Patent Application
20240136538
This application claims, under 35 U.S.C. § 119(a), the benefit of priority from Korean Patent Application No. 10-2022-0127064, filed on Oct. 5, 2022, the entire contents of which are incorporated herein by reference.
The present disclosure relates to an ionomer for a high-temperature polymer electrolyte membrane fuel cell. The ionomer may include a phosphorus (P)-containing functional group having proton conductivity and partially containing fluorine in the main chain thereof.
A high-temperature polymer electrolyte membrane fuel cell operating at high temperatures of 160° C. or greater is used in a dry environment without water. Therefore, as a binder for electrodes, Nafion, and the like for the existing low-temperature polymer electrolyte membrane fuel cell cannot be used. Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and the like having high thermal stability, are used as binders for electrodes of high-temperature polymer electrolyte membrane fuel cells, but they do not have proton conductivity, which is undesirable.
In order to improve electrode performance of the high-temperature polymer electrolyte membrane fuel cell, it is necessary to introduce an ionomer capable of transporting protons. However, since a material having proton conductivity is structurally hydrophilic, it may cause electrode poisoning and performance degradation by the generated water and phosphoric acid electrolyte of the high-temperature polymer electrolyte membrane fuel cell.
Accordingly, there is a great need for a novel ionomer that has proton conductivity, has high thermal stability, does not lose proton conductivity under dry conditions, and is resistant to acid.
In preferred aspects, provided is an ionomer capable of improving performance of a high-temperature polymer electrolyte membrane fuel cell.
The term “ionomer” as used herein refers to a polymeric material or resin that includes ionized groups attached (e.g., covalently bonded) to the backbone of the polymer as pendant groups. Preferably, such ionized groups may be functionalized to have ionic characteristics, e.g., cationic or anionic. In certain embodiments, the ionic characteristics may be implemented by phosphorus (P)-containing functional groups, e.g., phosphate group (e.g., —P(OH)2(O)) or a phosphonate group (e.g., —P(OR)2(O)).
The objects of the present disclosure are not limited to the foregoing. The objects of the present disclosure will be able to be clearly understood through the following description and to be realized by the means described in the claims and combinations thereof.
In an aspect, provided is an ionomer for a high-temperature polymer electrolyte membrane fuel cell, which may include a copolymer of a first repeat unit represented by Chemical Formula 1,
The copolymer may be an alternating copolymer, a random copolymer, or a block copolymer.
The copolymer may have a weight average molecular weight of about 30,000 g/mol to 100,000 g/mol.
The phosphorus (P)-containing functional group may include a phosphate group, a phosphonate group, or combinations thereof.
The copolymer may be represented by Chemical Formula 3,
The copolymer may be represented by Chemical Formula 4 below,
The compound may satisfy Relation 1,
In an aspect, provided is a high-temperature polymer electrolyte membrane fuel cell (“fuel cell”), including an electrolyte membrane, a cathode disposed on one surface of the electrolyte membrane, and an anode disposed on the remaining surface of the electrolyte membrane. Particularly, the cathode includes the ionomer described above.
In an aspect, provided is a method of preparing an ionomer for a high-temperature polymer electrolyte membrane fuel cell. The method includes steps of: preparing a first precursor compound represented by Chemical Formula 7 below, preparing a second precursor compound in which at least one of X5 to X8 is substituted with elemental bromine by reacting the first precursor compound with a compound containing elemental bromine, and substituting the elemental bromine with a phosphorus (P)-containing functional group by reacting the second precursor compound with a compound containing elemental phosphorus.
In Chemical Formula 7, each of R1 to R17 is independently hydrogen or fluorine (F), each of Y1 and Y2 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, each of X 5 to X8 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and m is an integer from 40 to 140.
The compound containing elemental bromine may include N-bromosuccinimide.
The compound containing elemental phosphorus may include triethyl phosphite.
The ionomer may include a copolymer represented by Chemical Formula 4 below.
