KR102293505B1 - Solid electrolyte membrane comprising porous organic polymer improved in hydrogen ion conductivity, and method of preparing the same - Google Patents

Abstract

The present invention relates to a solid electrolyte membrane comprising a porous organic polymer having improved hydrogen ion conductivity and a method for manufacturing the same, and more particularly, to an electrode electrolyte assembly in a proton exchange membrane fuel cell (PEMFC). , MEA), a porous organic polymer with improved hydrogen ion conductivity that can be used as a solid electrolyte, a solid electrolyte membrane comprising the same, and a method for manufacturing the same.
The present invention relates to a composition for a solid electrolyte comprising a porous organic polymer having improved hydrogen ion conductivity, a solid electrolyte membrane comprising the same, and a method for manufacturing the same. The electrolyte membrane is not only easy to synthesize, but also has remarkably high hydrogen ion conductivity and low activation energy, so it can be usefully used in a proton exchange membrane fuel cell.

Description

Solid electrolyte membrane comprising porous organic polymer improved in hydrogen ion conductivity, and method of preparing the same

The present invention relates to a solid electrolyte membrane comprising a porous organic polymer having improved hydrogen ion conductivity and a method for manufacturing the same, and more particularly, to an electrode electrolyte assembly in a proton exchange membrane fuel cell (PEMFC). , MEA), a porous organic polymer with improved hydrogen ion conductivity that can be used as a solid electrolyte, a solid electrolyte membrane comprising the same, and a method for manufacturing the same.

Nafion, developed by DuPont in the 1960s, has been used as a reference material in the field of proton exchange membrane fuel cells so far, and is a representative material that is being studied recently. Nafion shows a high hydrogen ion conductivity value of 0.1 S/cm under moisture conditions, but due to disadvantages such as performance degradation at high temperatures, research on alternative materials is being actively conducted.

On the other hand, porous organic polymers are a material that has been actively studied in recent years, and various structures with a large specific surface area are possible depending on the organic unit used for synthesis, and thus attracting attention in many fields. In particular, research on membrane manufacturing by mixing the material and various commercial polymers is being actively studied due to its high potential for application in various fields, but it is still at a basic stage.

Recently, studies have been conducted to utilize porous organic polymers as electrolyte materials for fuel cells, but studies have been conducted only on samples in powder form so far, and there are few examples that report their potential as electrolyte membranes by using them in the form of membranes. . In order to actually drive a fuel cell, since the electrolyte in the form of a membrane is much more useful, it is very important from the viewpoint of application of the fuel cell to convert the powder form of the porous organic polymer into the form of an electrolyte membrane.

Therefore, there is a demand for a new electrolyte membrane manufacturing technology that is stable to moisture and temperature while having high hydrogen ion conductivity using a porous organic polymer.

The present invention has been devised to solve the above problems. In the present invention, sulfuric acid is added to a porous organic polymer having high hydrogen ion conductivity and low activation energy, a solid electrolyte membrane based on the porous organic polymer, and a method for manufacturing the same would like to provide

The present invention, sulfuric acid; and a porous organic polymer skeleton represented by the following [Formula 1]: It provides a composition for a solid electrolyte comprising:

[Formula 1]

_{[C 8 H 5 O 2 ·} S 0. 47 O 1 .41] n · 0.5H 2 O

Wherein n is an integer from 1 to 100.

In addition, the present invention is the composition for the solid electrolyte; and a polymer film in which the composition for a solid electrolyte is dispersed.

The present invention relates to a composition for a solid electrolyte comprising a porous organic polymer having improved hydrogen ion conductivity, a solid electrolyte membrane comprising the same, and a method for manufacturing the same. The electrolyte membrane is not only easy to synthesize, but also has remarkably high hydrogen ion conductivity and low activation energy, so it can be usefully used in a proton exchange membrane fuel cell.

