Patent Application
20170309940
The present specification claims priority to and the benefits of Korean Patent Application No. 10-2015-0014693, filed with the Korean Intellectual Property Office on Jan. 30, 2015, the entire contents of which are incorporated herein by reference.
The present specification relates to a compound including an aromatic ring and a polymer electrolyte membrane using the same.
A fuel cell is an energy conversion device directly converting chemical energy of fuel into electric energy. In other words, a fuel cell employs a power generation method utilizing a fuel gas and an oxidizer, and using electrons generated during the oxidation and reduction reactions thereof to produce power. A membrane-electrode assembly (MEA) of a fuel cell is a part where an electrochemical reaction of hydrogen and oxygen occurs, and is formed with a cathode, an anode and an electrolyte membrane, that is, an ion conductive electrolyte membrane.
A redox flow battery (oxidation-reduction flow battery) is a system charged and discharged by active materials included in a liquid electrolyte being oxidized and reduced, and is an electrochemical storage device directly storing chemical energy of the active materials as electric energy. A unit cell of the redox flow battery includes an electrode, an electrolyte and an ion-exchange membrane (electrolyte membrane).
Due to their high energy efficiency and environmental friendly properties of low contaminant emissions, fuel cells and redox flow batteries have been researched and developed as a next generation energy source.
A core constituent in a fuel cell and a redox flow battery is a polymer electrolyte membrane capable of cation exchange, and properties of 1) excellent proton conductivity, 2) preventing electrolyte cross over, 3) high chemical resistance, 4) strengthening mechanical properties and/or 4) low swelling ratio are favorably required. The polymer electrolyte membrane is divided into fluorine-based, partial fluorine-based, hydrocarbon-based and the like, and the hydrocarbon-based polymer electrolyte membrane has an advantage of low costs compared to the fluorine-based electrolyte membrane.
As materials of the hydrocarbon-based polymer electrolyte membrane, monomers having a structure in which a cation transfer functional group is directly attached to the benzene ring of the polymer main chain or is away from the polymer main chain through a carbonyl functional group have been generally used, however, studies for solving problems of reactivity and durability deterioration have been continuously required.
The present specification is directed to providing a compound including an aromatic ring and a polymer electrolyte membrane using the same.
One embodiment of the present specification provides a compound represented by the following Chemical Formula 1:
In Chemical Formula 1,
R1 and R2 are the same as or different from each other, and each independently a halogen group or a hydroxyl group,
R3 is S, O, CF2, NH or SO2,
R4 is —SO3H, —SO3−M+, —COOH, —COO−M+, —OCF2CF2SO3H or —OCF2CF2 SO3−M+,
M is a group 1 element, and
n is an integer of 2 to 20.
One embodiment of the present specification provides a polymer including a monomer derived from the compound of Chemical Formula 1.
One embodiment of the present specification provides a polymer electrolyte membrane including a polymer including a monomer derived from the compound of Chemical Formula 1.
In addition, one embodiment of the present specification provides a membrane-electrode assembly including an anode; a cathode; and the polymer electrolyte membrane described above provided between the anode and the cathode.
In addition, one embodiment of the present specification provides a polymer electrolyte-type fuel cell including two or more of the membrane-electrode assemblies described above; a stack including a bipolar plate provided between the membrane-electrode assemblies; a fuel supplying unit supplying fuel to the stack; and an oxidizer supplying unit supplying an oxidizer to the stack.
One embodiment of the present specification also provides a redox flow battery including a positive electrode cell including a positive electrode and a positive electrode liquid electrolyte; a negative electrode cell including a negative electrode and a negative electrode liquid electrolyte; and the polymer electrolyte membrane described above provided between the positive electrode cell and the negative electrode cell.
A monomer derived from a compound according to one embodiment of the present specification provides high reactivity in a polymerization reaction process.
A polymer electrolyte membrane prepared using a polymer including a monomer derived from a compound according to one embodiment of the present specification has excellent ion conductivity. In a polymer electrolyte membrane prepared using a polymer including a monomer derived from a compound according to one embodiment of the present specification, phase separation readily occurs, and resultantly, ion conductivity is enhanced.