In Chemical Formula 4, n is an integer from 40 to 140.
A copolymer represented by Chemical Formula 3 below may be obtained by adding an acid solution to the copolymer represented by Chemical Formula 4 and then performing heat treatment.
In Chemical Formula 3, m is an integer from 40 to 140.
The thus prepared copolymer satisfies Relation 1
In another aspect, provided is a vehicle including the fuel cell as described herein.
Other aspect of the invention are disclosed infra.
The above and other features of the present disclosure will now be described in detail with reference to certain exemplary embodiments thereof illustrated in the accompanying drawings, which are given hereinbelow by way of illustration only, and thus are not limitative of the present disclosure, and wherein:
The above and other objects, features and advantages of the present disclosure will be more clearly understood from the following preferred embodiments taken in conjunction with the accompanying drawings. However, the present disclosure is not limited to the embodiments disclosed herein, and may be modified into different forms. These embodiments are provided to thoroughly explain the disclosure and to sufficiently transfer the spirit of the present disclosure to those skilled in the art.
Throughout the drawings, the same reference numerals will refer to the same or like elements. For the sake of clarity of the present disclosure, the dimensions of structures are depicted as being larger than the actual sizes thereof. It will be understood that, although terms such as “first”, “second”, etc. may be used herein to describe various elements, these elements are not to be limited by these terms. These terms are only used to distinguish one element from another element. For instance, a “first” element discussed below could be termed a “second” element without departing from the scope of the present disclosure. Similarly, the “second” element could also be termed a “first” element. As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It will be further understood that the terms “comprise”, “include”, “have”, etc., when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof. Also, it will be understood that when an element such as a layer, film, area, or sheet is referred to as being “on” another element, it may be directly on the other element, or intervening elements may be present therebetween. Similarly, when an element such as a layer, film, area, or sheet is referred to as being “under” another element, it may be directly under the other element, or intervening elements may be present therebetween.
Unless otherwise specified, all numbers, values, and/or representations that express the amounts of components, reaction conditions, polymer compositions, and mixtures used herein are to be taken as approximations including various uncertainties affecting measurement that inherently occur in obtaining these values, among others, and thus should be understood to be modified by the term “about” in all cases. Further, unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”
Furthermore, when a numerical range is disclosed in this specification, the range is continuous, and includes all values from the minimum value of said range to the maximum value thereof, unless otherwise indicated. Moreover, when such a range pertains to integer values, all integers including the minimum value to the maximum value are included, unless otherwise indicated. In the present specification, when a range is described for a variable, it will be understood that the variable includes all values including the end points described within the stated range. For example, the range of “5 to 10” will be understood to include any subranges, such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, and the like, as well as individual values of 5, 6, 7, 8, 9 and 10, and will also be understood to include any value between valid integers within the stated range, such as 5.5, 6.5, 7.5, 5.5 to 8.5, 6.5 to 9, and the like. Also, for example, the range of “10% to 30%” will be understood to include subranges, such as 10% to 15%, 12% to 18%, 20% to 30%, etc., as well as all integers including values of 10%, 11%, 12%, 13% and the like up to 30%, and will also be understood to include any value between valid integers within the stated range, such as 10.5%, 15.5%, 25.5%, and the like.
It is understood that the term “vehicle” or “vehicular” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g. fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.
In general, a vehicle including a fuel cell (hereinafter referred to as a “fuel cell vehicle”) requires various levels of power from the fuel cell. When a relatively high level of power is required from the fuel cell, the volume of the fuel cell mounted within the vehicle may increase. As a result, the amount of space occupied by the fuel cell in the fuel cell vehicle increases, which may cause various problems.
The electrolyte membrane 10 may include any material commonly used in the technical field to which the present disclosure belongs. For example, the electrolyte membrane 10 may include polybenzimidazole (PBI) to which phosphoric acid is added.
The cathode 20 and the anode 30 may include a catalyst and an ionomer.