1 is a solid electrolyte composition (1S1M, 1S2M, and 1S3M) comprising a porous organic polymer skeleton impregnated with sulfuric acid in pores according to the present invention, and a polymer (PVDF) film in which the porous organic polymer skeleton is dispersed. Preparation of electrolyte membranes (1S50P, 1S60P) and solid electrolyte membranes (1S1MP, 1S2MP and 1S3MP) comprising a polymer (PVDF) film in which a composition for a solid electrolyte including a porous organic polymer skeleton impregnated with sulfuric acid in pores is dispersed diagrammed the process.
2A is water vapor isotherms of 1S, 1S1M, 1S2M, and 1S3M prepared according to the present invention, and (b) is a Nyquist plot at 90% RH of 1S1M and various temperature ranges. (Nyquist plots), (c) shows the activation energy of 1S1M, and (d) is a diagram showing the comparison result with the previously reported activation energies of the solid electrolyte (> 0.01 S cm-1 &< 0.35 eV). (1S1M: red, BUT-8 (Cr) a: black, 1ES: green, PCMOF2 1/2 (Pz): blue, TfOH @ MIL-101: magenta, PCMOF2 1/2 (tz): yellow, UiO-66 (SO ₃ H) ₂ : dark yellow, 1S: navy, HOF-GS-11: purple, H ⁺ @Ni ₂ (dobdc)(H ₂ O) ₂ (pH = 2.4): wine, H ⁺ @Ni ₂ ( dobdc)(H ₂ O) ₂ (pH = 1.8): olive, PCMOF2 _1/2 : dark cyan, Nafion: royal, BUT-8(Cr): orange, MIL-101-SO ₃ H: violet, Fe-CAT -5: pink, H ₃ PO4@MIL-10141: gray
3 (a) is an optical image of 1S60P prepared according to the present invention, (b) is water vapor isotherms of 1S50P, 1S60P, (c) is 1S60P at 90% RH and various temperature ranges are Nyquist plots, and (d) shows the activation energies of 1S50P and 1S60P.
4 is an image of 1S3MP manufactured according to the present invention.
Figure 5 shows the results of measuring the Nyquist plots (Nyquist plots) and their activation energy at 90% RH and various temperature ranges of 1S1MP, 1S2MP, and 1S3MP prepared according to the present invention (30 ℃: black, 40 °C:red, 50 °C:blue, 60 °C:magenta, 70 °C:navy, and 80 °C:purple).
6 is a graph showing the results of measuring the hydrogen ion conductivity for 10 days at 80 ℃ and 90% RH for 1S3MP prepared according to the present invention.
7 shows the IR spectrum results of 1S1M, 1S2M, and 1S3M prepared according to the present invention.
^{8 shows solid-state 13} C NMR spectra of compound 1S, 1S1M and 1S2M prepared according to the present invention.
9 is an SEM image of 1S1M, 1S2M, and 1S3M prepared according to the present invention (x 5,000, x 10,000, and x 25,000).
10 shows the IR spectrum results of compounds 1S, PVDF, and 1S50P and 1S60P prepared according to the present invention.
11 is an XPS analysis result of 1S50P and 1S60P manufactured according to the present invention.
12 is an EDX spectrum analysis result of 1S50P(a) and 1S60P(b) prepared according to the present invention.
13 is an SEM image of 1S50P manufactured according to the present invention.
14 is an SEM image of 1S60P manufactured according to the present invention.
15 shows IR spectrum results of 1S1MP, 1S2MP, and 1S3MP prepared according to the present invention.
16 is an XPS analysis result of 1S1MP, 1S2MP, and 1S3MP prepared according to the present invention.
17 is an EDX spectrum analysis result of 1S1MP(a), 1S2MP(b), and 1S3MP(c) prepared according to the present invention.
18 is an SEM image of 1S1MP(a), 1S2MP(b), and 1S3MP(c) manufactured according to the present invention.

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

In the present invention, sulfuric acid; and a porous organic polymer skeleton represented by the following [Formula 1]: provides a composition for a solid electrolyte comprising.

[Formula 1]

[C ₈ H ₅ O ₂ S _0.47 O _1.41 ]n 0.5H ₂ O

Wherein n is an integer from 1 to 100.

In this case, the porous organic polymer skeleton represented by the [Formula 1] may also be represented by the following [Formula 1S]:

[Formula 1S]

.

.

The composition for a solid electrolyte according to the present invention may be characterized in that the porous organic polymer skeleton represented by the above [Formula 1] is dispersed in a sulfuric acid solution of a predetermined concentration containing the sulfuric acid.

In addition, the composition for a solid electrolyte according to the present invention may be characterized in that sulfuric acid is impregnated in the pores of the porous organic polymer skeleton represented by the above [Formula 1].

At this time, the molar concentration of the sulfuric acid solution is preferably 1 to 5M.

