High-temperature polymer electrolyte membrane fuel cell and preparation method thereof

Abstract

The invention relates to a high-temperature polymer electrolyte membrane fuel cell and a preparation method thereof. Specifically, disclosed is a high-temperature polymer electrolyte membrane fuel cell, the electrode of which includes a polymer including a phosphate group and a binaphthyl group, thereby preventing phosphoric acid poisoning of a catalyst due to strong interaction with phosphoric acid and porosity, and improving electrochemical performance.

Description

Technical Field

[0001] The present disclosure relates to a high temperature polymer electrolyte membrane fuel cell and a method for preparing the same. Background Art

[0002] High temperature polymer electrolyte membrane fuel cells (HT PEMFCs) generally operate at temperatures between 120° C. and 200° C. Currently, HT PEMFCs have problems such as phosphoric acid leakage from the polymer membrane during operation, resulting in reduced cation conductivity of the polymer membrane, and deteriorated electrochemical performance due to phosphoric acid poisoning of the catalyst.

[0003] However, high temperature polymer electrolyte membrane fuel cells have many advantages over low temperature fuel cells, such as no need for CO removal equipment, humidifiers and condensate handling equipment, CO resistance, high catalytic activity, etc. Therefore, it is necessary to develop new materials for high temperature polymer electrolyte membrane fuel cells. Summary of the invention

[0004] The present disclosure takes into account the problems encountered in the prior art and aims to provide a method for preparing an electrode using a polymer material, thereby reducing phosphoric acid leakage and phosphoric acid poisoning, thereby improving the performance of a high temperature polymer electrolyte membrane fuel cell.

[0005] The purpose of the present disclosure is not limited to the foregoing content. Through the following description, the purpose of the present disclosure will be clearly understood and achieved through the devices described in the present invention and their combinations.

[0006] The present disclosure provides a high-temperature polymer electrolyte membrane fuel cell, which includes an electrolyte membrane and electrodes, wherein the electrodes include a cathode disposed on one side of the electrolyte membrane and an anode disposed on the other side of the electrolyte membrane, wherein the electrodes may include a catalyst, an ionomer, and a polymer having a binaphthyl functional group.

[0007] As mentioned herein, the binaphthyl functional group is a moiety comprising at least two optionally substituted naphthyls. For example, a plurality of naphthyls can be covalently linked by one or more bonds. In some aspects, two or more naphthyls can be linked by an inserted non-aromatic ring (e.g., a 5-membered or 6-membered ring), wherein the atoms of each of the two naphthyls are ring members. The naphthyl is optionally substituted, and each or one of the naphthyls can suitably include one or more ring substituents, such as halogen (F, Cl, Br, I), optionally substituted alkyl (including C 1-12 alkyl), nitro, cyano, optionally substituted alkoxy (including C 1-12 alkoxy), carbocyclic aromatic groups (e.g., phenyl, naphthyl), etc.

[0008] In some aspects, the binaphthyl functional group can include the following structure of Formula A:

[0009]

[0010] In formula A, Z is an optional covalent linker (joiner) between the naphthyl groups and can provide one or more covalent bonds between the naphthyl groups. Z can suitably be a linker containing one or more carbon atoms such as 1 to 10 carbon atoms or 1, 2, 3, 4, 5 or 6 carbon atoms. The X and Y groups are linkers that can be covalently attached to a polymer structure (e.g., a polymer backbone (skeleton) linker). The X and Y groups can also form a condensed ring system with the naphthyl group. The X and Y groups can include one or more of those described for X and Y in the following formula B. Each of the units A, B, A' and B' of the naphthyl group can be optionally substituted at one or more available ring positions by groups such as the following: halogen (F, Cl, Br, I), optionally substituted alkyl (including C 1-12 alkyl), nitro, cyano, optionally substituted alkoxy (including C 1-12 alkoxy), carbocyclic aromatic groups (e.g., phenyl, naphthyl), etc.

