KR101773245B1 - Sulfonated hydrocarbon nanocomposite membrane comprising polyhedral oligomeric silsesquioxane with proton donor and proton acceptor and Method of preparing the same - Google Patents

Abstract

The present invention relates to a polyhedral oligomeric silsesquioxane (POSS) having a proton donor and a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor as an aromatic hydrocarbon having a sulfone group To a proton-conducting nanocomposite membrane introduced into a polymer membrane and a method for producing the same.
In the nanocomposite membrane of the present invention, POSS having a proton acceptor and POSS having a proton acceptor are added together, so that protons (cations) generated easily hop through hydrogen bonds in an ion channel to increase ion conductivity.
In addition, the POSS used in the present invention is very small in size, so that it does not substantially interfere with the movement of protons in the ion channel in the polymer membrane, and therefore, proton conductivity can be improved.
Also, the proton-conducting nanocomposite membrane of the present invention exhibits excellent mechanical strength despite increasing the degree of sulfonation of the polymer membrane.

Description

TECHNICAL FIELD The present invention relates to a hydrocarbon-based nanocomposite membrane comprising a polyhedral oligomeric silsesquioxane having a proton acceptor and a proton acceptor, and a process for producing the same. More particularly, the present invention relates to a hydrocarbon-based nanocomposite membrane comprising a polyhedral oligomeric silsesquioxane,

The present invention relates to a polyhedral oligomeric silsesquioxane (POSS) having a proton donor and a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor and a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor, A proton conducting nanocomposite membrane introduced into a polymer, and a method for producing the proton conducting nanocomposite membrane.

Recently, the fuel cell is a power generation system that converts the energy generated by electrochemically reacting fuel and oxidant directly into electric energy. As the environment problem, the depletion of energy source, and the practical use of fuel cell automobile are accelerated, the efficiency is increased A variety of polymer membranes have been developed which can be used at high temperatures.

Fuel cells include a solid oxide fuel cell that operates largely at 700 ° C or higher, a molten carbonate electrolyte fuel cell that operates at 500 to 700 ° C, a phosphoric acid electrolyte fuel cell that operates at or near 200 ° C, Alkaline electrolyte type fuel cells, and polymer electrolyte type fuel cells. In addition, direct methanol fuel cells among the fuel cells do not need to be reformed methanol, and miniaturization is possible.

Among them, the polymer electrolyte fuel cell is a clean energy source. However, since it can be operated at room temperature with high output density and energy conversion efficiency, it can be miniaturized and sealed, Business equipment, and the like, and the research is being concentrated more and more.

Particularly, a proton exchange membrane fuel cell (PEMFC) using a proton exchange membrane is a power generation system for producing direct current electricity from an electrochemical reaction between hydrogen and oxygen. The proton exchange membrane fuel cell And has a structure in which a conductive polymer membrane is interposed. Therefore, as hydrogen in the reactor is supplied, an oxidation reaction occurs in the anode, and hydrogen molecules are converted into hydrogen ions and electrons. At this time, the converted hydrogen ions are transferred to the cathode through the proton conductive polymer membrane. A reduction reaction that converts to oxygen ions occurs, and the generated oxygen ions are converted into water molecules by reacting with hydrogen ions transferred from the anode.

In this process, the proton-conducting polymer membrane for a fuel cell functions as an insulator electrically, but acts as a mediator for transferring hydrogen ions from the anode to the cathode during the operation of the battery, and simultaneously separates the fuel gas or the liquid and the oxidant gas. The chemical stability must be excellent, the thermal stability at the operating temperature, the possibility of manufacturing as a thin film to reduce the resistance, and the effect of the expansion at the time of liquid containment should be small.

