KR20160037138A - Anion exchange electrolyte membrane, method for preparing the same, energy storage and water treating apparatus comprising the same - Google Patents

Abstract

The present invention relates to an anion exchange membrane, and to a manufacturing method thereof and, more specifically, to an aromatic hydrocarbon polymer-based anion-conductive electrolyte membrane, and to an energy storage apparatus and a water treatment apparatus comprising the electrolyte membrane. The anion-conductive electrolyte membrane has excellent thermal stability, mechanical stability, and chemical stability, while maintaining the anion conductivity of an anion exchange membrane to be the same as or greater than that of a conventional anion exchange membrane.

Description

TECHNICAL FIELD The present invention relates to an anion exchange electrolyte membrane, an anion conductive electrolyte membrane, an anion conductive electrolyte membrane production method, and an energy storage device and a water treatment apparatus comprising the electrolyte membrane.

The present invention relates to an anion exchange membrane and a method for producing the same, and more particularly, to an energy storage device and a water treatment apparatus including an aromatic hydrocarbon-based polymer-based anion conductive electrolyte membrane and the electrolyte membrane.

The ion-exchange membrane is a type of polymer membrane, and can separate anions or cations selectively depending on the type of ion-exchangeable group introduced into the membrane. In the case of cation exchange membranes used for commercial purposes, the ion exchanger is largely divided into a strong acid sulfonic acid group (-SO ₃ -) and a weakly acidic carboxylic acid group (-COO-). In the case of anion exchange membranes, Group (-NR ₃ ) as an ion-exchange group.

 Current examples of ion exchange membrane applications include electrodialysis, water-splitting electrodialysis for desalination and purification, diffusion dialysis for recovery of acid from acidic wastewater and ultrapure water production And an electrode desorption process (electrodeionization process). Particularly recently, interest in ion exchange membranes has been increasing as the ion exchange membrane shows the possibility of exhibiting excellent performance of a polymer electrolyte fuel cell or a redox flow cell.

On the other hand, the principle of generating electricity in a fuel cell is that when fuel is supplied through a fuel electrode, the fuel is divided into hydrogen ions and electrons, and hydrogen ions combine with oxygen supplied from the air electrode through the electrolyte membrane to produce water. The electrons separated from the fuel of the fuel electrode proceed to an electrochemical reaction that generates a current through an external circuit to generate electricity and heat.

Among the fuel cells, a polymer electrolyte membrane fuel cell (PEMFC), a direct methanol fuel cell (DMFC), and a direct borohydride fuel cell (DBFC) A direct borohydride fuel cell (DBFC), and a solid alkaline fuel cell (SAFC) may be formed of a hydroxide ion conducting electrolyte membrane or a hydrogen ion conducting electrolyte membrane. Alternatively, a direct borohydride fuel cell Anion exchange membrane should be employed. Here, the direct boron hydride fuel cell can use both a cation exchange membrane and an anion exchange membrane.

The fuel cell employing the anion exchange membrane is characterized by being able to use a non-noble metal or a non-noble metal catalyst for the electrode as compared with the fuel cell employing the cation exchange membrane, and thus the price can be reduced.

In the case of a redox flow cell using a sulfuric acid vanadium electrolyte, a cation exchange membrane and an anion exchange membrane can be used. In order to lower the permeability of vanadium and to operate the system for a long time, development of an anion membrane having excellent durability in a sulfuric acid- have. In addition, in the case of a water treatment apparatus, especially CDI technology, development of anion membrane technology is urgently required to improve durability.

The present inventors have completed the present invention by developing a low-cost anion conductive electrolyte membrane applicable to both energy storage devices and water treatment devices.

Accordingly, an object of the present invention is to provide an anionic conductive polymer copolymer which is excellent in thermal stability, mechanical stability and chemical stability, and can maintain anion conductivity equal to or higher than that of a commercially available anion exchange membrane, Thereby providing an anionic conductive electrolyte membrane.

Another object of the present invention is to overcome the difficulty of the bromination reaction of the existing hydrocarbon-based polymer, and it is possible to overcome the difficulty of the bromination reaction of the conventional hydrocarbon polymer by using an aromatic hydrocarbon-based polymer as a base but also by carrying out a bromination reaction through an environmentally comparatively stable and safe synthetic route, The present invention provides a method for producing an anionic conductive electrolyte membrane capable of producing a high yield of an anionic conductive electrolyte membrane containing a copolymer.