[0011] In a preferred aspect, the binaphthyl functional group may include the following structure of Formula B:

[0012]

[0013] In formula B, T and U are each a linker containing one or more carbon atoms such as 1 to 10 carbon atoms or 1, 2, 3, 4, 5 or 6 carbon atoms or 1, 2 or 3 carbon atoms. In a preferred system, T and U form a 3-ring fused system with the naphthyl ring, wherein a non-aromatic ring (e.g., 5 or 6 ring members, wherein 2 ring members are from ring A' and / or B', and two ring members are from A and / or B) is inserted between two naphthyl rings. In some preferred systems in which T and U form a 3-ring fused system with the naphthyl ring, at least one ring member (e.g., a ring member of the linker U or T) includes a cation exchange group (exemplary cation exchange groups include sulfonic acid, carboxyl, phosphate, imide, sulfonimide, sulfonamide, hydroxyl). The X and Y groups are linkers that can be covalently attached to a polymer structure (e.g., a polymer backbone linker). Exemplary X and Y groups can include one or more heteroatoms (O, N or S), optionally substituted C 1-10 Alkylene (i.e. -(CH 2 ) n-, wherein n is 1 to 10), carbocyclic arylene (such as optionally substituted phenylene or naphthylene), etc. Each of the units A, B, A' and B' of naphthyl may be optionally substituted at one or more available ring positions by groups such as halogen (F, Cl, Br, I), optionally substituted alkyl (including C 1-12 alkyl), nitro, cyano, optionally substituted alkoxy (including C 1-12 alkoxy), carbocyclic aromatic groups (e.g., phenyl, naphthyl), etc.

[0014] In a preferred aspect, the polymer may include a structure of Formula 1 below.

[0015] [Formula 1]

[0016]

[0017] Among them, X includes C 6 -C 20 The aromatic functional group, Y includes a cation exchange group, and n is an integer of 5 to 1,000.

[0018] The aromatic functional group may be represented by Chemical Formula 2 below.

[0019] [Chemical formula 2]

[0020]

[0021] Wherein, * indicates the connection site.

[0022] R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 Alkoxy or perfluoroalkoxy.

[0023] The cation exchange group may include at least one selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a hydroxyl group, and a combination thereof.

[0024] The cation exchange groups may be phosphate groups.

[0025] The polymer may be represented by Chemical Formula 3 below.

[0026] [Chemical formula 3]

[0027]

[0028] Among them, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0029] The polymer may be attached to the surface of the catalyst.

[0030] The catalyst may include at least one selected from the group consisting of platinum, palladium, cobalt, gold, ruthenium, tin, molybdenum, rhodium, iridium, bismuth, copper, yttrium and chromium. The catalyst may be platinum.

[0031] The ionomer may include at least one ionomer selected from the group consisting of a perfluorosulfonic acid polymer, a hydrocarbon-based polymer, and a polybenzimidazole polymer.

[0032] In some embodiments, a high temperature polymer electrolyte membrane fuel cell may include an electrode. The electrode may include a catalyst and a polymer attached to a surface of the catalyst, wherein the aromatic functional group is represented by the following chemical formula 2:

[0033] [Chemical formula 2]

[0034]

[0035] In Chemical Formula 2, * may represent a linking site, and R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 alkoxy or perfluoroalkoxy, and

[0036] Y may include at least one group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a hydroxyl group, and a combination thereof.

[0037] The catalyst may include at least one selected from the group consisting of platinum, palladium, cobalt, gold, ruthenium, tin, molybdenum, rhodium, iridium, bismuth, copper, yttrium, and chromium.

[0038] In addition, the present disclosure provides a method for preparing a high temperature polymer electrolyte membrane fuel cell, including preparing a polymer having a binaphthyl functional group, preparing an electrode including a catalyst, an ionomer and the polymer, and stacking the electrodes on opposite sides of an electrolyte membrane.