A representative material widely used as an electrolyte membrane used in a typical typical polymer electrolyte fuel cell is Nafion developed by DuPont. However, Nafion has a drawback in that the tensile strength is low at 20 MPa and the water swelling is 40%, which is weak in mechanical strength, instead of good proton conductivity (0.1 S / cm). Nafion, which is the most commercially used fluorocarbon polymer, has a price range of 100 $ / cm2, while representative hydrocarbon polymers are 6 to 10 $ / cm2. Therefore, if Nafion is replaced with a hydrocarbon polymer, Or more. However, since the degree of phase separation between the hydrophobic main chain and the hydrophilic side chain is lower than that of the fluoropolymer, the diameter of the ion cluster is about 4 to 5 nm, which is about 50% smaller than that of Nafion. The ionic conductivity of the hydrocarbon polymer electrolyte membrane is about 0.05 S / cm due to the ion cluster formed 50% smaller than Nafion, and it is only about half of that of Nafion with 0.1 S / cm ion conductivity. Therefore, There is a study to increase the degree of sulfonation of the polymer. However, sulfonated polyetheretherketone (sPEEK), which is a typical hydrocarbon polymer, has a low water swelling of less than 20% through aromatic styrenes having high stiffness. However, when the degree of sulfonation is increased to 75% or more, water swelling rapidly increases, .

 Korean Patent No. 804195 proposes a hydrogen-ion conductive polymer electrolyte membrane in which a sulfonated group is introduced into inorganic nanoparticles such as silicon oxide and aluminum oxide, and then the polymer electrolyte is mixed with a polymer electrolyte. However, such a composite membrane has a problem in that inorganic particles having a size of several micrometers or several tens to several hundreds of nanometers interfere with the movement of protons in the ion channel, thereby deteriorating the proton conductivity. Also, there is a problem that the mechanical strength of the composite membrane is lowered due to the size and aggregation of the inorganic particles.

The proton-conducting polymer nanocomposite membrane using sulfonic acid group-containing silsesquioxane having a sulfonic acid group is disclosed in Japanese Laid Open Patent Application No. 10-2013-118075, which discloses an electrolytic solution in which a silsesquioxane having a sulfonic acid group is mixed with a fluorine-based proton- Film is disclosed. In the above-mentioned patent, the nanosized nanofiltration membrane with a sulfonic acid group is combined with Nafion to increase the mechanical strength and conductivity of the nanocomposite membrane, but a nanocomposite membrane electrolyte having a higher ionic conductivity is required to replace Nafion do.

The present invention provides a proton-conducting polymer nanocomposite membrane which provides excellent proton conductivity at a low temperature of 80 ° C or less and does not cause mechanical strength deterioration due to water swelling and prevents gas permeability.

One aspect of the present invention is

Polyhedral oligomeric silsesquioxane (POSS) with a proton donor and polyhedral oligomeric silsesquioxane (POSS) with a proton acceptor are introduced into a sulfonated aromatic hydrocarbon polymer membrane Lt; RTI ID = 0.0 > nanocomposite < / RTI >

In another aspect,

A polyhedral oligomeric silsesquioxane (POSS) having a proton donor and oligomeric silsesquioxane (POSS) having a proton acceptor and a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor were dissolved in a sulfonated aromatic hydrocarbon polymer solution Mixing; And

Casting the mixed solution and removing the solvent. The present invention also relates to a method for producing a proton-conducting nanocomposite membrane.

In another aspect, the present invention relates to a membrane electrode assembly for a fuel cell comprising a proton-conducting nanocomposite membrane.

In the nanocomposite membrane of the present invention, POSS having a proton acceptor and POSS having a proton acceptor are added together, so that the generated protons (positive ions) easily hop in the ion channel and the ion conductivity is increased.

In addition, the POSS used in the present invention is very small in size, so that it does not substantially interfere with the movement of protons in the ion channel in the polymer membrane, and therefore, proton conductivity can be improved.

In addition, the proton conducting nanocomposite membrane of the present invention exhibits excellent mechanical strength despite increasing the degree of sulfonation of the polymer membrane to DS = 70.

The proton-conducting nanocomposite membrane of the present invention can be used not only as a polymer electrolyte fuel cell but also as a polymer electrolyte membrane or separation membrane of a direct methanol fuel cell.

