KR101728839B1 - Polymer electrolyte compound and method for preparing the same, polymer electrolyte membrane using the same and electrochemical device including the membrane - Google Patents

Abstract

In embodiments of the present invention, a polymer electrolyte compound comprising a crosslinking functional group and a pyridine-containing functional group and a process for producing the same are disclosed. Also disclosed are a polymer electrolyte membrane and an electrochemical device using the same. The polymer electrolyte membrane composed of the polymer electrolyte compound exhibits long-term durability and exhibits equivalent levels of phosphoric acid absorption and ion conductivity as compared with the conventional polymer electrolyte membrane comprising pyridine-containing polymer compounds.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer electrolyte membrane and a method of preparing the same, a polymer electrolyte membrane comprising the polymer electrolyte compound, and an electrochemical device comprising the polymer electrolyte membrane,

TECHNICAL FIELD The present invention relates to a polymer electrolyte compound and a method for producing the same, a polymer electrolyte membrane using the polymer electrolyte compound, and an electrochemical device including the polymer electrolyte membrane.

Polymer electrolyte compounds containing pyridine in the main chain or side chain are well known. These types of compounds are used as polymer electrolyte membrane materials in fuel cells, electrolytic apparatuses, and the like, and are often doped with phosphoric acid, such as phosphoric acid doped polybenzimidazole.

Examples of such polymer electrolyte compounds are as follows.

For example, Non-Patent Document 1 discloses polymer electrolyte compounds having the following chemical formula.

[Chemical Formula 1]

(2)

Non-patent documents 2 to 4 also disclose, for example, polymer electrolyte compounds having the following chemical formulas.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

However, according to the study results of the present inventors, conventional polymer electrolyte compounds are still unsatisfactory in terms of long term durability.

For example, in the case of the compound of Formula 3, the alkyl chain is crosslinked, which can be rapidly degraded in the presence of activated oxygen species (e.g., OH * produced in a fuel cell).

Further, it is still necessary to study a polymer electrolyte membrane having excellent mechanical properties, thermal properties, acid (particularly phosphoric acid) water absorption, and proton conductivity.

US 8026339

Gourdoupi, N., J. K. Kallitsis, et al. (2009). J. Pow. Sour 195: 170-174. Morfopoulou, C., A. K. Andreopoulou, et al. (2011). J, Polym. Sci .: Part A: Polymer Chemistry 49: 4325-4334. Morfopoulou, C. I., A. K. Andreopoulou, et al. (2013). J. Mater. Chem. A 1: 1613-1622. Papadimitriou, Konstantinia D .; Geormezi, Maria; Neophytides, Stylianos G .; Kallitsis, Joannis K., Journal of Membrane Science (2013), 433, 1-9. Yang et al., Fuel Cells, 2014, 14, 7-15. ChemSus Chem, 2013, 6: 275-282.

In an exemplary embodiment of the present invention, in one aspect, it has a long term durability and can exhibit a phosphate absorption and proton conductivity equal to or higher than that of conventional pyridine-containing polymer compounds, Polymer electrolyte membrane and a polymer electrolyte membrane having excellent properties, a method for producing the same, and an electrochemical device using the same.

In one embodiment of the present invention, there is provided, in one aspect, a crosslinked compound that is a polymer having a repeating unit of the following formula (6) or (7).

[Chemical Formula 6]

(7)

Wherein A, B, D and E each independently represent a single bond, O, SO ₂ , C═O, CH ₃ -C -CH ₃ , Ph (phenyl) -P═O, S, N , CH ₃ -C- alkyl may be (wherein alkyl is a C1-C10 alkyl).

R 1, R 2, R 3 and R 4 in the above-mentioned formula (6) are each independently any one of the following (1), (2) and (3)

(1) hydrogen (H);

(2) a crosslinking group;

(3) a hetero atom containing group,

The crosslinking functional group forms a crosslinking point, -CH ₂ -CP-CH ₂ -, where CP is an imidazole, benzimidazole, 1,2,3 A group consisting of 1, 2, 3-triazole, 1,2,4-triazole, tetrazole, and 2-phenyltetrazole .

R5 in the above formula (7) is any one of the following (1), (2) and (3).