[0039] Herein, preparing a polymer may include preparing a compound B represented by the following Chemical Formula 5 by subjecting a compound A represented by the following Chemical Formula 4 to a Suzuki-Miyaura reaction, preparing a compound C represented by the following Chemical Formula 6 by subjecting the compound B to a demethylation reaction, and preparing a polymer represented by the following Chemical Formula 7 by subjecting the compound C to a nucleophilic substitution reaction.

[0040] [Chemical formula 4]

[0041]

[0042] [Chemical formula 5]

[0043]

[0044] Among them, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0045] [Chemical formula 6]

[0046]

[0047] Among them, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0048] [Chemical formula 7]

[0049]

[0050] Among them, X includes C 6 -C 20 The aromatic functional group, Y includes a cation exchange group, and n is an integer of 5 to 1,000.

[0051] In the Suzuki-Miyaura reaction, compound A reacts with 2,5-dialkoxy-1,4-dibromobenzene to produce compound B.

[0052] In the nucleophilic substitution reaction, compound C reacts with phosphorus oxychloride (POCl 3 ) to produce a polymer represented by Chemical Formula 7. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] The above-mentioned and other features of the present disclosure will now be described in detail with reference to certain exemplary embodiments of the present disclosure illustrated in the accompanying drawings, which are described hereinafter by way of illustration only and thus do not limit the present disclosure, and in which:

[0054] Figure 1 A high temperature polymer electrolyte membrane fuel cell according to the present disclosure is shown;

[0055] Figure 2 shows the results of TGA (thermogravimetric analysis) of preparation examples according to the present disclosure; and

[0056] Figure 3 The oxygen reduction reaction (ORR) activities of the Examples and Comparative Examples according to the present disclosure are shown. DETAILED DESCRIPTION

[0057] From the following preferred embodiments in conjunction with the accompanying drawings, the above and other purposes, features and advantages of the present disclosure will be more clearly understood. However, the present disclosure is not limited to the embodiments disclosed herein and can be modified into different forms. These embodiments are provided to fully explain the present disclosure and fully convey the spirit of the present disclosure to those skilled in the art.

[0058] Throughout the accompanying drawings, the same reference numerals will indicate the same or similar elements. For the sake of clarity of the present disclosure, the size of the structure is depicted as being larger than its actual size. It will be understood that although various elements may be described herein using terms such as "first", "second", etc., these elements are not limited by these terms. These terms are only used to distinguish one element from another. For example, without departing from the scope of the present disclosure, the "first" element discussed below may be referred to as the "second" element. Similarly, the "second" element may also be referred to as the "first" element. As used herein, unless the context clearly indicates otherwise, the singular form is intended to also include the plural form.

[0059] The terms used herein are only used for the purpose of describing specific embodiments, and are not intended to limit the present disclosure. As used herein, unless the context clearly indicates otherwise, the singular forms "a", "one" and "the" are intended to also include plural forms. These terms are only intended to distinguish one component from another component, and these terms do not limit the nature, order or sequence of the constituent components. It should also be understood that when the terms "include" and / or "include" are used in this specification, it specifies the presence of the features, wholes, steps, operations, elements and / or parts, but does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, parts and / or their combinations. As used in this article, the term "and / or" includes any and all combinations of one or more related listed items. Throughout the specification, unless explicitly described to the contrary, the word "include" and variants such as "include" or "contain" will be understood to mean including the elements, but do not exclude any other elements. In addition, the terms "unit", "device", "piece" and "module" described in the specification are meant to be used to process at least one function and operation unit, and can be implemented by hardware components or software components and their combinations.

[0060] Although the exemplary embodiments are described as using a plurality of units to perform the exemplary processes, it is to be understood that the exemplary processes may also be performed by one or more modules.

[0061] Unless otherwise specified or apparent from the context, as used herein, the term "about" should be understood to be within the normal tolerance range in the art, such as within 2 standard deviations of the mean. "About" can be understood to be within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05% or 0.01% of the value. Unless the context clearly indicates otherwise, all numerical values ​​provided herein are modified by the term "about".

[0062] Furthermore, it will be understood that when an element such as a layer, film, region, or sheet is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present therebetween. Similarly, when an element such as a layer, film, region, or sheet is referred to as being "under" another element, it can be directly under the other element or intervening elements may be present therebetween.