A polymer electrolyte membrane according to one embodiment of the present specification has excellent durability.
A fuel cell and/or a redox flow battery including the polymer electrolyte membrane have excellent durability and efficiency.
100: Electrolyte Membrane
200
a: Anode
200
b: Cathode
10, 20: Tank
11, 21: Pump
31: Electrolyte Membrane
32: Positive Electrode Cell
33: Negative Electrode Cell
41: Positive Electrode Liquid Electrolyte
42: Negative Electrode Liquid Electrolyte
60: Stack
70: Oxidizer Supplying Unit
80: Fuel Supplying Unit
81: Fuel Tank
82: Pump
Hereinafter, the present specification will be described in more detail.
One embodiment of the present specification provides a compound represented by Chemical Formula 1.
Specifically, the compound represented by Chemical Formula 1 includes a sulfonyl group (—SO2—) as a linker connecting two benzene rings. In existing technologies, a carbonyl group has been used as a linker. Using a structure introducing a sulfonyl group instead of a carbonyl group as in the compound represented by Chemical Formula 1 has an advantage of enhancing durability of an electrolyte membrane including the same. This is an effect caused by chemical stability of a sulfonyl group that is not readily decomposed by strong acids of the electrolyte or radicals generated in the electrolyte.
Meanwhile, in the compound represented by Chemical Formula 1, R1 and R2 that are each a halogen group or a hydroxyl group are each located in an ortho position and a para position with respect to the sulfonyl group (—SO2), a linker connecting the two benzene rings. Due to an electron withdrawing effect of the sulfonyl group, reactivity of R1 and R2 located in ortho and para with respect to the sulfonyl group readily increases in a nucleophilic substitution reaction of the benzene ring, and as a result, there is an advantage in that reactivity is enhanced in the polymerization reaction.
According to one embodiment of the present specification, M, a group 1 element, may be Li, Na or K.
According to one embodiment of the present specification, R1 and R2 are each fluorine (F), and in this case, the advantage may be maximized.
According to one embodiment of the present specification, R3 is S, NH or SO2.
According to one embodiment of the present specification, R3 is S or SO2. In this case, there is an advantage in that the compound represented by Chemical Formula 1 is more readily synthesized.
According to one embodiment of the present specification, R3 is SO2. When R3 is SO2, an electrolyte membrane including the same may exhibit enhanced durability due to chemical stability of the sulfonyl group that is not readily decomposed by strong acids of the electrolyte or radicals generated in the electrolyte.
Meanwhile, as the n value increases, the length of the pendant in a polymer including a monomer derived from the compound represented by Chemical Formula 1 increases, and as a result, phase separation readily occurs due to favorable agglomeration of hydrophilic parts, which leads to an advantage of exhibiting excellent ion conductivity when used in a polymer electrolyte membrane.
According to one embodiment of the present specification,
R4 is —SO3H, —SO3−M+, —OCF2CF2SO3H or —OCF2CF2 SO3−M+. R4 is included in the polymer electrolyte membrane and performs a role of an ion transfer functional group. A sulfonic acid group (—SO3H) absorbs a maximum of approximately 10 mole of water per 1 mole, and exhibits high proton conductivity of approximately 0.1 Scm−1.
According to one embodiment of the present specification, the compound represented by Chemical Formula 1 may be any one selected from among the following structures:
One embodiment of the present specification also provides a polymer including a monomer derived from the compound represented by Chemical Formula 1. As described above, the monomer has an advantage of exhibiting enhanced reactivity in the polymerization reaction.
In the polymer according to one embodiment of the present specification, the benzene ring substituted with R1 and R2 becomes a main chain, and with the sulfonyl group (—SO2—) as a linker, the benzene ring substituted with [—R3(CF2)nR4] is linked thereto in a pendant form.
In the present specification, the “monomer” means a structure including a compound in a divalent or higher form in a polymer by a polymerization reaction. Specifically, the monomer derived from the compound represented by Chemical Formula 1 may have a structure as follows. However, the structure is not limited thereto.