1 is a graph showing the ionic conductivity of the conductive nanocomposite membrane prepared in Example 1. FIG.
2 shows the stress when the content of POSS-N is fixed at 0.5 wt% and the content of POSS-SA is increased up to 10 wt%.
FIG. 3 compares the performance of a cell fabricated using the nanocomposite membrane prepared in Example 1 and Comparative Example 1. FIG.

Hereinafter, the present invention will be described in detail.

The present invention relates to a proton-conducting polymer nanocomposite membrane for a fuel cell. The proton-conducting nanocomposite membrane of the present invention comprises a polyhedral oligomeric silsesquioxane (POSS) having a proton donor and a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor Is introduced into an aromatic hydrocarbon polymer membrane having a sulfone group.

The polymer membrane of the present invention can use an aromatic hydrocarbon polymer having a sulfone group bonded thereto as a proton source.

The sulfonated aromatic hydrocarbon polymer membrane (sulphonated aromatic hydrocarbon polymer membrane) may be formed by using a sulfonated polyetheretherketone (sPEEK) polymer membrane, a sulfonated polyetherketone (sPEK), a sulfonated polyetheretherketone polyethersulfone (sPES) and sulfonated polyarylethersulfone (sPAES) and may be a sulfonated aromatic hydrocarbon having a nanochannel.

The sulfonated aromatic hydrocarbon polymer membrane, preferably polyetheretherketone and polyethersulfone, has a cation conductivity of about 50% of Nafion, excellent thermal and chemical properties, and is durable enough to have a long lifetime of 5000h.

The sulfonated aromatic hydrocarbon polymer has excellent proton conductivity as the degree of sulfonation (DS) increases, but has a problem in that the mechanical strength is lowered due to a higher water swelling phenomenon. The nanocomposite membrane of the present invention can prevent the mechanical strength from being drastically reduced due to water swelling even when an aromatic hydrocarbon polymer having a high degree of sulfonation is used.

The sulfonated aromatic hydrocarbon polymer membrane may have a degree of sulfonation of 55 to 80%, preferably 60 to 75%, and most preferably 65 to 75%.

In the present invention, polyhedral oligomeric silsesquioxane (POSS) is used as a filler of a sulfonated aromatic hydrocarbon polymer membrane. More specifically, in the present invention, a proton donor, Polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor and polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor are used together.

The polyhedral oligomeric silsesquioxane (POSS) having the proton donor may be represented by the following formula (1).

In the above formula (1), R is a proton donor.

Wherein R is < RTI ID = 0.0 >

R1 is (CH2) n, wherein n is an integer from 1 to 6, or phenylene,

 R2 is acetic acid, nitric acid, phosphoric acid, sulfonic acid, perchloric acid, hydrochloric acid, salts thereof, or a compound containing them.

The polyhedral oligomeric silsesquioxane (POSS) having the proton donor may preferably be a sulfonated octaphenyl polyhedral oligomeric silsesquioxane represented by the following formula (2).

Wherein at least one of R is SO3H.

In the above formula, R can be functionalized up to 16.

The polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor may be represented by the following formula (3).

In Formula 1, A is a compound containing nitrogen, oxygen, phosphorus, fluorine and chlorine atoms having a non-covalent electron pair.

Or A is -A1A2 wherein A1 is (CH2) n wherein n is an integer from 1 to 6 or phenylene and A2 is NH2, NO3-, NH3, PH3, NH2-, Cl-, -, S2-, F-, a salt thereof, or a compound containing them,

The polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor may be represented by the following formula (4).

Wherein at least one of A is NH2.

Where A can be functionalized with up to 16 Rs.

A polyhedral oligomeric silsesquioxane (hereinafter referred to as POSS-SA) having a polyhedral oligomeric silsesquioxane (hereinafter referred to as POSS-SA) and a proton acceptor having the proton donor N) may have a particle size of 1 to 5 nm, preferably 1 to 3 nm, more preferably 1 to 2 nm. Since the POSS has a small size, it does not interfere with the movement of ions in the ion channel of the aromatic hydrocarbon polymer membrane having a sulfone group, thereby solving the problem of lowering the ion conductivity, which is the biggest problem of the composite membrane.