[0063] As used herein, the term "ionomer" refers to a polymer material or resin comprising ionizing groups attached (e.g., covalently bonded) to the backbone of the polymer as pendant groups. Preferably, such ionizing groups may be functionalized to have ionic properties, such as cations or anions.

[0064] The ionomer may suitably include one or more polymers selected from the group consisting of fluorine-based polymers (fluoro-based polymers), perfluorosulfone-based polymers, benzimidazole-based polymers, polyimide-based polymers, polyetherimide-based polymers, polyphenylene sulfide-based polymers, polysulfone-based polymers, polyethersulfone-based polymers, polyetherketone-based polymers, polyetheretherketone-based polymers, polyphenylquinoxaline-based polymers and polystyrene-based polymers.

[0065] As used herein, the term "filler" refers to a material added to a matrix or admixture to improve properties but not reacting or reactive with any other compound or chemical in the surrounding matrix or admixture. The filler may be in the form of particles, fibers or resins, and preferably, the filler may be particles.

[0066] As used in this article, the term "adhesive" refers to a resin or polymer material that can be polymerized or cured to form a polymer matrix. The adhesive can be cured (polymerized) or partially cured during a curing process (such as heating, UV radiation, electron beam treatment, chemical polymerization using an additive, etc.). Preferably, the adhesive of the present invention can include polyamic acid (polyamic acid), which can be polymerized into polyimide when heated. Preferably, adhesive according to the present invention generally refers to a polyimide adhesive.

[0067] Unless otherwise stated, all numerical values, values, and / or expressed results used in this article to represent the amount of components, reaction conditions, polymer compositions, and mixtures should be considered as approximate values, including various uncertainties that affect measurement, which inherently occur in obtaining these values, etc., and should therefore be understood in all cases as being modified by the term "about". In addition, when a numerical range is disclosed in this specification, the range is continuous and includes all values ​​from the minimum value of the range to its maximum value, unless otherwise specified. In addition, when such a range involves integer values, it includes all integers from the minimum value to the maximum value, unless otherwise specified.

[0068] Figure 1 A high temperature polymer electrolyte membrane fuel cell according to the present disclosure is shown. The high temperature polymer electrolyte membrane fuel cell 1 may include an electrolyte membrane 10 and an electrode 20 including a cathode 21 disposed on one side of the electrolyte membrane 10 and an anode 22 disposed on the other side of the electrolyte membrane 10 .

[0069] The electrode 20 may include a catalyst, an ionomer, and a polymer. Specifically, the positive electrode 21 and / or the negative electrode 22 may include a catalyst, an ionomer, and a polymer.

[0070] The catalyst may include at least one selected from the group consisting of platinum, palladium, cobalt, gold, ruthenium, tin, molybdenum, rhodium, iridium, bismuth, copper, yttrium, and chromium, and may particularly include platinum and an alloy thereof.

[0071] The ionomer may include at least one selected from the group consisting of a perfluorosulfonic acid polymer, a hydrocarbon-based polymer, and a polybenzimidazole polymer.

[0072] Currently, commercial electrodes for high temperature polymer electrolyte membrane fuel cells have problems with catalytic performance and durability degradation due to activity loss caused by electrochemical catalyst poisoning. Therefore, it is necessary to introduce anti-poisoning adsorption materials on the surface of the catalyst that prevent the adsorption of toxic materials and allow ions and gases to penetrate. In order to solve this problem, the electrode 20 of the present disclosure may include a polymer that is strongly adsorbed to the surface of the catalyst and is resistant to toxic materials.

[0073] When the polymer is introduced as a single molecule, it can leak to the outside along with the fuel or electrolyte. On the other hand, when the fuel (hydrogen / air), electrolyte (phosphoric acid) and reaction product (water) continuously enter and leave the system, when a polymer with a large size is provided, the leakage of the material can be minimized.