It is another object of the present invention to provide an anion conductive electrolyte membrane which can be manufactured at a price two to ten times or more lower than that of a conventionally used Nafion membrane, a cation exchange membrane, and an anion exchange membrane used in a fuel cell or a water treatment apparatus, And a method for manufacturing the same.

Another object of the present invention is to provide an anionic conductive exchange membrane which is excellent in mechanical stability, thermal stability and chemical stability as well as anion conductivity and which maintains a level equal to or higher than that of a commercially available anion conductive membrane, And an energy storage device and a water treatment device which can be greatly improved.

The object of the present invention is not limited to the above-mentioned objects, and although not explicitly mentioned, the object of the invention which can be recognized by a person skilled in the art from the description of the detailed description of the invention .

In order to accomplish the above object of the present invention, the present invention provides an anionic conductive electrolyte membrane comprising an anionic conductive polymer represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ' and R ₄ 'are the same or different from each other and represent -H, -F, -Cl, -Br, An alkyl group, a fluoroalkyl group, -C ₆ H ₅ , - (C ₆ H ₄ ) _n -C ₆ H ₅ , -C ₆ F ₅ , - (C ₆ F ₄ ) _n -C ₆ F ₅ , R ₃ 'is selected from an anionic conductive group comprising an imidazolium group, a guanidine hydrochloride group or a phosphonium group, X ₁ and X ₂ are selected from -O-, -CO- , -SO ₂ -, and n is a real number between 0 and 1, representing the content in%.

In a preferred embodiment, in the anionic conductive polymer copolymer, the repeating unit of R ₃ 'is 1 to 99 mol%.

In a preferred embodiment, the imidazole (imidazolium) groups, guanidine hydrochloride (guanidine hydrochloride) or phosphonium group (phosphonium) groups are _{-H, - (CH 3) n} , - (C 6 H 5) n, - _{F, - (CF 3) n} , - (C 6 F 5) n, -Cl, - (CCl 3) n, - (C 6 Cl 5) n, -Br, - (CBr 3) n, - (C ₆ Br ₅ ) _n .

In a preferred embodiment, the film thickness in the no-humidified state is 5 to 500 mu m.

The present invention also relates to a process for producing a brominated aromatic hydrocarbon polymer, which comprises brominating an aromatic hydrocarbon polymer represented by the following formula (2)

(2)

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' are the same as or different from each other and represent -H, -F, -Cl, -Br , -I, an alkyl group, a fluorine group, a -C ₆ H _5, - consisting of _{(C 6 F 4) n -C} 6 F 5 - (C 6 H 4) n -C 6 H 5, -C 6 F 5, X ₁ and X ₂ are selected from -O-, -CO-, and -SO ₂ -, and n is a real number between 0 and 1, representing the weight percentage contained in the aromatic hydrocarbon-based polymer.

A first substitution step of substituting the anion-conducting group at the brominated position of the brominated aromatic hydrocarbon-based polymer; A film forming step of forming a precursor film with the substituted aromatic hydrocarbon-based polymer; And a second replacement step of replacing the precursor film with a hydroxyl group.

In a preferred embodiment, the bromination step is performed by reacting the aromatic hydrocarbon-based polymer with N-bromosuccinimide (NBS) or Bromine-solution.

In a preferred embodiment, the first substitution step is a step in which at least one substance selected from the group consisting of an imidazolium group, a guanidine hydrochloride group, and a phosphonium group is substituted with bromine of the aromatic hydrocarbon-based polymer .

In a preferred embodiment, the film forming step includes casting a solution of the aromatic hydrocarbon-based polymer substituted on the anionically conductive group obtained in the first substitution step on a flat plate; A primary drying step of removing the solvent at a temperature of 30 ° C to 100 ° C in the cast state to obtain a precursor film; And a secondary drying step of treating the precursor film under a temperature condition of 50 ° C to 200 ° C and a vacuum condition.

The present invention also provides an energy storage device comprising any one of the above-described anionically conductive electrolyte membranes or an anionically conductive electrolyte membrane produced by any one of the above-described production methods.

In a preferred embodiment, the energy storage device is a redox flow cell, a direct borohydride fuel cell (DBFC), or a solid alkaline fuel cell (SAFC).

The present invention also provides a water treatment apparatus comprising an anionic conductive electrolyte membrane described above or an anionic conductive electrolyte membrane produced by any one of the above-described manufacturing methods.