The sample of the composition for a solid electrolyte according to the present invention may exhibit a hydrogen ion conductivity of ^{1.92×10 −2} S/cm to 2.35×10 ⁻² S/cm in a temperature range of 30° C. to 70° C. under 90% relative humidity.

In addition, in the present invention, the composition for a solid electrolyte; and a polymer film in which the composition for a solid electrolyte is dispersed; provides a solid electrolyte membrane comprising.

At this time, the polymer film is, for example, polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide (PA), cellulose, polyvinyl chloride (PVC) And it may be selected from the group consisting of polyvinyl alcohol (PVA), preferably polyvinylidene fluoride (PVdF).

^{The solid electrolyte membrane according to the present invention may exhibit a hydrogen ion conductivity of 4.48×10 −3} S/cm to 2.13×10 ⁻² S/cm at a temperature of 80° C. and 90% relative humidity, and an activation energy of 0.039 eV to 0.082 eV. can represent

In addition, the present invention provides a method for preparing a composition for a solid electrolyte comprising the step of dispersing a porous organic polymer skeleton represented by the following [Formula 1] in a sulfuric acid solution of a predetermined concentration:

[Formula 1]

[C ₈ H ₅ O ₂ S _0.47 O _1.41 ]n 0.5H ₂ O

Wherein n is an integer from 1 to 100.

According to the present invention, drying the porous organic polymer skeleton represented by [Formula 1] dispersed in the sulfuric acid solution to obtain a porous organic polymer skeleton powder impregnated with sulfuric acid in the pores; may further include .

In addition, the molar concentration of the sulfuric acid solution may be 1 to 5M.

In addition, in the present invention, the step of dispersing the porous organic polymer skeleton represented by the following [Formula 1] in a sulfuric acid solution of a predetermined concentration; drying the porous organic polymer skeleton represented by [Formula 1] dispersed in the sulfuric acid solution to obtain a porous organic polymer skeleton powder impregnated with sulfuric acid in pores; dispersing the obtained porous organic polymer skeleton powder in a polymer solution; and forming a membrane by casting a polymer solution in which the porous organic polymer framework powder is dispersed; provides a method for manufacturing a solid electrolyte membrane comprising:

[Formula 1]

[C ₈ H ₅ O ₂ S _0.47 O _1.41 ]n 0.5H ₂ O

Wherein n is an integer from 1 to 100.

At this time, the polymer solution is polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide (PA), cellulose, polyvinyl chloride (PVC) and polyvinyl. It may be selected from the group consisting of alcohol (PVA), preferably polyvinylidene fluoride (PVdF).

Hereinafter, specific examples will be described for better understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the scope of the present invention is not limited by the following examples.

< Example >

Preparation of compounds, compositions for solid electrolytes, and solid electrolyte membranes

Preparation Example 1 Compound _{1 ([C 8 H 5 O} 2] n · 0.45H 2 O) and the compound _{1S ([C 8 H 5 O} 2 · S 0. 47 O 1 .41] n · 0.5H 2 O) synthesis of

Compound 1 and Compound 1S were synthesized as follows according to the method described in the conventional literature (Angew . Chem . Int . Ed. 2016 , 55, 16123).

First, 0.5 g of phloroglucinol (3.96 mmol) and 0.4 g of terephthaldehyde (2.98 mmol) were added to 15 mL of 1,4-dioxane and dissolved with a sonicator to make a transparent solution. This solution was transferred to a 35 mL pyrex cell for microwave, 1 mL of 35% HCl was added, and the inlet was closed with a PTFE cap. Then, after reacting with a microwave reactor (CEM Discover) at 220 °C for 2 hours, the product was stirred in 150 mL of THF for 1 hour and filtered. Then, it was washed with THF and methanol, dried in an oven at 100 ° C., and then the solvent molecules present in the internal cavity were removed at 120 ° C. for 10 hours using a vacuum pump to synthesize compound 1, and the final yield was about 94%. it was Next, 12 mL of methylene chloride and 100 mg of Compound 1 were added to a 100 mL round-bottom flask and stirred for 1 hour. The flask was placed in a bucket of ice water, and 1.2 mL of chlorosulfonic acid was slowly added dropwise and reacted for 4 days. Then, the product was poured into a 1000 mL beaker filled with ice and water, stirred for 6 hours, filtered, washed with water and methanol until pH 7, and dried in an oven at 100° C. overnight. Then, compound 1S was synthesized by removing solvent molecules present in the inner cavity at 120° C. for 10 hours.