(1) hydrogen (H);

(2) a crosslinking group;

(3) a hetero atom containing group,

Wherein the crosslinking functional group forms a crosslinking point, -CP-, wherein CP is selected from the group consisting of imidazole, benzimidazole, 1,2,3-triazole (1, 2, 3-triazole, 1, 2, 4-triazole, tetrazole, and 2-phenyltetrazole.

The molar ratio of the hetero atom containing functional group to the crosslinking functional group in the polymer having the repeating unit of the above formula (6) or the repeating unit of the above formula (7) is from 30: 1 to 1 : 10.

In another embodiment of the present invention, another aspect provides a polymer electrolyte membrane comprising the polymer electrolyte compound.

Further, in one embodiment of the present invention, in another aspect, there is provided an electrochemical device including the polymer electrolyte membrane, such as a fuel cell or an electrolytic device.

Further, in one embodiment of the present invention, there is provided a method for producing a polymer electrolyte membrane, comprising: performing hallomethylation of an aromatic polymer; And reacting the halomethylated aromatic polymer with a heteroatom-containing compound and an imidazolium-crosslinking functional group-containing compound. In one embodiment, the imidazolium crosslinking functional group-containing compound is selected from the group consisting of imidazole, benzimidazole, 1,2,3-triazole, 1,2, 4-triazole, tetrazole, 2-phenyltetrazole, and the like.

The polymer electrolyte compound of the exemplary embodiments of the present invention and the polymer electrolyte membrane using the polymer electrolyte membrane have long term durability and have a phosphoric acid absorption rate and proton conductivity equal to or higher than that of the conventional pyridine- And has excellent mechanical and thermal properties. The polymer electrolyte membrane can be usefully used as a polymer electrolyte membrane of an electrochemical device such as a fuel cell or an electrolyzer, and particularly as a polymer electrolyte membrane of a high temperature PEMFC (High Temperature PEMFC).

Hereinafter, exemplary embodiments of the present invention will be described in detail.

In one embodiment of the present invention, there is provided a crosslinked compound which is a polymer having a repeating unit of the following formula (6).

 [Chemical Formula 6]

Wherein A, B, D and E each independently represent a single bond, O, SO ₂ , C═O, CH ₃ -C -CH ₃ , Ph (phenyl) -P═O, S, N , CH ₃ -C- alkyl may be (wherein alkyl is a C1-C10 alkyl).

R 1, R 2, R 3 and R 4 in the above-mentioned formula (6) are each independently any one of the following (1), (2) and (3)

(1) hydrogen (H);

(2) a crosslinking group;

(3) a hetero atom containing group,

The crosslinking functional group forms a crosslinking point, -CH ₂ -CP-CH ₂ -, where CP is an imidazole, benzimidazole, 1,2,3 A group consisting of 1, 2, 3-triazole, 1,2,4-triazole, tetrazole, and 2-phenyltetrazole .

The molar ratio of the hetero atom containing functional group to the crosslinking functional group in the polymer having the repeating unit of the above formula (6) or the repeating unit of the above formula (7) is from 30: 1 to 1 : 10.

Also, in one embodiment of the present invention, there is provided a crosslinked compound which is a polymer having a repeating unit represented by the following formula (7).

(7)

R5 in the above formula (7) is any one of the following (1), (2) and (3).

(1) hydrogen (H);

(2) a crosslinking group;

(3) a hetero atom containing group,

Wherein the crosslinking functional group forms a crosslinking point, -CP-, wherein CP is selected from the group consisting of imidazole, benzimidazole, 1,2,3-triazole (1, 2, 3-triazole, 1, 2, 4-triazole, tetrazole, and 2-phenyltetrazole.

In the polymer having the repeating unit represented by the above formula (7), the molar ratio of the hetero atom-containing functional group to the crosslinking functional group is from 30: 1 to 1:10.

The details will be described in detail below. Imidazole leads to scission of the main chain when hydrolyzed, thereby lowering the molecular weight and reducing the stability (thermal and mechanical stability) of the film. For reference, the hydrolysis can take place not only in basic conditions but also in acidic conditions.

In exemplary embodiments of the present invention imidazolium is included in the side chain as a crosslinking functional group and also includes a heteroatomic functional group such as a pyridine functional group in the side chain. Accordingly, degradation is prevented, deterioration does not greatly affect the overall stability, and life time can be improved.

On the other hand, by introducing heteroatom-containing functional groups such as pyridine, the crosslinking functional group containing imidazolium can increase the acid (particularly phosphoric acid) absorption rate, increase the proton conductivity, and improve the mechanical and thermal properties of the membrane .