The present invention has the following excellent effects.

First, according to the anionic conductive electrolyte membrane including the anionic conductive polymer of the present invention, an electrolyte membrane using an aromatic hydrocarbon-based polymer is excellent in thermal stability, mechanical stability, and chemical stability, and is superior in anion conductivity Lt; / RTI >

The method for producing an anion conductive electrolyte membrane of the present invention overcomes the difficulty of bromination reaction of conventional hydrocarbon polymers, thereby enabling a bromination reaction to be carried out through an environmentally comparatively stable and safe synthesis route based on an aromatic hydrocarbon polymer, Through the amination reaction, an anionic conductive electrolyte membrane containing an anionic conductive polymer copolymer can be produced at a high yield.

Further, according to the anionically conductive electrolyte membrane and the method for producing the same of the present invention, it is possible to manufacture the anion conductive electrolyte membrane at an affordable price two to ten times that of the conventionally used Nafion membrane, cation exchange membrane, and anion exchange membrane used in a fuel cell or a water treatment apparatus Is possible.

In addition, since the energy storage device and the water treatment device of the present invention include an anion conductive exchange membrane which is superior in mechanical stability, thermal stability, and chemical stability as well as anion conductivity, The long-term stability of the system can be greatly improved.

These technical advantages of the present invention are not limited to the above-mentioned technical scope, and even if not explicitly mentioned, the effect of the invention which can be recognized by a person skilled in the art from the description of the concrete contents for carrying out the invention Of course.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the reaction and the degree of preparation of an anionic conductive electrolyte membrane containing an anionic conductive polymer according to an embodiment of the present invention.
FIGS. 2A to 2C are actual photographs of the reaction and degree of progression shown in FIG. 1. FIG.
FIG. 3 is a graph showing the reaction and the degree of the anionic conductive electrolyte membrane containing an anionic conductive polymer according to another embodiment of the present invention.
4 is a graph of ¹ HNMR analysis results for confirming the synthesis of B-PPO in the production method according to the preferred embodiment of the present invention.
5 is a graph showing FT-IR analysis results confirming the synthesis of BIM-PPO in the production method according to the preferred embodiment of the present invention.
6 is a graph showing the glass transition temperature of the anionic conductive electrolyte membrane obtained in FIG.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments. Also, in certain cases, there may be a term selected arbitrarily by the applicant, in which case the meaning thereof will be described in detail in the description of the corresponding invention. Accordingly, the terms used in the present invention should not be construed to be mere terms, but should be interpreted based on the ordinary meanings of the terms and contents described throughout the specification of the present invention.

Hereinafter, the technical structure of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals used to describe the present invention throughout the specification denote like elements.

Technical features of the present invention include an anionic conductive electrolyte membrane having improved mechanical, thermal and chemical stability while ensuring an anion conductivity of an appropriate level or higher by including an anionic conductive polymer copolymer formed by introducing an anionic conductive group into an aromatic hydrocarbon-based polymer copolymer, and Manufacturing method.

That is, in the case of the present invention, in order to introduce an anion-conductive group into the aromatic hydrocarbon-based polymer copolymer, a substituent formed by brominating or aminating an aromatic hydrocarbon-based polymer copolymer is first formed to introduce an anion-conducting group into a bromination site or an amination site This is because the anion conductivity of the entire anion conductive electrolyte membrane can be controlled by controlling the substitution degree of the substituent to control the content of the anion conductive group by forming the anion conductive electrolyte membrane in such a manner that the anion-

In addition, conventionally, the bromination reaction of the hydrocarbon-based polymer is difficult in the synthesis process using bromine gas. However, the present invention can provide a method that is relatively stable and safe as well as yielded in a relatively environmentally friendly manner.

Accordingly, the anionic conductive polymer included in the anionically conductive electrolyte membrane of the present invention may be represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ' and R ₄ 'are the same or different from each other and represent -H, -F, -Cl, -Br, An alkyl group, a fluoroalkyl group, -C ₆ H ₅ , - (C ₆ H ₄ ) _n -C ₆ H ₅ , -C ₆ F ₅ , - (C ₆ F ₄ ) _n -C ₆ F ₅ , R ₃ 'is selected from an anionic conductive group comprising an imidazolium group, a guanidine hydrochloride group or a phosphonium group, X ₁ and X ₂ are selected from -O-, -CO- , -SO ₂ -, and n is a real number between 0 and 1, representing the content in%. For reference, n used in the functional groups selected to be selected from among R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ' and R ₄ 'represents the content of each polymer N is an integer greater than zero as known to be different from n, 1-n for inclusion.