Preparation Example 2. Preparation of compositions for solid electrolytes (1S1M, 1S2M, 1S3M)

200 mg of porous organic polymer compound 1S was placed in 50 mL of 1M, 2M, and 3M sulfuric acid aqueous solution contained in a 70 mL vial, respectively, and the polymer was dispersed through ultrasonic grinding and stirring for 6 hours. After collecting the solids through centrifugation, they were dried under nitrogen and then dried in an oven at 100 ° C. for 12 hours. Compositions for solid electrolytes 1S1M (concentration of aqueous sulfuric acid solution used 1M), 1S2M (concentration of aqueous sulfuric acid solution used 2M), 1S3M ( A concentration of the aqueous sulfuric acid solution used was prepared (3M).

Preparation Example 3. Preparation of Solid Electrolyte Membrane

(1) 1S50P, 1S60P (50, 60 means the mass percentage of compound 1S in the solid electrolyte membrane)

Add 250 mg (for 1S50P) or 300 mg (for 1S60P) of porous organic polymer 1S to 5 mL of DMF in which 250 mg (for 1S50P) or 200 mg (for 1S60P) of PVDF is dissolved, and uniformly through stirring. to be dispersed. The dispersion solution was poured on a circular glass plate having a diameter of 8 cm, and DMF was allowed to evaporate as much as possible at 40 °C for 48 hours, and then the formed membrane was removed to prepare solid electrolyte membranes 1S50P and 1S60P.

(2) 1S1MP, 1S2MP, 1S3MP (At this time, the mass percentage for the solid electrolyte membrane of 1S1M, 1S2M and 1S3M is set to 60%)

300 mg of 1S1M, 1S2M, or 1S3M of the porous organic polymer mixed with sulfuric acid (composition for a solid electrolyte according to the present invention) was placed in 5 mL of DMF in which 200 mg of PVDF was dissolved and uniformly dispersed through stirring. The dispersion solution was poured on a circular glass plate with a diameter of 8 cm, and DMF was allowed to evaporate as much as possible at 40 °C for 48 hours, and then the formed membrane was removed to prepare solid electrolyte membranes 1S1MP, 1S2MP, and 1S3MP.

test example

Test Example 1. Confirmation of the structure and characteristics of a composition for a solid electrolyte and a solid electrolyte membrane

(1) Compound 1S was treated with a non-volatile inorganic acid (1M, 2M, 3M H ₂ SO ₄ aqueous solution) to prepare compositions 1S1M, 1S2M and 1S3M for solid electrolyte impregnated with _{H 2} SO _{4 .} In order to confirm the impregnation of sulfuric acid, element analysis (EA) of the sample was performed, and the results are shown in Table 1 below.

As shown in Table 1, it was found that the sulfur content in the sample increased as the concentration of _{H 2} SO _{4 increased.} In the infrared (IR) data, _{the sample impregnated with H 2} SO ₄ showed a broader peak than compound 1S in the range of 3300-2800 cm -1 , which is due to the additional hydrogen bonding between the proton source and the water molecule in the backbone. (Fig. 7). In the samples to which sulfuric acid was added (1S2M and 1S3M), S=O asymmetric and symmetric stretching peaks were ^{observed at 1121 and 1020 cm -1} , and SO stretching peaks were observed at ^{875 cm -1 .} Structural integrity after impregnation ^{was confirmed by solid-state 13} C NMR (Fig. 8). All peaks observed in the spectrum of Compound 1S were maintained in the sample impregnated with sulfuric acid. In addition, the _{morphological difference between the samples before and after H 2} SO ₄ impregnation was almost negligible ( FIG. 9 ).

To investigate the hydrophilicity of the sample, the moisture adsorption isotherm was measured at 25 °C, and the result is shown in FIG. 2A. As a result of the measurement, water absorption gradually increased _{from 1S (P/P 0} =0.87 to 468 cm ³ g ^{- 1} ) to 1S3M (P/P ₀ =0.87 to 1125 cm ³ g ^{- 1 ).} In particular, 1S3M exhibited the highest initial moisture adsorption at low pressure and the strongest hydrophilicity, and this tendency of moisture adsorption capacity was consistent with the amount of sulfonic acid groups present on the scaffold. High proton conductivity can be achieved by the presence of many water molecules in the conduction channel, and it is expected to have high proton conductivity due to this water adsorption ability.