When the crosslinking functional group is introduced and cross-linked, the mechanical stability can be increased by reducing the creep and the like.

For reference, the acid uptake (which is related to proton conductivity) is generally in a trade-off relationship to thermal mechanical stability. That is, as the acid absorption rate increases, the thermal mechanical stability decreases. As the acid absorption rate decreases, the thermal mechanical stability tends to increase. According to the embodiments of the present invention, the acid absorption rate and the thermal mechanical stability are optimized. )can do.

The molar ratio of hetero atom containing group to the crosslinking group of the heteroatom-containing functional group in the polymer of the exemplary embodiments (polymer having repeating units of formula [6] or [7]) is 30 : 1 to 1:10. That is, any repeating unit of the polymer contains at least a hetero atom-containing functional group and / or a crosslinking functional group, and the polymer has the above-mentioned molar ratio as a whole.

When a hetero atom (e.g., nitrogen) -containing functional group (for example, pyridine) is contained in a larger amount than the above range, the acid uptake becomes too large during acid-doping such as phosphoric acid and the mechanical and thermal characteristics become unstable have. On the other hand, if the content of the crosslinking functional group is larger than the above range, the manufacturing process becomes complicated and the acid uptake is lowered, so that the polymer electrolyte membrane (particularly, the polymer electrolyte membrane of the high temperature polyelectrolyte membrane fuel cell) The applicability may be limited.

On the other hand, in the illustrative embodiment, the polymer ([Chemical Formula 6] or a polymer having a repeating unit of Formula 7]) is CH ₂ - there is to include hetero atom bond (CH ₂ -Hetero atom bond), wherein per repeating unit CH ₂ - the hetero atom to which the average number of _{(CH 2 -Hetero atom bond) [} average number of CH 2 -Hetero atom bond per repeat unit] is from 0.05 to 3 is preferred.

If it is smaller than 0.05, the substitution effect of the functional group is insignificant. If it is larger than 3, the synthesis becomes very difficult and the mechanical thermal stability may be greatly deteriorated. For reference, as described above, too much heteroatom-containing functional groups may lower the mechanical and thermal stability.

In one exemplary embodiment, the crosslinker or crosslinking agent is -CH ₂ -CP-CH ₂ - for Formula 6 and -CP- for Formula 7.

Wherein CP is selected from the group consisting of imidazole, benzimidazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,4- triazole, tetrazole, and 2-phenyltetrazole.

In one exemplary embodiment, the cross-linking functional group CP is cross-linked at the position of the nitrogen atom and may be substituted at an atom other than nitrogen. The substituent may be, for example, hydrogen, a methyl group, an ethyl group or the like, or may be any one of the following.

In one exemplary embodiment, the cross-linking functional group may be a 2-substituted imidazole, or a 2-substituted benzimidazole, wherein the 2-substitutent is A C1-C10 alkyl group, a pyridine, a phenyl group, or a substituted phenyl group.

In one exemplary embodiment, the heteroatom-containing functional group may be CH ₂ -NH ₂ -4-pyridine, CH ₂ -O-R 5, CH ₂ -S-R 6, and R 5 and R 6 are It can be either.

In a non-limiting example of one, and in the compound of [Chemical Formula 6] A is CH ₃ -C-CH _3, or a single bond, B is O, D is SO _2, E may be a O, and also hetero The atom containing functional group is CH ₂ -NH ₂ -4-pyridine or CH ₂ -O-pyridine and the cross-linking group is -CH ₂ -CP-CH ₂ - wherein CP is imidazole ( imidazole), either R1 or R2 is a pyridine-containing functional group and the other is a crosslinking group, and R3, R4 may be hydrogen.

Preferably, the pyridine containing functional group may be 4-aminopyridine.

In one non-limiting example, the polyelectrolyte compound according to embodiments of the present invention may be, for example, a compound of the following formula:

[Chemical Formula 8]

According to another embodiment of the present invention, there is provided a polymer electrolyte membrane comprising the polymer electrolyte compound.

In one embodiment, the polyelectrolyte membrane may have a phosphate absorption of 50 to 500%. The proton conductivity of the polyelectrolyte membrane may be 1 to 70 mS / cm at 20 to 200 캜.