[0074] In addition, molecular weight is a factor that can have an impact on oxygen access by affecting the crystallinity, density, etc. of the polymer. Since the polymer is provided, the physical properties of the material can be controlled by adjusting its molecular weight. High molecular weight can achieve high crystallinity, low gas permeability, and high oxygen permeability.

[0075] The polymer may include a polymer having binaphthyl functional groups.

[0076] By introducing a binaphthyl group having, for example, a tweezer-like structure, the polymer is effective for obtaining porosity in an electrode and preventing phosphoric acid poisoning of a catalyst. Such a structure (e.g., as described as a tweezer-like structure) can be formed by a non-aromatic ring including a ring atom of each of the two naphthyl moieties of the binaphthyl functional group (e.g., 2 naphthyl ring atoms of each of the two naphthyl groups) and a cation exchange group (e.g., Y in the above chemical formula 1).

[0077] The polymer may be represented by Chemical Formula 1 below.

[0078] [Chemical formula 1]

[0079]

[0080] In Chemical Formula 1, X includes C 6 -C 20 The aromatic functional group, Y includes a cation exchange group, and n is an integer of 5 to 1,000.

[0081] Only when n satisfies the above range, it can have a form in which chemical properties based on the molecular weight and physical properties work together.

[0082] The aromatic functional group may be represented by Chemical Formula 2 below.

[0083] [Chemical formula 2]

[0084]

[0085] In Chemical Formula 2, * represents a linking site.

[0086] In formula 2, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 Alkoxy or perfluoroalkoxy.

[0087] The polymer is advantageously capable of being 1 and R 2 Various changes in the groups can control physical properties such as hydrophobicity, porosity, molecular density, etc., making it easy to form three-phase boundaries and optimize oxygen permeability.

[0088] The cation exchange group may include at least one selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a hydroxyl group, and a combination thereof, and particularly may include a phosphoric acid group.

[0089] The introduction of phosphate groups into the polymer has the effect of improving proton conductivity and promoting the formation of hydrophilic channels.

[0090] The presence of an appropriate amount of phosphoric acid electrolyte in the electrode and the effective distribution of the electrolyte can maximize the conductivity. The polymer according to the present disclosure has both binaphthyl and phosphoric acid functional groups, so it can have phosphoric acid nearby as a proton carrier or can act as a proton carrier itself, and in addition, its tweezer-like structure can prevent excessive entry of phosphoric acid, allowing oxygen to fully approach the surface of the catalyst to a certain extent.

[0091] The polymer may be represented by Chemical Formula 3 below.

[0092] [Chemical formula 3]

[0093]

[0094] In chemical formula 3, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0095] The polymer may be attached to the surface of the catalyst.

[0096] The polymers according to the present disclosure are electrochemically inert and are capable of capturing molecules, thereby inhibiting phosphate poisoning of the platinum catalyst surface.

[0097] The electrolyte membrane 10 may include the polymer in an amount of about 50 wt % to 99 wt %, about 60 wt % to 90 wt %, or about 70 wt % to 90 wt %. The remainder thereof may be additives such as a binder, a filler, and the like.

[0098] A method of preparing a high temperature polymer electrolyte membrane fuel cell may include: preparing a polymer having a binaphthyl functional group; obtaining an electrode including the polymer; and forming a cathode on one side of the electrolyte membrane and an anode on the other side of the electrolyte membrane.

[0099] Specifically, preparing the polymer may include preparing compound B represented by the following Chemical Formula 5 by subjecting compound A represented by the following Chemical Formula 4 to a Suzuki-Miyaura reaction, preparing compound C represented by the following Chemical Formula 6 by subjecting compound B to a demethylation reaction, and preparing a polymer represented by the following Chemical Formula 7 by subjecting compound C to a nucleophilic substitution reaction.

[0100] [Chemical formula 4]

[0101]

[0102] [Chemical formula 5]

[0103]

[0104] In Chemical Formula 5, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0105] [Chemical formula 6]

[0106]

[0107] In Chemical Formula 6, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0108] [Chemical formula 7]

[0109]

[0110] In Chemical Formula 7, X includes C 6 -C 20 The aromatic functional group, Y includes a cation exchange group, and n is an integer of 5 to 1,000.