Herein, the anion conductive group imidazolium group, guanidine hydrochloride group or phosphonium group is -H, - (CH ₃ ) _n , - (C ₆ H ₅ ) _n , -F _{, - (CF 3) n,} - (C 6 F 5) n, -Cl, - (CCl 3) n, - (C 6 Cl 5) n, -Br, - (CBr 3) n, - (C 6 Br ₅ ) _n may be introduced. The n used in the functional group is an integer greater than zero.

On the other hand, in the negative ion-conducting polymer copolymer, R ₃ 'in the repeating units may be a 1 mol% to 99 mol%, thus R _3' is obtained from the formula (I) according to the anion content of the conductive group is introduced into the negative ion-conducting polymer Aerial Physical properties such as mechanical properties, thermal stability, chemical stability, and anion conductivity of the anion-conductive electrolyte membrane containing the polymer and the anion-conductive electrolyte membrane may vary. That is, when the degree of substitution of the anionic conductive group is increased, the hydrophilic property is increased and the anionic conductivity is increased, but the mechanical properties may be deteriorated. Since the anion-conducting group in the formula (1) of the present invention is introduced by substituting the brominated green or aminated substituent as described above, the substitution amount (1-n) of the anion-conducting group in the formula You can control through the type.

The anionically conductive electrolyte membrane of the present invention having such characteristics may have a thickness of 5 to 500 mu m in a non-humidified state.

Next, in the method for producing an anionic conductive electrolyte membrane of the present invention, the order of the precursor film forming step and the anion conductive group replacing step is different, as the substituent is a brominated substituent or an aminated substituent.

First, a method for producing an anion-conductive electrolyte membrane using a brominated substituent comprises: a step of brominating an aromatic hydrocarbon-based polymer represented by Formula 2;

(2)

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' are the same as or different from each other and represent -H, -F, -Cl, -Br , -I, an alkyl group, a fluorine group, a -C ₆ H _5, - consisting of _{(C 6 F 4) n -C} 6 F 5 - (C 6 H 4) n -C 6 H 5, -C 6 F 5, X ₁ and X ₂ are selected from -O-, -CO-, and -SO ₂ -, and n is a real number between 0 and 1, representing the weight percentage contained in the aromatic hydrocarbon-based polymer.

A first substituting step of substituting the anion conducting group at the brominated position of the brominated aromatic hydrocarbon polymer; A film forming step of forming a precursor film with a substituted aromatic hydrocarbon polymer; And a second replacement step of replacing the precursor film with a hydroxyl group.

Here, the bromination step may be performed by reacting an aromatic hydrocarbon-based polymer with a compound containing bromine, for example, by reacting N-bromosuccinimide (NBS) or Bromine-solution.

The first substitution step may be carried out by replacing one or more materials selected from the group consisting of an imidazolium group, a guanidine hydrochloride group and a phosphonium group with bromine of a brominated aromatic hydrocarbon-based polymer.

Casting the aromatic hydrocarbon polymer solution substituted on the anion conductive group obtained in the first substitution step on a flat plate; A primary drying step of removing the solvent at a temperature of 30 DEG C to 100 DEG C in a cast state to obtain a precursor film; And a secondary drying step of treating the precursor film at a temperature condition of 50 ° C to 200 ° C and a vacuum condition. The plate used for casting is not limited as long as it is a plate having a flat surface, but it may be a glass plate.

Also, a method for preparing an anionic conductive electrolyte membrane using an aminated substituent includes a film forming step of forming a precursor film with an aromatic hydrocarbon-based polymer represented by Formula 2 above; An amination step of aminating an aromatic hydrocarbon-based polymer having a precursor film formed thereon; And a substitution step of replacing the aminated precursor membrane with a chlorinating group.

Here, the film forming step includes casting a solution prepared by dissolving an aromatic hydrocarbon-based polymer on a flat plate; And drying in a cast state. The plate used in casting is not limited as long as it is a plate having a flat surface, but it may be a glass plate.

The amination step may involve introducing the anionic conductive group while reacting the precursor membrane with a solution of trimethylamine to amidize it.

The substitution step can be performed by treating the aminated precursor membrane with a hydrochloric acid solution or a hydrochloric acid solution.