The polyhedral oligomeric silsesquioxane (POSS) has a very small particle size and has a very compact chemical structure in which a phenyl group and a sulfonic acid group (or an amine group) are bonded to a stable silica cage structure, which is very easy to disperse.

In the present invention, since a proton acceptor acts as a Bronsted base such as an amine group, it forms a strong hydrogen bond with an excess amount of protons additionally introduced into the nanochannel, and through the Grotthuss mechanism by the hopping of protons, .

The nanocomposite membrane of the present invention is complexed with less than 5 wt% of POSS-N, preferably less than 1 wt%, so that it does not interfere with proton transfer in the channel or lower the overall ion exchange capacity. In addition, the proton acceptor may have a Grotthuss mechanism through which a further proton source generated by the proton donor mediates hydrogen bonding.

More specifically, the hopping mechanism (or Grotthuss mechanism) is a mechanism in which a proton is hopped and conducted through a hydrogen bonding network, and a cation capable of acting as a strong Bronsted base (amine group) When the acceptor is introduced, the hydrogen bond medium is increased and the Bronsted acid - base hopping distance is reduced. Therefore, the Grotthuss mechanism can be further activated and the proton conductivity can be drastically increased.

The nanocomposite membrane of the present invention is capable of remarkably increasing the ionic conductivity and significantly increasing the ionic conductivity in the channel even when the weight range of the polyhedral oligomeric silsesquioxane (POSS) is increased up to 20 wt% And strength) can be increased at the same time. The nanocomposite membrane of the present invention can produce a thinner film of 30 microns or less since tensile strength is increased without loss of ductility by the addition of polyhedral oligomeric silsesquioxane (POSS). That is, the nanocomposite film of the present invention can be produced as an ultra-thin film.

The polyhedral oligomeric silsesquioxane (POSS) can increase the mechanical strength of the nanocomposite membrane and inhibit swelling of the membrane due to moisture. In addition, the polyhedral oligomeric silsesquioxane (POSS) added nanocomposite membrane can maintain a high ion conduction capability at 80 degrees or less.

The polyhedral oligomeric silsesquioxane (POSS) may be contained in an amount of 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 1 to 2% by weight based on the total weight of the proton-conducting nanocomposite membrane .

Wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor and the polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor are mixed at a weight ratio of 1: 1, preferably 1; 0.05 to 0.3, and more preferably 1: 0.1 to 0.25.

The polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor may be contained in an amount of 5 wt% or less, preferably 1 wt% or less, based on the nanocomposite membrane.

The polyhedral oligomeric silsesquioxane (POSS) having the proton donor is added to the nanocomposite membrane in an amount of 1 to 10 wt%, preferably 1 to 5 wt%, more preferably 1 to 2 wt% .

When the content of the polyhedral oligomeric silsesquioxane is within the above range, it has a conductivity higher than that of the Nafion membrane (0.1 S / cm) currently commercialized at 80 ° C / 100% RH.

In the present invention, a polymer membrane having a high degree of sulfonation of 55 to 70% is used, but the POSS-SA has a strong mechanical strength because it forms a molecular composite within the polymer membrane.

That is, in the present invention, the conductivity and the mechanical strength of the proton-conducting composite membrane can be simultaneously increased.

In another aspect, the invention relates to a method of making a proton conducting nanocomposite membrane.

The method comprises reacting a polyhedral oligomeric silsesquioxane (POSS) having a proton donor with a polyhedral oligomeric silsesquioxane (POSS) having a proton donor and a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor with an aromatic hydrocarbon having a sulfone group Mixing with the polymer solution; And

Casting the mixed solution and removing the solvent.

The sulfone group-containing aromatic hydrocarbon polymer membrane may be formed of a sulfonated polyetheretherketone (sPEEK) polymer membrane, a sulfonated polyetherketone (sPEK), a sulfonated polyether sulfone (sPES) Which may be sulfonated polyarylethersulfone (sPAES).