The polymer electrolyte membrane can be used as an electrochemical device or the like, and can be particularly useful as a polymer electrolyte membrane of a fuel cell or an electrolyzer, and particularly as a polymer electrolyte membrane of a high temperature PEMFC.

Meanwhile, in one embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: performing hallomethylation of an aromatic polymer; And reacting the halomethylated aromatic polymer with a heteroatom-containing compound and an imidazolium-crosslinking functional group-containing compound. Herein, the imidazolium crosslinking functional group is, for example, imidazole, benzimidazole, 1,2,3-triazole, 1,2,4-triazole, (1, 2, 4-triazole), tetrazole, and 2-phenyltetrazole. The hetero atom-containing compound may be, for example, a pyridine compound.

In one exemplary embodiment, the polymer having repeating units of formula (6) is subjected to chloromethylation, and the polymer having repeating units of formula (7) is subjected to bromomethylation.

Hereinafter, the manufacturing process and results will be described in detail by way of examples and experiments, but the present invention is not limited to the following description.

Of polysulfone polymer Chloromethylation

Polysulfone polymer (Solvay, Udel P-3500) (10.00 g, 22.6 mmol) was dissolved in CHCl ₃ 500 ml.

A solution of stannic chloride (9.4 ml, 4.52 mmol) in methylene chloride with trimethylchlorosilane (24.55 g, 225.60 mmol), paraformaldehyde (6.785 g, 226.0 mmol) Was added.

The temperature was increased to 50 < 0 > C and controlled with an internal thermometer. The reaction mixture was stirred at 50 < 0 > C for 72 hours.

The resulting polymer was precipitated in 1200 ml of ethanol and stirred for at least 2 hours. The polymer was then washed with 1200 ml ethanol for at least 4.5 hours and finally vacuum dried at 60 < 0 > C. The polymer yield was 88-96% and the degree of chloromethylation was 90-95% (measured by proton nuclear magnetic resonance spectroscopy).

Comparative Example  One

4-Aminopyridine (0.58 g, 6.049 mmol) and chloromethylated polysulfone (3.00 g, 6.110 mmol, chloromethylation degree 90%) were dissolved in chloroform (2.4 ml) and N, N- Was mixed with N, N-dimethylformamide (34.0 ml) and stirred at 40 ° C for 20 hours. The solvent was evaporated at 60 < 0 > C for 2 hours and at 60 [deg.] C under vacuum for 14 hours.

The obtained polymer was dissolved in dimethylsulfoxide to prepare a 15 wt. % Solution. The solution was filtered with a syringe filter (pore size 45 mu m) and cast on a glass plate using a 400 mu m doctor blade. The membrane was dried at 80 ° C for 2 hours and finally dried at 80 ° C under vacuum for 20 hours. The resulting membrane was washed with deionized water for 12 hours and dried at 60 DEG C under vacuum for 24 hours.

Example  One

4-Aminopyridine (0.499 g, 5.196 mmol) and imidazole (0.040 g, 0.577 mmol) were added to the above chloromethylated polysulfone (3.00 g, 6.110 mmol, chloromethylation degree 90% Was mixed with chloroform (2.7 ml) and N, N-dimethylformamide (38.7 ml), and the mixture was stirred at 40 ° C for 20 hours.

The solution was filtered with a syringe filter (pore size 45 mu m) and cast using petri dishes. The solvent was evaporated at 60 < 0 > C for 3 hours and finally at 60 [deg.] C in vacuo for 20 hours. The resulting membrane was washed with deionized water for 12 hours and dried at 60 DEG C under vacuum for 24 hours.

Example  2

4-aminopyridine (0.569 g, 5.925 mmol) and imidazole (0.081 g, 1.185 mmol) were added to the above chloromethylated polysulfone (3.50 g, 7.128 mmol, chloromethylation degree 95% Was mixed with chloroform (3.2 ml) and N, N-dimethylformamide (45.4 ml), and the mixture was stirred at 40 ° C for 24 hours. The solution was filtered with a syringe filter (pore size 45 mu m) and cast using petri dishes. The solvent was evaporated at 60 < 0 > C for 1 hour and finally at 60 [deg.] C in vacuo for 24 hours. The obtained membrane was washed with deionized water for 12 hours and dried at 60 캜 under vacuum for 17 hours.