[0111] In the Suzuki-Miyaura reaction, the compound A represented by Chemical Formula 4 is reacted with 2,5-dialkoxy-1,4-dibromobenzene. Specifically, 3,3'-bis(dihydroxyborane)-2,2'-dimethoxy-1,1'-binaphthyl and 2,5-dialkoxy-1,4-dibromobenzene are reacted with 10 mol% of Pd(PPh 3 ) 4 、Ba(OH) 2 ·H 2 O, 4-dioxane and H 2O to synthesize a compound B represented by Chemical Formula 5, which is a binaphthyl polymer containing a methoxy group.

[0112] In the demethylation reaction, the methyl group of compound A is removed and a hydroxyl group is added. Specifically, compound C represented by Chemical Formula 6 can be reacted with BBr 3 It is prepared by reacting with dichloromethane (DCM) for 3 to 5 hours.

[0113] In a nucleophilic substitution reaction, compound C reacts with phosphorus oxychloride (POCl 3 ) to react so that the polymer includes a phosphate group. Specifically, the polymer represented by Chemical Formula 7 can be obtained by reacting Compound B with POCl 3 , pyridine and H 2 O reaction to prepare.

[0114] The polymer may include a phosphate group and may be represented by Chemical Formula 9 below.

[0115] [Chemical formula 9]

[0116]

[0117] In Chemical Formula 9, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0118] The following reaction formula 1 shows a reaction for preparing a polymer according to an exemplary embodiment of the present disclosure.

[0119] [Reaction formula 1]

[0120]

[0121] The polymer according to the present disclosure is prepared by a relatively easy and simple synthesis route as described above, has few side reactions, and is therefore effective for commercialization, large-scale production, and economic efficiency. In addition, the polymer contains a phosphate group and a binaphthyl group, thereby preventing phosphoric acid poisoning of the catalyst due to strong interaction with phosphoric acid and porosity, and improving electrochemical performance.

[0122] A better understanding of the present disclosure can be obtained through the following examples. However, these examples should not be interpreted as limiting the technical spirit of the present disclosure.

[0123] Preparation Example

[0124] 1 equivalent of 3,3'-bis(dihydroxyborane)-2,2'-dimethoxy-1,1'-binaphthyl, 1 equivalent of 2,5-dialkoxy-1,4-dibromobenzene, 10 mol% of Pd(PPh 3 ) 4 and 3 equivalents of Ba(OH) 2 ·H 2 O and 1,4-dioxane and H 2 O (0.25 M) and stirred at 90° C. for 12 hours. After the solvent was removed from the reaction solution under reduced pressure, 4 equivalents of BBr 3 and dichloromethane (0.25 M), and the dimethylation reaction was carried out at room temperature for 4 hours. Thereafter, 2 equivalents of POCl 3 and pyridine (0.25 M) were added to the reaction material and stirred at room temperature. After 12 hours, distilled water (1.0 M) was added thereto, followed by a reaction for 6 hours, thereby preparing a polymer represented by the following chemical formula.

[0125]

[0126] Among them, R 1 and R 2 Each independently includes substituted or unsubstituted C 1 -C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

[0127] Example

[0128] By adding 10 mg of 50 wt% TKK Pt / C (TEC10E50E loading: 20 μg / cm 2 ), IPA (isopropyl alcohol) and DIW as solvents, a perfluorosulfonic acid polymer as an ionomer, and 1 mg of the polymer prepared according to the Preparation Example to prepare an electrode.

[0129] Comparative Example

[0130] An electrode was prepared in the same manner as in Example, except that no polymer was added.

[0131] Test Example 1: Confirmation of Thermal Stability

[0132] In order to confirm the thermal stability of the polymer prepared in the preparation example, TGA (thermogravimetric analysis) was performed under nitrogen and air conditions. The temperature at which 5% weight loss occurred based on the initial weight was denoted as T d .