The anion conductive electrolyte membranes thus formed are classified into the Nafion series, the ketone series (sPEEK, sPEK), the sulphone series (sPAES, sPAEES), and the sulphonic series (sPAES, sPAEES) in terms of physical properties such as ionic conductivity, permeability, chemical / thermal / mechanical / , Imide series (sPI), the physical properties of the polymer electrolyte membrane of the present invention are not only equal to or better than those of the polymer electrolyte membrane of the present invention, but also are extremely low in cost, with a manufacturing cost of 2 to 10 times lower. In addition, the long-term chemical stability in the sulfuric acid solution is also very excellent, and the long-term stability can be greatly improved.

Next, the energy storage device including the anionically conductive electrolyte membrane of the present invention can exhibit an improved effect in terms of cell performance, as well as an anion conductivity as well as an excellent stability, so that the long-term stability of the system can be greatly improved.

In addition, the water treatment apparatus including the anionically conductive electrolyte membrane of the present invention is excellent in mechanical, chemical, and thermal stability as well as anion conductivity, and is thus excellent in stability during driving, and the long-term stability of the system can be greatly improved.

Example 1

Anionic conductive electrolyte membrane 1 (M1, BIM-PPO) containing an anion conductive polymer was prepared according to the reaction scheme shown in FIG. 1 and the brominated substituents according to FIGS. 2A to 2C as follows.

1. Bromination step of brominating an aromatic hydrocarbon-based polymer

① Dissolve 12 g of PPO (polyphenylene oxide) as a solute in 100 cc of chlorobenzene as a solvent in a three-necked reactor for 20 minutes, add 9.8 g of N-bromosuccinimide (NBS) and 0.5 g of AIBN and stir. At this time, the stirring speed in the reactor is maximized to proceed for 3.5 hours. After 7 hours, the temperature of the reactor is maintained at 140 占 폚 for 3 hours or more. Add the reaction mixture to ice water for 20 minutes while stirring in a beaker.

② After that, precipitate in 500cc of isopropyl alcohol (IPA) and proceed with filtering. The IPA washing process is carried out once more and then the reaction is resolved by precipitating in 120 cc of Chloroform. The solution is subjected to IPA precipitation and filtering to obtain a brominated aromatic hydrocarbon polymer, i.e., B-PPO (or BPPO). The B-PPO obtained is dried in an oven at 55 캜 under vacuum for one day.

2. A first substitution step of substituting an anion-conducting group at the brominated position of the brominated aromatic hydrocarbon-based polymer

(3) 3 g of B-PPO, 17 g of NMP and 0.42 cc of imidazole are stirred in a hot-plate at 40 ° C for 12 hours.

3. Film formation step of forming precursor film with substituted aromatic hydrocarbon polymer

(4) The prepared solution is cast on a glass plate through casting in an oven at 80 ° C for 12 hours to remove the solvent, and then dried in a vacuum oven at 100 ° C for 24 hours.

4. A second displacement step of replacing the precursor membrane with a hydroxyl group

(5) If the prepared precursor membrane is put in 1 mmol of aqueous NaOH solution for 24 hours, anion conductive electrolyte membrane 1 (M1, BIM-PPO) can finally be obtained.

Example 2

Anionic conductive electrolyte membrane 2 (M2) containing the anionic conductive polymer copolymer was prepared as follows using an aminated substituent.

1. A film forming step of forming a precursor film with an aromatic hydrocarbon polymer

20 g of PPO (aromatic hydrocarbon polymer) and 100 ml of chloroform are added to a 250 ml three-necked round bottom reactor. Add 13.5 g of anhydrous aluminum chloride and stir thoroughly to dissolve completely. To this solution, a small amount of 1,3-bis-chlroacetyl is added, followed by stirring at 40 ° C for 4 hours. The resulting solution is filtered using ethanol and finally dried at 60 ° C for 48 hours. A 15 wt% solution of the dried material is made with DMF and cast on a glass plate. Dried at room temperature for 24 hours and dried at 60 DEG C for 24 hours to form a precursor film.

2. Amination step of amination of aromatic hydrocarbon polymer forming precursor film

The prepared precursor membrane proceeds quaternary amination in a trimethylamine aqueous solution.

3. Substitution step of replacing the aminated precursor membrane with a chlorinating group

The anion conducting electrolyte membrane 2 (M2) was prepared by washing the precursor membrane with 0.5 M HCl and 1 M NaCl to replace the chloride form.