Example  3

4-aminopyridine (0.293 g, 3.047 mmol) and imidazole (0.110 g, 1.596 mmol) were added to the above chloromethylated polysulfone (3.00 g, 6.110 mmol, chloromethylation degree 95% Was mixed with N, N-dimethylacetamide (41.5 ml) and stirred at 40 ° C for 24 hours. The solution was filtered with a syringe filter (pore size 45 mu m) and cast using petri dishes. The solvent was evaporated at 40 < 0 > C for 2 hours and finally at 40 [deg.] C in vacuo for 14 hours. The resulting membrane was washed with deionized water for 12 hours and dried at 60 DEG C under vacuum for 24 hours.

The following table shows the molar ratio (molar ratio) of 4-aminopyridine: imidazole to the reaction solvent of each of the examples [reaction solvent of chloromethylated polysulfone (chloromethylated degree 90-95%) and 4-aminopyridine / imidazole] ) (according to the reagent feed), and the gel content (DMSO, RT).

In addition, the table shows phosphoric acid uptake (PA uptake) at 30 ° C and 80 ° C, and proton conductivity at 160 ° C in Examples 2 and 4.

Comparative Example 1
(Comparative example 1) Example 1
(Example 1) Example 2
(Example 2) Example 3
(Example 3) Reaction solvent DMF: CHCl ₃ DMF: CHCl ₃ DMF: CHCl ₃ DMAc 4-aminopyridine
: Molar ratio 1: 0 9: 1 5: 1 2: 1 Gel content
(DMSO, RT) 0 % 56% 100% 100% PA absorption rate (30 DEG C)
[Proton conductivity at 160 占 폚] 285% 215%
[50 mS / cm] 231%
[55 mS / cm] 105%
[20 mS / cm] PA absorption rate (80 DEG C)
[Proton conductivity at 160 占 폚] 457% 295%
[64 mS / cm] 283%
[N // A] 127%
[39 mS / cm]

As can be seen from the above, when imidazole was added, the examples became crosslinked membranes. This is known from the gel content.

For reference, the gel content should be as high as possible. The higher the gel content, the lower the solubility and insoluble when the gel content is 100%. In relation to this, the gel content increases as the crosslinking amount increases.

However, when the crosslinking amount is increased (that is, when the crosslinking group substitution is increased), the basic sites are reduced and the swelling of the polymer electrolyte membrane is limited when the acid is doped, The absorption rate can be reduced (the higher the absorption rate of phosphoric acid is, the better). In the membranes of the examples, the absorption rate of phosphoric acid decreased as the gel content increased.

Therefore, it is preferable to determine the proper proportions of the pyridine group and the crosslinking group, which can contain the pyridine group as much as possible and have a high gel content.

As a comparative example of the membrane of the above embodiments, the doping level or proton conductivity of the conventional polymer electrolyte compound is as follows.

(1) 85% phosphoric acid (PA) doped polybenzimidazole has a PA absorption ratio of 345% (high molecular weight PBI: 78,000 g / mol) and 411% (intermediate molecular weight PBI: 37,000 g / mol). (Non-Patent Document 5)

(2) The pyridine-containing blend film (PPyPO / PPy (50) coPSF 50/50) has a doping level of 200% at 80 캜 (Non-Patent Document 1)

(3) The proton conductivity of pyridine-containing polymer tough (Terp.IX) [193% PA and 170% PA doping] is about 65-70 mS / cm at 160 占 폚.

(4) A PA-doped polysulfone-based membrane having aliphatic amine or propylated imidazole in its side chain has a proton conductivity of about 4-25 mS / cm at 150 ° C (Patent Document 1)

(5) The anhydrous proton conductivity of acid-doped SO ₂ PBI and its crosslinked counterparts is about 60-95 mS / cm at 160 ° C for various materials (Non-Patent Document 6)

(6) PA doping meta-PBI (not crosslinked) has a proton conductivity of about 140 mS / cm at 160 캜 (Non-Patent Document 5).

For reference, the proton conductivity at 160 ° C of the membrane of Example 3, the weight gain during doping, and the tensile strength (not crosslinked) of a commercially available meta-PBI membrane (not crosslinked) obtained from Daposy tensile strength, and Young modulus were measured. Table 2 shows the measurement results.

