WO2016089154A1 - Polymère et membrane électrolytique polymère en comprenant - Google Patents

Polymère et membrane électrolytique polymère en comprenant Download PDF

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WO2016089154A1
WO2016089154A1 PCT/KR2015/013206 KR2015013206W WO2016089154A1 WO 2016089154 A1 WO2016089154 A1 WO 2016089154A1 KR 2015013206 W KR2015013206 W KR 2015013206W WO 2016089154 A1 WO2016089154 A1 WO 2016089154A1
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group
formula
polymer
present specification
cathode
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PCT/KR2015/013206
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English (en)
Korean (ko)
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강에스더
한중진
김영제
정세희
류현욱
장용진
유소영
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주식회사 엘지화학
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Priority claimed from KR1020150134774A external-priority patent/KR20160067720A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201580066249.5A priority Critical patent/CN107001595B/zh
Priority to EP15865952.4A priority patent/EP3228646B1/fr
Priority to US15/531,702 priority patent/US10361447B2/en
Publication of WO2016089154A1 publication Critical patent/WO2016089154A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present specification relates to a polymer and a polymer electrolyte membrane including the same.
  • a fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy.
  • a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction.
  • the membrane electrode assembly (MEA) of a fuel cell is a portion in which an electrochemical reaction between hydrogen and oxygen occurs and is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane.
  • a redox flow battery (redox flow battery) is an electrochemical storage device that directly stores the chemical energy of an active material as electrical energy by redoxing and charging and discharging the active material contained in the electrolyte.
  • the unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).
  • Fuel cells and redox flow cells are being researched and developed as next generation energy sources due to their high energy efficiency and eco-friendly features with low emissions.
  • the key components of fuel cell and redox flow cell are polymer electrolyte membranes capable of cation exchange, including 1) excellent proton conductivity 2) prevention of crossover of electrolyte, 3) strong chemical resistance, 4) mechanical It is desirable to have properties of enhanced physical properties and / or 4) low swelling ratio.
  • the polymer electrolyte membrane is classified into fluorine-based, partially fluorine-based, hydrocarbon-based, and the like, and the partial fluorine-based polymer electrolyte membrane has a fluorine-based main chain, which has advantages of excellent physical and chemical stability and high thermal stability.
  • the partial fluorine-based polymer electrolyte membrane has a cation transfer functional group attached to the end of the fluorine-based chain, and thus has the advantages of a hydrocarbon-based polymer electrolyte membrane and a fluorine-based polymer electrolyte membrane.
  • the partial fluorine-based polymer electrolyte membrane has a problem that the cation conductivity is relatively low because the fine phase separation of the cation transport functional group and the control of the aggregation phenomenon are not effectively performed. Therefore, research has been conducted toward securing high cationic conductivity through the control of the distribution of sulfonic acid groups and microphase separation.
  • the present specification is to provide a polymer having a strong acid resistance and a polymer electrolyte membrane comprising the same.
  • first monomer represented by the formula (1); And different from the first monomer, and fluorine; And a second monomer having at least one of trifluoroalkyl groups.
  • A is -SO 3 H, -SO 3 - M + , -COOH, -COO - M + , -PO 3 H 2 , -PO 3 H - M + , -PO 3 2- 2M + , -O (CF 2 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 ) m PO 3 H 2, -O (CF 2) m PO 3 H - m + , or -O (CF 2) m PO 3 and 2- 2M +,
  • n 1 to 6
  • M is a group 1 element
  • R1 and R2 are the same as or different from each other, and each independently a halogen group
  • n is an integer from 1 to 10
  • the present disclosure provides a polymer electrolyte membrane including the polymer described above.
  • the present specification provides a reinforcing film comprising the polymer.
  • the present specification is an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.
  • the present specification is an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described reinforcement film provided between the anode and the cathode.
  • the present specification includes two or more of the aforementioned membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
  • the present specification is a positive electrode cell comprising a positive electrode and a positive electrode electrolyte;
  • a cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising the above-described polymer electrolyte membrane provided between the cathode cell and the anode cell.