[0133] Figure 2The results of TGA according to Example 1 of the present disclosure are shown. Referring to this, the decomposition temperature was measured to be 500°C under nitrogen conditions, and the decomposition temperature was measured to be 400°C under air conditions, which was evaluated to be significantly higher than the typical decomposition temperature range of 150 to 200°C for medium / high temperature polymer electrolyte membrane fuel cells, confirming that the polymer according to the present disclosure has excellent thermal stability.

[0134] Test Example 2: Confirmation of anti-poisoning effect

[0135] In order to confirm the anti-poisoning effect of the intrinsic microporous polymer, the electrodes of the examples and comparative examples were prepared. 2 Saturated 0.1M HClO 4 and O 2 Saturated 0.1M HClO 4 Under the condition of +0.05M phosphoric acid, the ORR (oxygen reduction reaction) activity of the electrodes of the examples and comparative examples was measured. The results are shown in the following Tables 1 and Figure 3 middle.

[0136] [Table 1]

[0137] category △MA(%) <![CDATA[△E 1 / 2 (mV)]]> Comparative Example 58 39 Example 57 35

[0138] Figure 3 The measurement results of oxygen reduction reaction (ORR) activity according to the embodiment and comparative example of the present disclosure are shown. With reference to this, the half-wave potential difference measured in the comparative example is 39mV, while the half-wave potential difference measured in the embodiment is 35mV. Compared with the comparative example, the mass active reduction rate (%) is smaller in the embodiment, and the reduction rate in the embodiment is about 1 / 4, confirming that the electrode according to the embodiment includes the polymer according to the present disclosure and therefore has an anti-poisoning effect in a phosphoric acid electrolyte environment.

[0139] As is apparent from the above description, a fuel cell according to the present disclosure includes a polymer containing a phosphoric acid group and a binaphthyl group, thereby preventing phosphoric acid poisoning of a catalyst due to strong interaction with phosphoric acid and porosity and increasing electrochemical performance.

[0140] The effects of the present disclosure are not limited to the above-mentioned effects. It should be understood that the effects of the present disclosure include all effects that can be inferred from the description of the present disclosure.

[0141] Although the embodiments of the present disclosure have been described, those skilled in the art will recognize that the present disclosure can be embodied in other specific forms without changing its technical spirit or its basic features. Therefore, the above embodiments should be understood to be non-restrictive and illustrative in any way.

Claims

1. A polymer electrolyte membrane fuel cell, comprising: Electrolyte membrane; as well as an electrode including a cathode disposed on one side of the electrolyte membrane and an anode disposed on the other side of the electrolyte membrane, The electrode comprises a catalyst, an ionomer and a polymer containing a binaphthyl functional group.

2. The polymer electrolyte membrane fuel cell according to claim 1, wherein the polymer is represented by the following Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, X includes C6-C 20 The aromatic functional group, Y includes a cation exchange group, and n is an integer of 5 to 1,000.

3. The polymer electrolyte membrane fuel cell according to claim 2, wherein the aromatic functional group is represented by the following Chemical Formula 2: [Chemical formula 2] In Chemical Formula 2, * represents a linking site, and R1 and R2 each independently include a substituted or unsubstituted C1-C 20 Alkoxy or perfluoroalkoxy.

4. The polymer electrolyte membrane fuel cell according to claim 2, wherein the cation exchange group comprises at least one selected from the group consisting of sulfonic acid group, carboxyl group, phosphoric acid group, imide group, sulfonimide group, sulfonamide group, hydroxyl group and combinations thereof.

5. The polymer electrolyte membrane fuel cell according to claim 4, wherein the cation exchange group is a phosphate group.

6. The polymer electrolyte membrane fuel cell according to claim 1, wherein the polymer is represented by the following Chemical Formula 3: [Chemical formula 3] In Chemical Formula 3, R1 and R2 each independently include substituted or unsubstituted C1-C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

7. The polymer electrolyte membrane fuel cell according to claim 1, wherein the polymer is attached to a surface of the catalyst.