Example 3

Anion conductive electrolyte membrane 3 (M3, BIM-PPO) containing an anion conductive polymer was prepared using a brominated substituent.

1. Bromination step of brominating an aromatic hydrocarbon-based polymer

6.81 g of PPO (aromatic hydrocarbon polymer) and 27 cc of chlorobenzene are added to a 250 ml 3-necked round bottom reactor. The reaction temperature is 125 ° C and 0.382 cc of Bromine solution is added. Then, the reaction is applied for 12 hours.

2. A first substitution step of substituting an anion-conducting group at the brominated position of the brominated aromatic hydrocarbon-based polymer

3 g B-PPO, 17 g NMP and 0.42 cc Phosphonium are mixed and mixed in a hot-plate at 40 ° C for 12 hours.

3. Film formation step of forming precursor film with substituted aromatic hydrocarbon polymer

The resulting solution was cast on a glass plate through casting in an oven at 80 ° C for 12 hours to remove the solvent and then dried in a vacuum oven at 100 ° C for 24 hours.

4. A second displacement step of replacing the precursor membrane with a hydroxyl group

Finally, the prepared precursor membrane was placed in a 1 mmol aqueous NaOH solution for 24 hours to finally form an anionic conductive electrolyte membrane (M3).

Example 4

According to the reaction scheme shown in FIG. 3, an anionic conductive electrolyte membrane 4 (BIM-Modified-PPO) containing an anion conductive polymer was prepared using a brominated substituent. Here, in order to improve the durability and chemical properties of the finally obtained anion-conducting electrolyte membrane 4, Modified-BPPO having a phenol group-substituted modified PPO, which is an aromatic hydrocarbon-based polymer, is used as a brominated substituent.

1. Bromination step of brominating an aromatic hydrocarbon-based polymer

0.041 g CuCl, 0.031 g TMEDA and 2 g Anhydrous magnesium sulfate are added to 35 ml 1,2-dichlorobenzene. Add to the oil bath at 65 ° C and mix with a stirrer. When the mixture is green through bubbling with Oxygen for 10 minutes, dissolve 5 g of diphenylphenol in dichloromethane (40 ml) slowly for 20 minutes. If you see a dark red color, it reacts for 24 hours. Filter, add 400 ml of methanol, mix several times, and filter to obtain polymer. It is then reslocated in 40 ml of chloroform and filtered into 400 ml of methanol. The obtained polymer is about 3 g, and is dried in a vacuum oven at 80 DEG C for 24 hours. 5 g of the obtained Modified-PPO is mixed with 50 ml of CHCl3. Dilute bromine in 10 ml of chloroform and mix 8 to 10 ml of the mixture over 30 minutes. Maintains the dark red color during the Bromination reaction. To remove HBr from the reactor, argon is bubbled and reacted at room temperature for 1 hour, then 800 ml of ethanol is mechanically reacted with a stirrer. After filtering, allow to dry in a vacuum oven.

2. A first substitution step of substituting an anion-conducting group at the brominated position of the brominated aromatic hydrocarbon-based polymer

3g Modified-BPPO, 17g NMP and 0.42cc imidazole are stirred in a hot-plate at 40 占 폚 for 12 hours.

3. Film formation step of forming precursor film with substituted aromatic hydrocarbon polymer

The prepared solution is cast on a glass plate through casting in an oven at 80 ° C for 12 hours to remove the solvent, and then dried in a vacuum oven at 100 ° C for 24 hours.

4. A second displacement step of replacing the precursor membrane with a hydroxyl group

When the prepared precursor film is placed in 1 mmol of aqueous NaOH solution for 24 hours, finally anion conductive electrolyte membrane 4 (BIM-Modified-PPO) can be obtained.

Experimental Example 1

¹ H NMR analysis and FT-IR analysis were performed to confirm the synthesis of B-PPO and BIM-PPO in Example 1, and the results are shown in FIG. 4 and FIG.

That is, the result of FIG. 4 shows that B-PPO was prepared and dissolved in DMSO-d6 and then analyzed by 500 MHz NMR. The characteristic peak of -CH ₂ Br group was confirmed at 4,3 ppm, I was able to see that it was done perfectly.

In addition, the results shown in FIG. 5 show FT-IR analysis results of a film in which a brominated film and imidazole group were introduced, that is, BIM-PPO, and a new peak was observed at 750 cm ^-1 . .