(2) A solid electrolyte membrane was prepared by mixing Compound 1S and a PVDF polymer matrix (FIG. 1), and the image is shown in FIG. 3A. The mass fraction of 1S was 50% for 1S50P and 60% for 1S60P. In order to confirm the successful mixing of the two components, IR spectroscopy data were collected (FIG. 10), through which IR peaks corresponding to compound 1S and PVDF were clearly observed, confirming that these components coexist in the solid electrolyte membrane. . In addition, as a result of confirming the element content of the membrane surface by performing X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX), sulfur of sulfonic acid and sulfuric acid and F in the PVDF matrix were present on the surface of the solid electrolyte membrane. It was confirmed ( FIGS. 11 and 12 ), and it was confirmed that the particle shape of Compound 1S was maintained in the solid electrolyte membrane through the SEM image ( FIGS. 13 and 14 ). In the water absorption isotherm, the water absorption capacities of 1S50P and 1S60P corresponded to 208 and 330 cm ³ g ^-1 _{at P/P 0} = 0.87, respectively. was confirmed (Fig. 3b).

(3) Composition for Solid Electrolyte Compounds 1S1M, 1S2M, and 1S3M were mixed with a PVDF polymer matrix to prepare solid electrolyte membranes 1S1MP, 1S2MP and 1S3MP, of which 1S3MP images are shown in FIG. 4 . In addition, the presence of the mixed components was confirmed through IR spectrum (FIG. 15), XPS (FIG. 16) and EDX (FIG. 17) analysis, and the particle shapes of 1S1M, 1S2M, and 1S3M were solid through the SEM image (FIG. 18). It was confirmed that the electrolyte membrane was maintained.

Test Example 2. Evaluation of hydrogen ion conductivity and activation energy according to temperature increase using impedance equipment

(1) The powdered 1S1M sample was transformed into pellets using a press. Next, the pellet was placed on a self-made platinum electrode, and the hydrogen ion conductivity and activation energy values were evaluated using an impedance device (Solartron SI 1260) while changing the temperature in a thermo-hygrostat with a fixed relative humidity of 90%.

Specifically, (b) of Figure 2 below is a Nyquist plot (Nyquist plots) at 90% RH and various temperature ranges of 1S1M, (c) is an activation energy (Activation energy) of 1S1M, (d) ) is a diagram showing the results of comparison with the previously reported activation energies of the solid electrolyte (> 0.01 S cm-1 &< 0.35 eV). (1S1M: red, BUT-8 (Cr) a: black, 1ES: green, PCMOF2 1/2 (Pz): blue, TfOH @ MIL-101: magenta, PCMOF2 1/2 (tz): yellow, UiO-66 (SO ₃ H) ₂ : dark yellow, 1S: navy, HOF-GS-11: purple, H ⁺ @Ni ₂ (dobdc)(H ₂ O) ₂ (pH = 2.4): wine, H ⁺ @Ni ₂ ( _{dobdc) (H 2 O) 2} (pH = 1.8): olive, PCMOF2 1/2: dark cyan, Nafion: royal, BUT-8 (Cr): orange, MIL-101-SO 3 H: violet, Fe-CAT -5: pink, H ₃ PO4@MIL-10141: gray