  • the present specification is a positive electrode cell comprising a positive electrode and a positive electrode electrolyte;
  • a cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising the above-described reinforcement film provided between the positive electrode cell and the negative electrode cell.
  • a polymer electrolyte membrane including a polymer according to one embodiment of the present specification easily forms a hydrophilic-hydrophobic phase separation structure.
  • the polymer electrolyte membrane effectively forms a hydrophilic channel in the polymer electrolyte membrane by controlling the phase separation structure.
  • the polymer electrolyte membrane has excellent proton conductivity.
  • the result is a high performance of fuel cells and / or redox flow cells comprising the same.
  • the polymer electrolyte membrane including the polymer according to the exemplary embodiment of the present specification has a vanadium permeability superior to that of the polymer electrolyte membrane including Nafion in the prior art and has a vanadium redox flow battery (VRFB: Vanadium Redox Flow Battery) When applied to, the capacity reduction range of the electrolyte is excellent.
  • VRFB Vanadium Redox Flow Battery
  • the polymer electrolyte membrane according to one embodiment of the present specification prevents the electrical negativeness from being extremely divided, thereby enhancing acid resistance to radicals.
  • a redox flow battery including a reinforcing film may reduce crossover of vanadium ions.
  • FIG. 1 is a schematic diagram illustrating a principle of electricity generation of a fuel cell.
  • FIG. 2 is a view schematically showing an embodiment of a redox flow battery.
  • FIG 3 is a view schematically showing an embodiment of a fuel cell.
  • Example 4 is a view showing a single cell evaluation results of Example 2 of the present invention and Nafion.
  • the first monomer represented by Formula 1 and different from the first monomer, and fluorine; And a second monomer having at least one of trifluoroalkyl groups.
  • an S atom is used as a linker of the-[CR1R2] n- A structure and the benzene ring in the general formula (1).
  • S atoms due to the electron withdrawing character of-[CR1R2] n -A linked by S atoms, it is possible to provide a polymer that is easy to form and stable.
  • R1 and R2 are the same as or different from each other, and are each independently a halogen group. Specifically, R1 and R2 are each independently F; Cl; Br; And I can be selected from the group consisting of.
  • R1 and R2 substituted in the carbon adjacent to A in Formula 1 may serve to increase decationic.
  • the polymer according to an exemplary embodiment of the present specification is different from the first monomer, fluorine; And a second monomer having at least one of trifluoroalkyl groups.
  • the electric negative degree can be prevented from being extremely divided, and acid resistance to radicals can be enhanced.
  • n is an integer of 2 to 10. In another embodiment of the present specification, n is an integer of 2 to 6.
  • the monomer represented by Formula 1 may adjust the number of n.
  • n may be controlled by controlling the length of the structure in the parentheses, it may serve to facilitate the phase separation phenomenon of the polymer electrolyte membrane, it is possible to facilitate the movement of hydrogen ions in the polymer electrolyte membrane.
  • n is 2.
  • n 3.
  • n 4.
  • n is 5.
  • n is 6.
  • n 7.
  • n 8.
  • n 9.
  • n 10
  • A is -SO 3 H or -SO 3 - M + .
  • A is -SO 3 H.
  • any of formulas A 1 -SO 3 H or -SO 3 - M + may be the case, form a stable polymer chemically.
  • M is a Group 1 element.
  • the Group 1 element may be Li, Na, or K.
  • the monomer represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-9.
  • the second monomer is derived from a compound represented by Formula 2 or Formula 3 below.
  • A1 to A4 are the same as or different from each other, and each independently a hydroxyl group; Or a halogen group,
  • R3 to R6 are the same as or different from each other, and each independently hydrogen; An alkyl group; Fluorine; Haloalkyl group; Or a phenyl group,
  • S1 to S3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Haloalkyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • s1, s2 and s3 are each an integer of 1 to 4,
  • n m ' is an integer from 1 to 5
  • Formula 2 and Formula 3 are at least one fluorine; Or a haloalkyl group.