Experimental Example 2

The properties of the anionically conductive electrolyte membranes M1 to M3 prepared in Examples 1 to 3 were evaluated in the following manner. The results are summarized in Table 1.

<IEC measurement>

After cutting the membrane to a size of 4 cm x 4 cm, place it in 1 mole NaCl solution for 24 hours. The membrane is immersed in 0.5 moles Na ₂ SO ₄ solution for two days. The Cl ^- ions separated from the film are titrated with AgNO ₃ solution, and the indicator is K ₂ Cr ₂ O ₇ . The detailed calculation method is as follows.

 &Lt; Measurement of ion conductivity &

Ion conductivity was measured using Electrochemical Impedance Spectroscopy (IviumStat, IVIUM technologies). The prepared polymer electrolyte membrane was impregnated in distilled water for 24 hours or more, and placed in the center of the ion conductivity measuring cell, and the electrical resistance of the membrane was measured in a constant temperature water tank filled with distilled water. The frequency range was 1MHz at 1000Hz and the amplitude was 0.01 ~ 0.5V. After measuring the electrical resistance, calculate the conductivity by substituting the following equation.

<Water content measurement>

The prepared polymer electrolyte membrane is fully immersed in distilled water at room temperature for 24 hours or more, and then the mass of the membrane is measured. The measured membrane is placed in a vacuum oven for 24 hours or longer and vacuum dried to completely remove water and then the mass is measured again. Calculate the water content using the following equation.

(G) is the mass of the film containing moisture, and (g) is the mass of the vacuum dried film.

 &Lt; Measurement of dimensional change rate &

Calculate the dimensional stability using the following equation after measuring the length of the film in the wet state and the film in the dry state.

(G) is the length of the film containing moisture, and (g) is the length of the vacuum dried film.

Anion conductive electrolyte membrane Moisture content (%) Dimensional change rate
(%) Resistance (Ωcm ² ) IEC
(meq./g) Example 1 (M1) 25 10 1.4 1.8 Example 2 (M2) 27 12 1.6 1.8 Example 3 (M3) 26 11 1.5 1.8 Example 4 (M4) 24 10 1.3 1.8 Commercial membranes (pumice) 28 10 1.5 1.0

As can be seen from Table 1, the chemical structures of the anion conductive electrolyte membranes obtained in Examples 1 to 4 and the water content, dimensional change rate and ionic conductivity according to the IEC changes were compared with those of the conventional membrane, Resistance. This is because the anion conductive electrolyte membrane of the present invention is more easily chemically ion-conductive than the commercial anion conductive membrane (Fumion) and has a structure excellent in mechanical properties.

Experimental Example 3

The glass transition temperatures of the anion conducting electrolyte membranes M1 to M3 prepared in Examples 1 to 3 were measured and the results are summarized in Table 2. [

Commercial membrane
(Puomyion) Example 1
(M1) Example 2
(M2) Example 3
(M3) Example 4
(M4) Tg (占 폚) 108 240 215 220 230

From Table 2, it can be seen that the glass transition temperatures of Examples 1 to 4 are relatively higher than those of the comparative film, so that the thermal stability is excellent. It is considered that this is due to the chemical structure of the present invention in which the phenyl group in the main chain structure is abundant. In addition, IEC was higher than that of the comparative example, suggesting that the increase of the glass transition temperature was induced by the interaction between the ion conductive groups.

Experimental Example 4

The solubility experiments of B-PPO and M1 (BIM-PPO) prepared in Example 1 were carried on various solvents, and the results are shown in Table 3.

The solvent B-PPO BIM-PPO Chloroform + - DMF - - NMP + - DMAc - - Acetone - - DMSO - - Methyl alcohol - - benzene + - Dichloroethane + - THF + - Sulfuric acid (H ₂ SO ₄ ) - - Fuming, H ₂ SO ₄ - - m-Cresol + -

From Table 3, it can be seen that the solubility of the membrane (B-PPO) in the bromination step (B-PPO) to commercial solvents is higher than that of the imidazole group in the bromination step, The solubility characteristics of the substitution film hardly appeared and it was indirectly confirmed that the durability was excellent.

Experimental Example 5

13 mg of BIM-Modified-PPO obtained in Example 4 was prepared for differential scanning calorimeter (DSC) measurement. The experimental conditions were -40 ℃ ~ 350 ℃ and the temperature increase was 10 ℃ / min. The results are shown in Fig.