(List of prior literature: (1) BUT-8(Cr) _a , BUT-8(Cr), MIL-101-SO ₃ H: F. Yang, G. Xu, Y. Dou, B. Wang, H. Zhang , H. Wu, W. Zhou, J.-R. Li and B. Chen, Nat. Energy, 2017, 2, 877-883., (2) 1ES: DW Kang, JH Song, KJ Lee, HG Lee, JE Kim, HY Lee, JY Kim and CS Hong, J. Mater Chem A, 2017, 5, 17492-17498, (3) PCMOF2 1/2 (Pz), PCMOF2 1/2 (tz):... S. Kim, B. Joarder, JA Hurd, J. Zhang, KW Dawson, BS Gelfand, NE Wong and GKH Shimizu, J. Am. Chem. Soc., 2018, 140, 1077-1082., (4) TfOH@MIL- 101: DN Dybtsev, VG Ponomareva, SB Aliev, AP Chupakhin, MR Gallyamov, NK Moroz, BA Kolesov, KA Kovalenko, ES Shutova and VP Fedin, ACS Appl. Mater. Interfaces, 2014, 6, 5161-5167., (5 ) UiO-66(SO ₃ H) ₂ : WJ Phang, H. Jo, WR Lee, JH Song, K. Yoo, B. Kim and CS Hong, Angew. Chem. Int. Ed., 2015, 54, 5142-5146., (6) 1S: DW Kang, KS Lim, KJ Lee, JH Lee, WR Lee, JH Song, KH Yeom, JY Kim and CS Hong, Angew. Chem. Int. Ed., 2016, 55, 16123-16126., (7) HOF-GS-11: A. Karmakar, R. Illathvalappil, B. Anothumakkool, A. Sen, P. Samanta, AV Desai, S. Kurungot and SK Ghosh , Angew. Chem. Int. Ed., 2016, 55, 10667-10671., (8) H ⁺ @Ni ₂ (dobdc)(H ₂ O) ₂ , H ⁺ @Ni ₂ (dobdc)(H ₂ O) ₂ : A. Karmakar, R Illathvalappil, B. Anothumakkool, A. Sen, P. Samanta, AV Desai, S. Kurungot and SK Ghosh, Angew. Chem. Int. Ed, 2016, 55, 10667-10671, (9) PCMOF2 1/2:.. S. Kim, KW Dawson, BS Gelfand, JM Taylor and GK Shimizu, J. Am. Chem. Soc., 2013, 135, 963-966., (10) Nafion: RCT Slade, A. Hardwick and PG Dickens, Solid State Ionics, 1983, 9, 1093-1098., (11) Fe-CAT-5: NT Nguyen, H. Furukawa, F. Gandara, CA Trickett, HM Jeong, KE Cordova and OM Yaghi, J. Am. Chem. Soc., 2015, 137, 15394-15397., (12) H ₃ PO4@MIL-101: VG Ponomareva, KA Kovalenko, AP Chupakhin, DN Dybtsev, ES Shutova and VP Fedin, J. Am. Chem. Soc., 2012, 134, 15640-15643.

As a result of the measurement, 1S1M according to the present invention showed a value of 1.92×10 ^-1 S cm ^-1 at 30 °C and 2.35×10 ^-2 S cm ^-1 at 70 °C. This value is the highest value among the porous organic materials developed so far, and it was confirmed as a very high value for the overall porous material. In addition, it was confirmed to have the lowest activation energy value (0.075 eV) among values reported for conventional proton-conducting materials. This exceptionally low activation energy provides a minimal change in conductivity with temperature, which can provide ideal performance for fuel cell applications. As such, in order to obtain high proton conductivity and low activation energy, the proton donor plays an important role. In the compositions 1S1M to 1S3M for a solid electrolyte prepared according to the present invention, not only the sulfonic acid groups covalently bonded to the skeleton but also the sulfate groups impregnated in the pores can act as a proton donor, constituting an effective water-mediated conduction pathway, leading to low activation energy.

(2) Hydrogen ion conductivity and activation energy values using impedance equipment (Solartron SI 1260) while changing the temperature in a thermo-hygrostat with high, fixed relative humidity of 90% on a platinum electrode manufactured by the solid electrolyte membrane 1S50P, 1S60P was evaluated, and the results are shown in (c) and (d) of FIG. 3 below. ^{As a result of the measurement, 1S50P and 1S60P showed conductivity values of 1.82×10 -3} and 5.54×10 ^-3 S cm ^-1 under the conditions of 30 ℃ and 90% RH, respectively, and 4.06× under the conditions of 80 ℃ and 90% RH. 10 ^-3 and 8.83×10 ^-3 S cm ^{-1 As} it was shown to increase, it was confirmed that the conductivity increased as the mass percentage of Compound 1S increased. Through this, it was confirmed that the performance of 1S50P and 1S60P is related to the percolation pathway of the solid electrolyte membrane produced by the conductive compound 1S.