As described above, the polymer according to one embodiment of the present specification includes a monomer derived from the compound represented by Chemical Formula 1. Accordingly, an ion transfer functional group including a partial fluorine-based is present in a pendant form in the polymer, and an ion transfer functional groups are readily agglomerated in the polymer facilitating phase separation, and therefore, ion channels are readily formed, which resultantly leads to an advantage of obtaining an effect of enhancing ion conductivity in a polymer electrolyte membrane including the polymer.
According to one embodiment of the present specification, the polymer may be a random polymer. In this case, a polymer having a high molecular weight may be obtained using a simple polymerization method.
Herein, the monomer derived from the compound represented by Chemical Formula 1 performs a role of controlling ion conductivity of a polymer electrolyte membrane including the polymer, and a co-monomer (second monomer) in the remaining ratio polymerized in a random form performs a role of enhancing mechanical strength.
According to one embodiment of the present specification, the monomer derived from the compound represented by Chemical Formula 1 may be included in 0.1 mol % to 100 mol % of the whole polymer. Specifically, the polymer includes only the monomer derived from the compound represented by Chemical Formula 1. In another embodiment, the polymer may further include a second monomer in addition to the monomer derived from the compound represented by Chemical Formula 1. In this case, the content of the monomer derived from the compound represented by Chemical Formula 1 is preferably from 0.5 mol % to 65 mol %. More preferably, the content may be from 5 mol % to 65 mol %. A polymer including the monomer derived from the compound in the above-mentioned range has mechanical strength and high ion conductivity.
As the second monomer, those known in the art may be used. Herein, the second monomer may be used in one, two or more types.
Examples of the second monomer may include monomers forming perfluorosulfonic acid polymers, hydrocarbon-based polymers, polyimide, polyvinylidene fluoride, polyether sulfone, polyphenylene sulfide, polyphenylene oxide, polyphosphazene, polyethylene naphthalate, polyester, doped polybenzimidazole, polyetherketone, polysulfone, acids thereof, or bases thereof.
According to one embodiment of the present specification, the content of the co-monomer that is the second monomer in the polymer may be greater than 0% by weight and less than or equal to 99.9% by weight.
According to one embodiment of the present specification, when the polymer includes the second monomer, the polymer may be a random polymer.
One embodiment of the present specification also provides a polymer electrolyte membrane including the polymer. The polymer electrolyte membrane may exhibit effects described above.
In the present specification, the “electrolyte membrane” includes, as a membrane capable of exchanging ions, a membrane, an ion-exchange membrane, an ion-transfer membrane, an ion-conductive membrane, a separator, an ion-exchange separator, an ion-transfer separator, an ion-conductive separator, an ion-exchange electrolyte membrane, an ion-transfer electrolyte membrane, an ion-conductive electrolyte membrane or the like.
The polymer electrolyte membrane according to the present specification may be prepared using materials and/or methods known in the art except that the polymer electrolyte membrane includes a monomer derived from the compound represented by Chemical Formula 1.
According to another embodiment, a weight average molecular weight of the polymer included in the polymer electrolyte membrane may be greater than or equal to 500 and less than or equal to 5,000,000 (g/mol), specifically, greater than or equal to 20,000 and less than or equal to 2,000,000 (g/mol), and more specifically, greater than or equal to 50,000 and less than or equal to 1,000,000 (g/mol).
When the copolymer has a weight average molecular weight of greater than or equal to 500 and less than or equal to 5,000,000 (g/mol), mechanical properties of the electrolyte membrane do not decline, and proper polymer solubility is maintained, and as a result, the electrolyte membrane may be readily manufactured.
According to one embodiment of the present specification, the polymer electrolyte membrane has an ion exchange capacity (IEC) value of 0.01 mmol/g to 5 mmol/g. When the polymer electrolyte membrane has an ion exchange capacity value in the above-mentioned range, ion channels are formed in the polymer electrolyte membrane, and the polymer may exhibit ion conductivity.
According to one embodiment of the present specification, the electrolyte membrane may have a thickness of 1 μm to 500 μm, and specifically 10 μm to 200 μm. When the electrolyte membrane has a thickness of 1 μm to 500 μm, electric short and electrolyte material cross over are reduced, and an excellent cation conductivity property may be exhibited.