The catalyst may include any material commonly used in the technical field to which the present disclosure belongs. Examples thereof may include a noble metal catalyst such as platinum (Pt), a non-noble metal catalyst, an alloy catalyst thereof, and the like.
The ionomer may include a copolymer obtained by copolymerizing a first repeat unit represented by Chemical Formula 1 below and a second repeat unit represented by Chemical Formula 2 below,
Each of Y1 and Y2 may include hydrogen or an alkyl group having 1 to 4 carbon atoms.
The copolymer may include an alternating copolymer, a random copolymer, or a block copolymer of the first repeat unit and the second repeat unit.
The copolymer may have a weight average molecular weight of about 30,000 g/mol to 100,000 g/mol. When the weight average molecular weight of the compound is greater than about 100,000 g/mol, solubility may decrease, whereas when it is less than about 30,000 g/mol, the compound may be difficult to deposit on the electrode.
The ionomer according to the present disclosure is characterized in that fluorine (F) is introduced into the first repeat unit. The introduction of fluorine (F) increases hydrophobicity of the ionomer, thereby facilitating treatment of excessively generated water and phosphoric acid, which are problematic at the cathode 20, and increasing chemical stability in an acid atmosphere and under high-temperature conditions. This leads to reduced catalyst poisoning, and consequently, it is of great help in improving electrode performance of high-temperature polymer electrolyte membrane fuel cells.
The phosphorus (P)-containing functional group may be a functional group for proton conduction. The phosphorus (P)-containing functional group may include at least one selected from the group consisting of a phosphate group, a phosphonate group, and combinations thereof.
The phosphate group may be represented by Chemical Formula 5 below,
The phosphonate group may be represented by Chemical Formula 6 below,
The ionomer according to the present disclosure is characterized in that a phosphorus (P)-containing functional group having proton conductivity is introduced into the second repeat unit. In particular, by appropriately adjusting the proportion of introduction of the phosphorus (P)-containing functional group, proton conductivity and chemical stability may be increased in a balanced manner. The compound may satisfy Relation 1 below.
The copolymer may be obtained in a manner in which a polymer therefor may be synthesized and then subjected to bromination such that any one of X1 to X4 in the second repeat unit is substituted with bromine (Br), followed by substitution of bromine (Br) with a phosphorus (P)-containing functional group. Briefly, the proportion of introduction of bromine (Br) may be substantially the same as the proportion of introduction of the phosphorus (P)-containing functional group. Relation 1 can be said to express the degree of bromination of the compound differently. The degree of bromination of the compound may be analyzed through NMR spectroscopy.
When the proportion of introduction of the phosphorus (P)-containing functional group in the compound is less than about 28%, proton conductivity of the ionomer may be less, whereas when it is about 86% or greater, the effect of introduction of fluorine (F) may be deteriorated due to increased hydrophilicity of the ionomer.
The compound is preferably represented by Chemical Formula 3 below,
The compound is preferably represented by Chemical Formula 4 below,
A better understanding of the present disclosure may be obtained through the following examples. These examples are merely set forth to illustrate the present disclosure, and are not to be construed as limiting the scope of the present disclosure.
Partially fluorinated poly(arylene ether) (FPAE) was synthesized through the following reaction mechanism using components in the amounts shown in Table 1 below.
A specific preparation method was as follows.
(7) The product was precipitated in ethanol, filtered, and then dried.
(8) The result was dissolved in chloroform, reprecipitated in ethanol, filtered, and then dried to obtain partially fluorinated poly(arylene ether) (FPAE).
The amounts of components that were used and the properties of the product are shown in Table 1 below.
BFPAE was synthesized through the following reaction mechanism using components in the amounts shown in Table 2 below.
The amounts of components that were used and the properties of the product are shown in Table 2 below.