The method comprises controlling the degree of sulfonation of the aromatic hydrocarbon polymer having sulfone groups to 55 to 80% and adjusting the content of the polyhedral oligomeric silsesquioxane (POSS) to 1 to 5, based on the total weight of the aromatic hydrocarbon polymer and POSS Weight%.

The method comprises reacting a polyhedrin oligomeric silsesquioxane (POSS) having a proton donor with a polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor at a weight ratio of 1 : 0.05 to 1, preferably 1; 0.05 to 0.3, and more preferably 1: 0.1 to 0.25.

The sulfonated polyetheretherketone (sPEEK) having the above degree of sulfonation can be produced by a known method. For example, sulfuric acid is fed into a polyether ether ketone (PEEK) solution and reacted at room temperature, Can be manufactured.

As the sulfonating agent, compounds known in the field such as sulfonic acid and the like can be used. The sulfonation of the PEEK can be controlled by reacting at 60 to 150 ° C. for 1 to 30 hours. More specifically, after PEEK is dried at 100 ° C for 12 hours, 10 g of PEEK may be added to 200 ml of sulfuric acid and stirred at 60 ° C for 24 hours.

In another aspect, the present invention relates to a membrane electrode assembly for a fuel cell comprising a fuel electrode, an oxygen electrode, and the proton-conducting nanocomposite membrane positioned between the fuel electrode and the oxygen electrode. For the fuel electrode, the oxygen electrode, and the like, well-known contents can be referred to. The proton conducting nanocomposite membrane functions as a mediator for transferring protons generated from the fuel electrode and electrons to the oxygen electrode, and functions as a separation membrane for separating hydrogen and oxygen.

The proton-conducting nanocomposite membrane may be the nanocomposite membrane of the present invention described above.

The present invention relates to a fuel cell having the membrane-electrode assembly.

The fuel cell according to one embodiment can be manufactured by a known method using the membrane-electrode assembly obtained as described above. That is, the fuel cell stack can be manufactured by constructing the unit cells by interposing the both sides of the membrane-electrode assembly described above with graphite, and arranging a plurality of unit cells.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example  One

1. Synthesis of Polyhedral Oligomeric Silsesquioxane (POSS-SO3H (POSS-SA)) having a sulfonic acid group

First, 1 g of octaphenyl poss was mixed with 5 ml of chlorosulfonic acid and stirred overnight at room temperature. The solution was poured into 200 ml of THF and the resulting powder was filtered and repeated until the pH was neutral. Lt; / RTI > and dried under reduced pressure to give a brown solid.

H-NMR (D2O) -7.54 (dd; ArHmeta to POSS), 7.81-7.83 (2dd; ArH para to SO3H, ArHpara to POSS), 8.03 (dd; ArH ortho to SO3HandPOSS).

FT-IR: 3070 (OH of SO3H), 2330 (SO3H-H2O), 1718,1590,1470,1446,1395,1298,1132 (SO3 asymm), 1081 (SO3 symm), 1023 (SiOSi asymm) 806 (SiOSi symm)

2. Synthesis of Polyhedral Oligomeric Silsesquioxane (POSS-NH2 (POSS-N)) having an amine group

<Create ONP (Octaphenyl POSS)>

5 g of OPS and 30 ml of fuming nitric acid were added to ice water and mixed for 30 min. The reaction was carried out at room temperature for about 20 hours. The solution was poured into ice water to give a flour and then filtered. Subsequently, the solid residue obtained by filtration was washed with water and further washed twice with 100 ml of ethanol (ONP obtained).