According to one embodiment of the present specification, the polymer electrolyte membrane has ion conductivity of greater than or equal to 0.001 S/cm and less than or equal to 0.5 S/cm, and specifically, greater than or equal to 0.01 S/cm and less than or equal to 0.5 S/cm.
According to another embodiment, ion conductivity of the polymer electrolyte membrane may be measured under a humidity condition. The humidity condition may mean a full humidity condition, may mean relative humidity (RH) of 10% to 100%, or may mean relative humidity (RH) of 30% to 100%.
According to one embodiment of the present specification, the polymer electrolyte membrane may have ion conductivity of greater than or equal to 0.001 S/cm and less than or equal to 0.5 S/cm, and the ion conductivity may be measured under relative humidity (RH) of 10% to 100%. According to another embodiment, the polymer electrolyte membrane may have ion conductivity of greater than or equal to 0.01 S/cm and less than or equal to 0.5 S/cm, and the ion conductivity may be measured under relative humidity (RH) of 30% to 100%.
According to one embodiment of the present specification, at least a part of the polymer may have a metal salt form. In addition, the metal salt may be substituted with an acid form.
Specifically, an electrolyte membrane including a polymer substituted with hydrogen (H) instead of metal M may be formed by adding an acid solution to a polymer having —SO3−M+ or —OCF2CF2SO3−M+ as R4 in Chemical Formula 1.
According to one embodiment of the present specification, general acid solutions may be used in the acid treatment, and specifically, hydrochloric acid or sulfuric acid may be used.
According to one embodiment of the present specification, the acid solution may have a concentration of greater than or equal to 0.1 M and less than or equal to 10 M, and specifically, greater than or equal to 1 M and less than or equal to 2 M. When the acid solution has a concentration of greater than or equal to 0.1 M and less than or equal to 10 M, substitution with hydrogen instead of metal M may be readily carried out without damaging the electrolyte membrane.
One embodiment of the present specification also provides a membrane-electrode assembly including an anode; a cathode; and the polymer electrolyte membrane described above provided between the anode and the cathode.
The membrane-electrode assembly (MEA) means an assembly of electrodes (cathode and anode) in which an electrochemical catalyst reaction of fuel and air occurs and a polymer membrane in which hydrogen ion transfer occurs, and is a single assembled unit in which electrodes (cathode and anode) and an electrolyte membrane are adhered.
The membrane-electrode assembly of the present specification has a form of a catalyst layer of an anode and a catalyst layer of a cathode being brought into contact with an electrolyte membrane, and may be prepared using common methods known in the art. As one example, the membrane-electrode assembly may be prepared through thermocompressing the cathode; the anode; and the electrolyte membrane located between the cathode and the anode at 100° C. to 400° C. while sticking these together.
The anode electrode may include an anode catalyst layer and an anode gas diffusion layer. The anode gas diffusion layer may again include an anode micropore layer and an anode electrode substrate.
The cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer. The cathode gas diffusion layer may again include a cathode micropore layer and a cathode electrode substrate.
The anode electrode catalyst layer is a place where an oxidation reaction of fuel occurs, and catalysts selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloys, platinum-osmium alloys, platinum-palladium alloys and platinum-transition metal alloys may be preferably used. The cathode electrode catalyst layer is a place where a reduction reaction of an oxidizer occurs, and platinum or platinum-transition metal alloys may be preferably used as catalysts. The catalysts may be used as they are, or may be used while being supported on a carbon-based carrier.
The process of introducing the catalyst layer may be carried out using common methods known in the art, and for example, a catalyst ink may be directed coated on the electrolyte membrane, or a catalyst ink may be coated on the gas diffusion layer to form the catalyst layer. Herein, the coating method of the catalyst ink is not particularly limited, and methods of spray coating, tape casting, screen printing, blade coating, die coating, spin coating or the like may be used. The catalyst ink may be typically formed with a catalyst, a polymer ionomer and a solvent.