  • Formula 2 and Formula 3 in the present specification are at least one fluorine;
  • the meaning of being substituted with a haloalkyl group may be as follows.
  • the second monomer when the second monomer is derived from Formula 2, and L1 is CR3R4 or SiR5R6, it means that at least one of R3 to R6, S1 and S2 is a fluorine or haloalkyl group.
  • the second monomer is derived from Formula 2, wherein L 1 is C ⁇ O; O; S; Or in the case of SO 2 , at least one of S1 and S2 may mean a fluorine or haloalkyl group.
  • the second monomer when the second monomer is derived from Chemical Formula 2 and L1 is a substituted or unsubstituted fluorenylene group, at least one of substituents S1 and S2 of the fluorenylene group may be fluorine or halo. It may mean an alkyl group.
  • At least one of S 3 may mean a fluorine or haloalkyl group.
  • the second monomer is derived from Chemical Formula 2.
  • L1 is CR3R4.
  • R3 is a haloalkyl group.
  • R3 is a trifluoromethyl group.
  • R4 is a haloalkyl group.
  • R4 is a trifluoromethyl group.
  • the second monomer is derived from Chemical Formula 3.
  • m ' is 2.
  • S3 is a halogen group.
  • S3 is fluorine
  • A1 to A4 are fluorine.
  • A1 to A4 are hydroxy groups.
  • the second monomer is derived from a compound represented by any one of the following Formulas 2-1, 2-2 and 3-1 to 3-3.
  • A1 'to A4' are the same as or different from each other, and are each independently a halogen group.
  • the halogen group is fluorine; Goat; bromine; Or iodine.
  • the term "derived" means that a bond is broken or a new bond is generated while a substituent is separated, and the monomer derived from the compound may mean a repeating unit constituting the polymer.
  • the monomer may be included in the main chain in the polymer to constitute the polymer.
  • hydrogen may be separated from the hydroxy group (-OH) substituted with the above Chemical Formulas 2 and 3 and included in the polymer to form a repeating unit, that is, a monomer.
  • the polymer may further include a brancher.
  • Branchers herein serve to link or crosslink the polymer chains.
  • the brancher may directly constitute the main chain of the polymer, and may improve the mechanical density of the thin film.
  • the branched polymers of the present invention can be post-treated sulfonated by polymerizing branched hydrophobic blocks that do not contain acid substituents and branched hydrophilic blocks that include acid substituents. Without the post-sulfonation or cross-linking of the sulfonated polymer, the brancher directly forms the main chain of the polymer and maintains the mechanical density of the thin film. Minority blocks and hydrophilic blocks that impart ionic conductivity to the thin film may alternately lead to chemical bonding.
  • the polymer further includes a brancher derived from a compound of Formula 4 or a brancher represented by Formula 5 below.
  • X is S; O; CO; SO; SO 2 ; NR; Hydrocarbon-based or fluorine-based conjugates,
  • l is an integer from 0 to 10
  • Y1 and Y2 are the same as or different from each other, and each independently NRR; An aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group,
  • R is an aromatic ring substituted with a halogen group; Or an aliphatic ring substituted with a halogen group,
  • Z is a trivalent organic group.
  • a brancher derived from the compound of Formula 4 may include an aromatic ring substituted with a halogen group of each of Y1 and Y2; Or a halogen group in the aliphatic ring substituted with a halogen group may act as a branch while being separated from the aromatic ring or aliphatic ring.
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • the hydrocarbon-based means an organic compound consisting of only carbon and hydrogen, and includes a straight chain, branched chain, cyclic hydrocarbon, and the like, but is not limited thereto. In addition, it may include a single bond, a double bond or a triple bond, but is not limited thereto.
  • the fluorine-based conjugate means that some or all of the carbon-hydrogen bonds in the hydrocarbon system are substituted with fluorine.