<Create OAPS>

0.5 g of the ONP obtained above was mixed with 0.06 g of 10 wt% Pd / C and pulverized. 20 ml of THF and 20 ml of triethylamine were added thereto. Add a small amount of formic acid to the mixture and allow to react for 5 hours. By reaction, it was separated into two layers. The transparent layer above was discarded and the black layer below was collected, and then 50 ml of THF and 50 ml of water were mixed. The mixed solution was subjected to column chromatography using celite to obtain Octa nitrophenyl POSS (ONPS). Then, 50 ml of ethyl acetate was added to the filterate and 100 ml of pure water was poured into the solution.

The EA layer (upper layer) was taken out and the brown crystals were filtered, and then mixed with 500 ml of hexane to prepare Octa aminophenyl POSS (OAPS).

3. Making Nanocomposite Membrane

A 5 wt% solution was made by dissolving 5 g of sulfonated polyetheretherketone (sPEEK, sulphonation degree (DS) 65, purchased from fumatech, DS 60 sPEEK, and 70 and 75 through this) in 95 g of N, N-dimethylacetamide .

11.76 g of the 5 wt% solution (0.588 g of sPEEK) was placed in each of the four vials. The sPEEK / POSS-SA / POSS-N nanocomposite membrane was prepared by fixing the POSS-SA content to 2 wt% and the POSS-N content to sPEEK to 0 to 1 wt%.

POSS-SA and POSS-N prepared previously were mixed in four sPEEK vials, respectively, and stirred for one day. The stirred solution of sPEEK / POSS-SA 2 wt% / POSS-N 0 to 1 wt% solution was poured into each of the chalets, and then cast in an oven at 100 ° C. overnight. After casting, distilled water was poured into the chalette and the nanocomposite membrane was carefully removed from the chalette.

Comparative Example  One

POSS-N was added to sulfonated polyetheretherketone (sPEEK, sulfonation degree (DS) 65) without using POSS-SA to prepare a nanocomposite membrane as in Example 1.

Experiment: Ion conductivity measurement

After measuring the thickness of the composite membrane samples obtained in Comparative Example 1 and Example 1, the ion conductivity was measured at 80 ° C / 100% RH after connecting 4 probe conductivity cells of Bekktech Co. with AC impedance. The measured ionic conductivity is shown in Fig.

Experiment 2: Measurement of tensile strength

After drying the membrane of Example 1 and Comparative Example 1, the mechanical strength of the nanocomposite membrane was measured at room temperature using a universal testing machine (UTM) according to the standard method of ASTM d882. The tensile strength of the nanocomposite membrane obtained in Example 1 and Comparative Example 1 was measured and shown in FIG.

Experiment 3: Performance comparison of fuel cell

A commercial catalyst electrode layer was coated on both sides of the nanocomposite membrane prepared in Example 1 and Comparative Example 1 by a hot-press method to prepare a membrane-electrode assembly (MEA).

The electrode used was a single-sided ELAT (R) electrode available from E-TEK Inc., with a platinum-rubidium black catalyst on the anode and a platinum black catalyst on the anode. The conditions used for the hot-press were fixed by applying a pressure of about 60 kgf / cm &lt; 2 &gt; at 140 DEG C for 5 minutes. A silicon-coated glass fiber gasket was placed above and below the membrane-electrode assembly, and a unit cell was assembled by compression-sealing with a collector plate made of carbon material.

The stoichiometric ratios of pure hydrogen and oxygen introduced into the anode and cathode were fixed at 2.0 and 3.0, respectively. The inlet pressure was 30 psi and the performance of the cell was measured at 80 ℃ and 100% And the results are shown in Fig.

1, when the content of POSS-N is fixed to 2 wt% and the content of POSS-N is changed from 0 to 1 wt%, when the content of POSS-N is 0.5 wt%, the ion conductivity is 0.12 S / cm.

2 shows the stress when the content of POSS-N is fixed at 0.5 wt% and the content of POSS-SA is increased up to 10 wt%. Referring to FIG. 2, in the embodiment of the present invention, it is confirmed that the stress is maintained even when the strain is increased from 80% to 120%. That is, the nanocomposite membrane of the present invention shows that the addition of the polyhedral oligomeric silsesquioxane (POSS) increases the tensile strength without loss of ductility.

