 were calculated and shown in FIGS. 5 to 7.

2) The current efficiency, the voltage efficiency and the energy efficiency of the vanadium redox flow battery (VRFB) including the ion exchange membranes of Example 1 and Comparative Example 3 were calculated and shown in FIG.

The test results are summarized in Table 2 below.

50 cycle average Current efficiency (%) Voltage efficiency (%) Energy efficiency (%) Example 1 99.4 92.9 92.4 Comparative Example 1 96.3 93.1 89.6 Comparative Example 2 99.0 92.6 91.7 Comparative Example 3 98.7 92.3 91.1

Compared with Comparative Example 1, which is a fluorine-based ion exchange membrane, Comparative Example 2, which is a partial fluorine-based ion exchange membrane, shows that although the current efficiency is high due to the low cross-over of vanadium ions, the ion conductivity is low and the voltage efficiency is somewhat lower. In the case of Comparative Example 3 in which only the ACN salt was added to the partially fluorinated ion exchange membrane, the current efficiency, the voltage efficiency and the energy efficiency were all reduced.

Example 1, which is a partial fluorine-based ion exchange membrane including an inorganic filler surface-modified with ACN according to the present invention, has a current efficiency improved by 0.4%, a voltage efficiency of 0.3%, an energy efficiency Was improved to 0.7%. Therefore, when ACN is added to an ion exchange membrane simply in the form of a salt, the performance of the vanadium redox flow battery is lowered. However, when the ACN is added to the ion exchange membrane in the form of an inorganic filler surface-modified with ACN, Respectively.

Claims (11)

An inorganic filler whose inorganic particle surface is coated with Ammonium cerium (IV) nitrate (ACN).
The method according to claim 1,
Wherein the inorganic filler comprises 80 to 95% by weight of inorganic particles and 5 to 20% by weight of ammonium cerium nitrate.
The method of claim 1, wherein
Wherein the inorganic particles are at least one selected from TiO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , MnO ₂ , BaTiO ₃ , CaCO ₃ , Montmorillonite and Mordenite. filler.
The method according to claim 1,
Wherein the inorganic particles have an average particle diameter of 1 to 1000 nm.
Ion conductors; And
An inorganic filler impregnated in the ion conductor;
/ RTI >
Wherein the inorganic filler is coated on the surface of the inorganic particles with ammonium cerium nitrate (ACN).
A porous substrate;
An ion conductor provided in the pores of the porous substrate; And
An inorganic filler impregnated in the ion conductor;
/ RTI >
Wherein the inorganic filler is coated on the surface of the inorganic particles with ammonium cerium nitrate (ACN).
The method according to claim 5 or 6,
The ion conductor may be at least one selected from the group consisting of perfluorosulfonic acid polymer, hydrocarbon polymer, aromatic sulfon polymer, aromatic ketone polymer, polybenzimidazole polymer, polystyrene polymer, polyester polymer, polyimide polymer, polyvinylidene fluoride Based polymer, polyether sulfone type polymer, polyphenylene sulfide type polymer, polyphenylene oxide type polymer, polyphosphazene type polymer, polyethylene naphthalate type polymer, polyester type polymer, doped polybenzimidazole type polymer, poly A sulfonated polyether ether ketone-based polymer, a sulfonated polyether ether ketone-based polymer, a sulfonated polyamide-based polymer, a sulfonated polyimide-based polymer, a sulfonated polyimide-based polymer, A sulfonated polyimide-based polymer, a sulfonated polyphosphazene-based polymer, Chemistry polystyrene-based polymer and a radiation polymerization of a sulfonated polystyrene-based low density polyethylene -g- ion exchange membrane comprises a polymer at least one member selected from the group selected from the group consisting of.
The method according to claim 5 or 6,
Wherein the inorganic filler is impregnated in an amount of 0.1 to 5% by weight based on the ionic conductor content.
The method according to claim 5 or 6,
Wherein the cerium ion (Ce ^{4 +} ) of the inorganic filler is ion-bonded to a sulfonic acid group (SO ₃ ^- ) existing in the ion conductor.
The method according to claim 6,
The porous substrate may be made of a high density polyethylene (HDPE), a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), an ultra high molecular weight polyethylene (UMWPE), an ethylene vinyl acetate copolymer (EVA), a polypropylene (PP), a polycarbonate , Polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyimide (PI), polyvinylchloride, polyvinylidene chloride, polyether sulfone, polysulfone, polyethersulfone, polyarylene ether sulfone (PAES), polyetherketone, polyetheretherketone (PEEK), polyethylene ether nitrile, polyethylene terephthalate (PET) ), And a combination thereof.
cathode; anode; And an ion exchange membrane disposed between the cathode and the anode, the vanadium redox flow battery comprising:
The vanadium redox flow battery according to claim 5 or 6, wherein the ion exchange membrane is the ion exchange membrane.

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