In order to control the degree of bromination of BFPAE according to Preparation Examples 1 to 3 and Comparative Preparation Example 1, NBS, which is a bromine precursor, was added in different amounts. Specifically, in Preparation Example 1, Preparation Example 2, Preparation Example 3, and Comparative Preparation Example 1, the molar ratio of FPAE to NBS was set to 1:1.5, 1:2, 1:3, and 1:5.
FPAE-PN represented by Chemical Formula 4 was synthesized through the following reaction mechanism using components in the amounts shown in Table 3 below.
The amounts of components that were used and the properties of the product are shown in Table 3 below.
FPAE-PA represented by Chemical Formula 3 was synthesized through the following reaction mechanism using components in the amounts shown in Table 4 below.
The amounts of components that were used and the properties of the product are shown in Table 4 below.
The performance of the high-temperature polymer electrolyte membrane fuel cell depending on the proportion of introduction of the phosphorus (P)-containing functional group in FPAE-PN was evaluated.
In FPAE-PN according to Preparation Example 1, the proportion of introduction of the phosphorus (P)-containing functional group resulting from the degree of bromination was 28%. In FPAE-PN according to Preparation Example 2, the proportion of introduction of the phosphorus (P)-containing functional group was 41%. In FPAE-PN according to Preparation Example 3, the proportion of introduction of the phosphorus (P)-containing functional group was 60%. In FPAE-PN according to Comparative Preparation Example 1, the proportion of introduction of the phosphorus (P)-containing functional group was 86%.
Respective high-temperature polymer electrolyte membrane fuel cells were manufactured using FPAE-PN of Preparation Examples 1 to 3, FPAE without introducing a phosphorus (P)-containing functional group in the process of Comparative Preparation Example 1, and FPAE-PN of Comparative Preparation Example 1 as the ionomer for a cathode, and were set as Examples 1 5 to 3, Comparative Example 1, and Comparative Example 2.
Each item in
With reference thereto, Comparative Examples 1 and 2 exhibited poor performance due to the solubility problem of the ionomer. All of Examples 1 to 3 showed greater performance than Comparative Examples 1 and 2, and in particular, Example 3, in which the proportion of introduction of the phosphorus (P)-containing functional group was 60%, exhibited the best performance.
Respective high-temperature polymer electrolyte membrane fuel cells were manufactured using FPAE, BFPAE, FPAE-PN, and FPAE-PA, which are the results of individual steps of Preparation Example 3, as the ionomer for a cathode, and were set as Comparative Example 3, Comparative Example 4, Example 4, and Example 5.
Each item in
Comparative Example 4 using BFPAE showed very poor performance, which is considered to be due to poisoning of the platinum catalyst by bromine (Br). In contrast, Examples 4 and 5 exhibited vastly superior performance compared to Comparative Examples 3 and 4, and in particular, Example 4 including a phosphonate group as the phosphorus (P)-containing functional group showed the best results. This is because of proper balancing between hydrophobicity due to the introduction of fluorine (F) and hydrophilicity due to the introduction of the phosphorus (P)-containing functional group.
As is apparent from the above description, an ionomer according to various exemplary embodiments of the present disclosure is capable of reducing resistance to proton conduction in the cathode, thereby achieving an improvement in performance of a high-temperature polymer electrolyte membrane fuel cell.
The use of the ionomer according to various exemplary embodiments of the present disclosure enables proton conductivity to be maintained while decreasing the amount of a phosphoric acid electrolyte that is used.
Since fluorine (F) is introduced into the main chain of the ionomer according to various exemplary embodiments of the present disclosure, it is possible to solve problems at the cathode such as overflow of phosphoric acid electrolyte and generated water, catalyst poisoning, decreased activity, etc.
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.
Although specific embodiments of the present disclosure have been described through the test examples and examples above, these examples are not construed as limiting the scope of the present disclosure, and various modifications and improvements by those skilled in the art using the basic concept of the present disclosure as defined in the following claims are also included in the scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0127064 | Oct 2022 | KR | national |