(3) Hydrogen ion conductivity and activation using impedance equipment (Solartron SI 1260) while changing the temperature in a thermo-hygrostat with high relative humidity fixed at 90% and high on a self-manufactured platinum electrode with solid electrolyte membranes 1S1MP, 1S2MP, and 1S3MP Energy values were evaluated, and the results are shown in FIG. 5 below. Measurement results, is 1S1MP showed a value of 4.48 × 10 ^-3 S cm ^-1 at 80 ℃, 1S2MP is showed a value of ^{6.26 × 10 -3 S cm -1,} 1S3MP is 2.13 × 10 ^-2 S cm ^{- A value of 1} indicates that the proton conductivity is very high. In addition, the respective activation energies were found to be very low as 0.082, 0.047, and 0.039 eV, respectively.

Test Example 3. Evaluation of maintaining hydrogen ion conductivity for a long time

In order to evaluate whether the solid electrolyte membrane 1S3MP can maintain stable performance for a long period of time, hydrogen ion conductivity was evaluated every week after exposure to 80 °C and 90% normal humidity.

As a result of the measurement, as shown in FIG. 6 , the initial performance was maintained for at least 10 days, and through this, it was confirmed that the solid electrolyte membrane according to the present invention could be usefully used in a fuel cell due to the stability of the performance.

Claims (14)

sulfuric acid; and
Including the porous organic polymer skeleton represented by the following [Formula 1]:
The composition for a solid electrolyte, characterized in that the molar concentration of the sulfuric acid solution containing the sulfuric acid is 1 to 3M:
[Formula 1]
[C ₈ H ₅ O ₂ S _0.47 O _1.41 ]n 0.5H ₂ O
Wherein n is an integer from 1 to 100. According to claim 1,
The composition for a solid electrolyte, characterized in that the porous organic polymer skeleton represented by the [Formula 1] is dispersed in the sulfuric acid solution. According to claim 1,
A composition for a solid electrolyte, characterized in that sulfuric acid is impregnated in the pores of the porous organic polymer skeleton represented by the [Formula 1]. delete According to claim 1,
The composition for a solid electrolyte has a hydrogen ion conductivity of 1.92×10 ^-2 S/cm to 2.35×10 ^-2 S/cm in a temperature range of 30° C. to 70° C. under 90% relative humidity. The composition for a solid electrolyte according to claim 1; and
A solid electrolyte membrane comprising a; a polymer film in which the composition for a solid electrolyte is dispersed. 7. The method of claim 6,
The polymer film is polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide (PA), cellulose, polyvinyl chloride (PVC) and polyvinyl alcohol ( A solid electrolyte membrane, characterized in that it is selected from the group consisting of PVA). 7. The method of claim 6,
The solid electrolyte membrane has a hydrogen ion conductivity of 4.48×10 ^-3 S/cm to 2.13×10 ^-2 S/cm at a temperature of 80° C. and 90% relative humidity. 7. The method of claim 6,
The solid electrolyte membrane has an activation energy of 0.039 eV to 0.082 eV. Dispersing the porous organic polymer skeleton represented by the following [Formula 1] in a sulfuric acid solution of a predetermined concentration;
The method for preparing a composition for a solid electrolyte, characterized in that the molar concentration of the sulfuric acid solution is 1 to 3M:
[Formula 1]
[C ₈ H ₅ O ₂ S _0.47 O _1.41 ]n 0.5H ₂ O
Wherein n is an integer from 1 to 100. 11. The method of claim 10,
Drying the porous organic polymer skeleton represented by [Formula 1] dispersed in the sulfuric acid solution to obtain a porous organic polymer skeleton powder impregnated with sulfuric acid in the pores; delete Dispersing a porous organic polymer skeleton represented by the following [Formula 1] in a sulfuric acid solution of a predetermined concentration;
drying the porous organic polymer skeleton represented by [Formula 1] dispersed in the sulfuric acid solution to obtain a porous organic polymer skeleton powder impregnated with sulfuric acid in the pores;
dispersing the obtained porous organic polymer skeleton powder in a polymer solution; and
forming a film by casting a polymer solution in which the porous organic polymer skeleton powder is dispersed;
The method for producing a solid electrolyte membrane, characterized in that the molar concentration of the sulfuric acid solution is 1 to 3M:
[Formula 1]
[C ₈ H ₅ O ₂ S _0.47 O _1.41 ]n 0.5H ₂ O
Wherein n is an integer from 1 to 100. 14. The method of claim 13,
The polymer solution is polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide (PA), cellulose, polyvinyl chloride (PVC) and polyvinyl alcohol ( PVA), a method of manufacturing a solid electrolyte membrane, characterized in that selected from the group consisting of.

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