FIG. 3 compares the performance of a cell fabricated using the nanocomposite membrane prepared in Example 1 and Comparative Example 1. FIG. Referring to FIG. 3, it can be seen that the cell performance of Comparative Example 1 (sPEEK composite membrane) was 3 times higher than that of 40 A / cm 2 when the composite membrane prepared in Example 1 was used at 0.6 V and 120 A / cm 2. This is because the ions are easily hopped through the hydrogen bond through the cation-acceptor and the ionic conductivity is greatly increased

Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (14)

Polyhedral oligomeric silsesquioxane (POSS) with a proton donor and polyhedral oligomeric silsesquioxane (POSS) with a proton acceptor are introduced into a sulfonated aromatic hydrocarbon polymer membrane Of proton conducting nanocomposite membrane. The method of claim 1, wherein the hydrocarbon polymer membrane is selected from the group consisting of a sulfonated polyetheretherketone (sPEEK), a sulfonated polyetherketone (sPEK), a sulfonated polyethersulfone (sPES) Wherein the proton conducting nanocomposite membrane is selected from the group of sulfonated polyarylethersulfone (sPAES) and is a sulfonated aromatic hydrocarbon having a nano channel. The proton-conducting nanocomposite membrane according to claim 1, wherein the sulfonated aromatic hydrocarbon polymer membrane has a sulfonation degree of 55 to 70%. The method of claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor and the polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor are Wherein the nanocomposite membrane comprises 1 to 5% by weight of the nanocomposite membrane. The method according to claim 4, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor and the polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor are Wherein the proton conducting nanocomposite membrane is contained in a weight ratio of 1: 0.05 to 1. The proton-conducting nanocomposite membrane according to claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) particles have a size of 1 to 3 nm. The proton-conducting nanocomposite membrane according to claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor is represented by the following formula (1).
[Chemical Formula 1]

In the above formula (1), R is a proton donor,
The R is at least one selected from the group consisting of acetic acid, nitric acid, phosphoric acid, sulfonic acid, perchloric acid, hydrochloric acid, 8. The compound according to claim 7, wherein R is-R1-R2,
Wherein R1 is (CH2) n, wherein n is an integer from 1 to 6, or phenylene,
Herein, R 2 is a compound containing acetic acid, nitric acid, phosphoric acid, sulfonic acid, perchloric acid, hydrochloric acid, carbonic acid salt thereof, or a compound thereof. The proton-conducting nanocomposite membrane according to claim 7, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor is represented by the following formula (2).
(2)

Wherein at least one of R is SO3H and the R can be functionalized up to 16. The proton-conducting nanocomposite membrane according to claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor is represented by the following formula (3).
(3)

In Formula 3, A is a compound containing nitrogen, oxygen, phosphorus, fluorine and chlorine atoms having a non-covalent electron pair. 11. The compound according to claim 10, wherein A is -A1A2,
Wherein A1 is (CH2) n wherein n is an integer from 1 to 6 or phenylene and A2 is NH2, NO3-, NH3, PH3, NH2-, Cl-, O2-, S2-, Salt or a compound containing them. The proton-conducting nanocomposite membrane according to claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor is represented by the following formula (4).
[Chemical Formula 4]

Wherein at least one of A is NH2 and A can be functionalized up to 16. Polyhedral oligomeric silsesquioxane (POSS) with a proton donor and polyhedral oligomeric silsesquioxane (POSS) with a proton acceptor were synthesized in an aromatic hydrocarbon polymer solution having sulfone groups Mixing; And
Casting the mixed solution and removing the solvent. The method according to claim 13, wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor and the polyhedral oligomeric silsesquioxane (POSS) having the proton acceptor are Wherein the polyhedral oligomeric silsesquioxane (POSS) having the proton donor and the polyhedral oligomeric oligomer having the proton acceptor are added to the nanocomposite membrane in an amount of 1 to 20 wt% Wherein the weight ratio of silsesquioxane (POSS) is 1: 0.05 to 1.

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