From FIG. 6, DSC was measured for comparison of the glass transition temperature with the commercial film. As a result, the glass transition temperature of the commercial film, pumilon, was found to be 108 degrees, while the glass transition temperature of the anionic conductive material of the present invention was found to be about 240 degrees, It can be seen that the anionic conductive material of the present invention has excellent thermal stability.

From the above-described experimental results, it can be seen that the anionic conductive electrolyte membrane of the present invention can maintain a level equal to or higher than that of the existing commercialized polymer electrolyte membrane in terms of thermal stability, mechanical stability, permeability, film forming ability, and the like.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, Various changes and modifications will be possible.

Claims (11)

An anionic conductive electrolyte membrane comprising an anionic conductive polymer represented by the following formula (1)
[Chemical Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ' and R ₄ 'are the same or different from each other and represent -H, -F, -Cl, -Br, An alkyl group, a fluoroalkyl group, -C ₆ H ₅ , - (C ₆ H ₄ ) _n -C ₆ H ₅ , -C ₆ F ₅ , - (C ₆ F ₄ ) _n -C ₆ F ₅ , R ₃ 'is selected from an anionic conductive group comprising an imidazolium group, a guanidine hydrochloride group or a phosphonium group, X ₁ and X ₂ are selected from -O-, -CO- , -SO ₂ -, and n is a real number between 0 and 1, representing the content in%.
The method according to claim 1,
In the anionic conductive polymer copolymer, the repeating unit of R ₃ 'is 1 to 99 mol%.
The method according to claim 1,
The imidazole (imidazolium) groups, guanidine hydrochloride (guanidine hydrochloride) or phosphonium group (phosphonium) groups are _{-H, - (CH 3) n} , - (C 6 H 5) n, -F, - (CF 3 _{) n, - (C 6 F} 5) n, -Cl, - (CCl 3) n, - (C 6 Cl 5) n, -Br, - (CBr 3) n, - (C 6 Br 5) n of Wherein at least one of the anion-conducting electrolyte membrane and the anion-conducting electrolyte membrane is introduced.
The method according to claim 1,
Wherein the membrane has a thickness of 5 to 500 占 퐉 in a non-humidified state.
A step of brominating an aromatic hydrocarbon-based polymer represented by Formula 2 below;
(2)

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₁ ', R ₂ ', R ₃ 'and R ₄ ' are the same as or different from each other and represent -H, -F, -Cl, -Br , -I, an alkyl group, a fluorine group, a -C ₆ H _5, - consisting of _{(C 6 F 4) n -C} 6 F 5 - (C 6 H 4) n -C 6 H 5, -C 6 F 5, X ₁ and X ₂ are selected from -O-, -CO-, and -SO ₂ -, and n is a real number between 0 and 1, representing the weight percentage contained in the aromatic hydrocarbon-based polymer.
A first substitution step of substituting the anion-conducting group at the brominated position of the brominated aromatic hydrocarbon-based polymer;
A film forming step of forming a precursor film with the substituted aromatic hydrocarbon-based polymer; And
And a second replacement step of replacing the precursor film with a hydroxyl group.
6. The method of claim 5,
Wherein the bromination step is performed by reacting the aromatic hydrocarbon-based polymer with N-bromosuccinimide (NBS) or a bromine-solution.
6. The method of claim 5,
Wherein the first substitution step is carried out by replacing one or more substances selected from the group consisting of an imidazolium group, a guanidine hydrochloride group and a phosphonium group with bromine of the aromatic hydrocarbon-based polymer A method for producing an anionic conductive electrolyte membrane. 6. The method of claim 5,
Casting the aromatic hydrocarbon-based polymer solution substituted with the anion conductive group obtained in the first substitution step on a flat plate; A primary drying step of removing the solvent at a temperature of 30 ° C to 100 ° C in the cast state to obtain a precursor film; And a secondary drying step of treating the precursor film under a temperature condition of 50 ° C to 200 ° C and a vacuum condition.
An energy storage device comprising an anionically conductive electrolyte membrane according to any one of claims 1 to 4 or an anionically conductive electrolyte membrane produced by the production method according to any one of claims 5 to 8.
10. The method of claim 9,
Wherein the energy storage device is a redox flow cell, a direct borohydride fuel cell (DBFC), or a solid alkaline fuel cell (SAFC).
A water treatment apparatus comprising an anionically conductive electrolyte membrane according to any one of claims 1 to 4 or an anionically conductive electrolyte membrane produced by the production method according to any one of claims 5 to 8.

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