8. The polymer electrolyte membrane fuel cell according to claim 1, wherein the catalyst comprises at least one selected from the group consisting of platinum, palladium, cobalt, gold, ruthenium, tin, molybdenum, rhodium, iridium, bismuth, copper, yttrium and chromium.

9. The polymer electrolyte membrane fuel cell according to claim 8, wherein the catalyst is platinum.

10. The polymer electrolyte membrane fuel cell according to claim 1, wherein the ionomer comprises at least one selected from the group consisting of a perfluorosulfonic acid polymer, a hydrocarbon-based polymer, and a polybenzimidazole polymer.

11. A polymer electrolyte membrane fuel cell, comprising: an electrode comprising a catalyst and a polymer attached to a surface of the catalyst, The polymer is represented by the following chemical formula 1: [Chemical formula 1] In Chemical Formula 1, X includes C6-C 20 an aromatic functional group, Y comprises a cation exchange group, and n is an integer from 5 to 1000, wherein Y comprises at least one selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a hydroxyl group, and a combination thereof, The aromatic functional group is represented by the following chemical formula 2: [Chemical formula 2] In Chemical Formula 2, * represents a linking site, and R1 and R2 each independently include a substituted or unsubstituted C1-C 20 Alkoxy or perfluoroalkoxy.

12. The polymer electrolyte membrane fuel cell according to claim 11, wherein the catalyst comprises at least one selected from the group consisting of platinum, palladium, cobalt, gold, ruthenium, tin, molybdenum, rhodium, iridium, bismuth, copper, yttrium and chromium.

13. A method for preparing a polymer electrolyte membrane fuel cell, comprising: Preparation of polymers having binaphthyl functional groups; preparing an electrode comprising a catalyst, an ionomer and the polymer; as well as The electrodes are stacked on respective opposite sides of an electrolyte membrane.

14. The method of claim 13, wherein preparing the polymer comprises: Compound B represented by the following Chemical Formula 5 is prepared by subjecting Compound A represented by the following Chemical Formula 4 to a Suzuki-Miyaura reaction; preparing a compound C represented by the following Chemical Formula 6 by subjecting the compound B to a demethylation reaction; and A polymer represented by the following Chemical Formula 7 is prepared by subjecting Compound C to a nucleophilic substitution reaction, [Chemical formula 4] [Chemical formula 5] In Chemical Formula 5, R1 and R2 each independently include substituted or unsubstituted C1-C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer from 5 to 1000; [Chemical formula 6] In Chemical Formula 6, R1 and R2 each independently include substituted or unsubstituted C1-C 20 alkoxy or perfluoroalkoxy, and n is an integer from 5 to 1000; and [Chemical formula 7] In Chemical Formula 7, X includes C6-C 20 The aromatic functional group, Y includes a cation exchange group, and n is an integer of 5 to 1,000. 15 . The method according to claim 14 , wherein in the Suzuki-Miyaura reaction, compound A reacts with 2,5-dialkoxy-1,4-dibromobenzene to produce compound B. 16 . The method according to claim 14 , wherein in the nucleophilic substitution reaction, compound C reacts with phosphorus oxychloride to produce a polymer represented by Chemical Formula 7.

17. The method according to claim 14, wherein the aromatic functional group is represented by the following Chemical Formula 8: [Chemical formula 8] In Chemical Formula 8, * represents a linking site, and R1 and R2 each independently include a substituted or unsubstituted C1-C 20 Alkoxy or perfluoroalkoxy.

18. The method according to claim 14, wherein the cation exchange group comprises at least one selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a hydroxyl group, and a combination thereof.

19. The method according to claim 13, wherein the polymer is represented by the following Chemical Formula 9: [Chemical formula 9] In Chemical Formula 9, R1 and R2 each independently include substituted or unsubstituted C1-C 20 An alkoxy group or a perfluoroalkoxy group, and n is an integer of 5 to 1,000.

20. The method of claim 13, wherein the polymer is attached to the surface of the catalyst.

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