The gas diffusion layer becomes a migration path of reaction gases and water while performing a role of a current conductor, and has a porous structure. Accordingly, the gas diffusion layer may be formed including a conductive substrate. As the conductive substrate, carbon paper, carbon cloth or carbon felt may be preferably used. The gas diffusion layer may be formed further including a micropore layer between the catalyst layer and the conductive substrate. The micropore layer may be used for enhancing fuel cell performance under a low humidity condition, and performs a role of allowing the electrolyte membrane to be under a sufficiently wet condition by having the amount of water escaping outside the gas diffusion layer being small.
One embodiment of the present specification provides a polymer electrolyte-type fuel cell including two or more of the membrane-electrode assemblies; a stack including a bipolar plate provided between the membrane-electrode assemblies; a fuel supplying unit supplying fuel to the stack; and an oxidizer supplying unit supplying an oxidizer to the stack.
When using the electrolyte membrane according to one embodiment of the present specification as an ion-exchange membrane of a fuel cell, effects described above may be obtained.
A fuel cell is an energy conversion device directly converting chemical energy of fuel into electric energy. In other words, a fuel cell employs a power generation method utilizing a fuel gas and an oxidizer, and using electrons generated during the oxidation and reduction reactions thereof to produce power.
The fuel cell may be prepared through common methods known in the art using the membrane-electrode assembly (MEA) described above. For example, the fuel cell may be prepared forming with the membrane-electrode assembly (MEA) prepared above and a bipolar plate.
The fuel cell of the present specification is formed including a stack, a fuel supplying unit and an oxidizer supplying unit.
The oxidizer supplying unit (70) performs a role of supplying an oxidizer to the stack (60). As the oxidizer, oxygen is typically used, and oxygen or air may be injected with a pump (70) to be used.
The fuel supplying unit (80) performs a role supplying fuel to the stack (60), and may be formed with a fuel tank (81) storing fuel, and a pump (82) supplying the fuel stored in the fuel tank (81) to the stack (60). As the fuel, hydrogen or hydrocarbon fuel in a gas or liquid state may be used. Examples of the hydrocarbon fuel may include methanol, ethanol, propanol, butanol or natural gas.
The fuel cell may include a polymer electrolyte fuel cell, a direct liquid fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell, a direct ethanol fuel cell, a direct dimethyl ether fuel cell or the like.
In addition, one embodiment of the present specification provides a redox flow battery including a positive electrode cell including a positive electrode and a positive electrode liquid electrolyte; a negative electrode cell including a negative electrode and a negative electrode liquid electrolyte; and the polymer electrolyte membrane according to one embodiment of the present specification provided between the positive electrode cell and the negative electrode cell.
A redox flow battery (oxidation-reduction flow battery) is a system charged and discharged by active materials included in a liquid electrolyte being oxidized and reduced, and is an electrochemical storage device directly storing chemical energy of the active materials as electric energy. A redox flow battery uses a principle of being charged and discharged from the exchange of electrons occurring when liquid electrolytes including active materials in different oxidation states meet with an ion-exchange membrane in between. A redox flow battery is generally formed with a tank holding a liquid electrolyte, a battery cell where charge and discharge occur, and a circulating pump for circulating the liquid electrolyte between the tank and the battery cell, and a unit cell of the battery cell includes an electrode, an electrolyte and an ion-exchange membrane.
When using the electrolyte membrane according to one embodiment of the present specification as an ion-exchange membrane of the redox flow battery, effects described above may be obtained.
The redox flow battery of the present specification may be prepared using common methods known in the art except that the redox flow battery includes the polymer electrolyte membrane according to one embodiment of the present specification.
As illustrated in
One embodiment of the present specification also provides a method for preparing the polymer electrolyte membrane. The polymer electrolyte membrane may be prepared using materials and/or methods known in the art except that a polymer including a monomer derived from the compound represented by Chemical Formula 1 is included. For example, the polymer electrolyte membrane may be prepared by preparing a polymer solution through adding the polymer to a solvent, and then forming a film using a solution casting method.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2015-0014693 | Jan 2015 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2016/001091 | 2/1/2016 | WO | 00 |