Whether it is cross-linked
(Crosslinked) Proton conductivity
(proton conductivity) Weight gain during doping (%) The tensile strength
(tensile strength) Young Modulus
(Young modulus)
Example 3 Bridging (Yes) 39 mS / cm 122 ± 5 11.9 ± 2.7 222 ± 41 Meta-PBI (Daposy) No bridging (No) 13 mS / cm 150 6.8 ± 1.1 134 ± 16

As can be seen from the results in Table 2, the membrane of Example 3 has higher conductivity than the conventional meta-PBI membrane and has a lower phosphoric acid uptake rate, thus exhibiting improved tensile strength and Young's modulus.

From the above, it can be seen that the membrane made of the crosslinked polymer electrolyte compound of the embodiments of the present invention exhibits a doping level and ion conductivity equal to or higher than that of the conventional polymer electrolyte membrane. In addition, the film is excellent in mechanical and thermal properties and exhibits long-term durability.

Claims (12)

Is a crosslinking polymer having a repeating unit of the following formula (6) or (7).
[Chemical Formula 6]

(7)

Wherein A, B, D and E each independently represent a single bond, O, SO ₂ , C═O, CH ₃ -C -CH ₃ , Ph (phenyl) -P═O, S, N , it is CH ₃ -C- alkyl (wherein alkyl is an alkyl C1-C10).
R 1, R 2, R 3 and R 4 in the above-mentioned formula (6) are each independently any one of the following (1), (2) and (3)
(1) hydrogen (H);
(2) a crosslinking point;
(3) a hetero atom containing group which is CH ₂ -NH ₂ -4-pyridine or CH ₂ -O-pyridine,
The crosslinking point is -CH ₂ -CP-CH ₂ -, which is a crosslinking point connecting the polymer chain represented by the repeating unit of formula (6), wherein CP is imidazole, Benzimidazole, 1, 2, 3-triazole, 1,2,4-triazole, tetrazole, 2, R2, R3 and R4 are not a monovalent group when R1, R2, R3 and R4 are cross-linking points.
R5 in the above formula (7) is any one of the following (1), (2) and (3).
(1) hydrogen (H);
(2) a crosslinking point;
(3) a hetero atom containing group which is CH ₂ -NH ₂ -4-pyridine or CH ₂ -O-pyridine,
Wherein the crosslinking point is -CP-, a crosslinking point connecting the polymer chain represented by the repeating unit of formula (7), wherein CP is imidazole, benzimidazole, , 1,2,3-triazole, 1,2,4-triazole, tetrazole, 2-phenyltetrazole (2, 3, -phenyltetrazole), and when R5 is a point of crosslinking, R5 is not a monovalent group.
The molar ratio of hetero atom containing group to the crosslinking point of the heteroatom-containing functional group in the polymer having the repeating unit of the above formula (6) or the repeating unit of the formula (7) is from 30: 1 to 1 : 10.
The method according to claim 1,
The polymer CH ₂ - hetero atom bond (CH ₂ -Hetero atom bond) and including a repeating CH ₂ per unit - the average number of hetero atom _{(CH 2 -Hetero atom bond) [} average number of CH 2 -Hetero atom bond per repeat unit] is from 0.05 to 3.
The method according to claim 1,
Wherein the CP is substituted at an atomic position other than nitrogen, and the substituent is hydrogen, a methyl group, an ethyl group, or any one of the following.

The method according to claim 1,
The CP is a 2-substituted imidazole or a 2-substituted benzimidazole wherein the 2-substitutent is a C1-C10 alkyl group, a pyridine, a phenyl group, (phenyl) or a substituted phenyl group.
delete The method according to claim 1,
A is CH ₃ -C-CH _3, or a single bond,
B is O,
D is SO ₂ ,
E is O,
Wherein the point of crosslinking is -CH ₂ -CP-CH ₂ -, wherein CP is imidazole.
delete A polymer electrolyte membrane comprising the polymer electrolyte compound according to any one of claims 1 to 4.
9. The method of claim 8,
Wherein the polyelectrolyte membrane has a phosphoric acid absorption rate of 50 to 500%.
An electrochemical device comprising the polymer electrolyte membrane according to claim 8.
11. The method of claim 10,
Wherein the electrochemical device is a fuel cell or an electrolyser.
A process for producing a polymer electrolyte compound according to any one of claims 1 to 4,
Performing a hallomethylation of an aromatic polymer; And
Reacting the halomethylated aromatic polymer with a heteroatom-containing compound which is CH ₂ -NH ₂ -4-pyridine or CH ₂ -O-pyridine and an imidazolium crosslinking functional group-containing compound ≪ / RTI >