  • the aromatic ring may be an aromatic hydrocarbon ring or an aromatic hetero ring, and may be monocyclic or polycyclic.
  • aromatic hydrocarbon ring monocyclic aromatic and naphthyl groups, binaphthyl groups, anthracenyl groups, phenanthrenyl groups, pyrenyl groups, peryllenyl groups, tetrasenyl groups, chrysenyl groups such as phenyl groups, biphenyl groups and terphenyl groups
  • polycyclic aromatics such as fluorenyl group, acenaphthasenyl group, triphenylene group, and fluoranthene group, and the like.
  • the aromatic heterocycle means a structure including one or more hetero atoms such as O, S, N, Se, or the like instead of a carbon atom in the aromatic hydrocarbon ring.
  • thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimid
  • the aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic hetero ring, and may be monocyclic or polycyclic.
  • Examples of the aliphatic ring include a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.
  • an organic group an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc. are mentioned.
  • This organic group may contain the bond and substituents other than hydrocarbon groups, such as a hetero atom, in the said organic group.
  • the organic group may be any of linear, branched and cyclic.
  • the trivalent organic group means a trivalent group having three bonding positions in an organic compound.
  • the organic group may form a cyclic structure, may form a cyclic structure, and may form a bond including a hetero atom so long as the effect of the invention is not impaired.
  • the bond containing hetero atoms such as an oxygen atom, a nitrogen atom, and a silicon atom
  • hetero atoms such as an oxygen atom, a nitrogen atom, and a silicon atom
  • the cyclic structure may include the aforementioned aromatic ring, aliphatic ring, and the like, and may be monocyclic or polycyclic.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl groups.
  • the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and especially cyclopentyl group, cyclohexyl group, and the like, but is not limited thereto.
  • l is 3 or more.
  • X is S.
  • X is a haloalkyl group.
  • X is NR.
  • Y1 and Y2 are the same as or different from each other, and are each independently a halogen substituted aromatic ring.
  • Y1 and Y2 are the same as or different from each other, and are each independently a fluorine-substituted aromatic hydrocarbon ring.
  • Y1 and Y2 are the same as or different from each other, and are each independently NRR.
  • Y1 and Y2 are each a fluorine substituted phenyl group.
  • 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl and the like are not limited thereto.
  • the compound represented by Formula 4 may be represented by any one of the following structures.
  • X, 1 and R are the same as defined in the formula (4).
  • Z in Chemical Formula 5 may be represented by any one of the following Chemical Formulas 5-1 to 5-4.
  • L2 To L8 are the same as or different from each other, and each independently a direct bond; -S-; -O-; -CO-; Or -SO 2- ,
  • R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • a, b, c, f, h, i and j are each an integer of 1 to 4,
  • d, e and g are each an integer of 1 to 3
  • k is an integer from 1 to 6
  • L1 is CO
  • L1 is SO 2 .
  • L1 is S.
  • L2 is CO
  • L2 is SO 2 .
  • L2 is S.
  • L3 is CO.
  • L3 is SO 2 .
  • L3 is S.
  • L4 is CO
  • L4 is SO 2 .
  • L5 is a direct bond
  • L6 is a direct bond
  • L7 is a direct bond
  • R10 to R20 are hydrogen.
  • R16 is a halogen group.
  • R16 is fluorine
  • brancher represented by Chemical Formula 5 may be represented by any one of the following structures.
  • the weight average molecular weight of the polymer is 500 g / mol to 2,000,000 g / mol.
  • the mechanical properties of the electrolyte membrane including the polymer are not lowered, and the solubility of the polymer may be maintained to facilitate the preparation of the electrolyte membrane.
  • the first monomer represented by Formula 1 and the first monomer and different from each other, fluorine; And the second monomer having at least one of trifluoroalkyl groups may constitute a random polymer.
  • the polymer including the monomer represented by the formula (1) has a structure of-[CR1R2] n -A in the form of a pendant (pendant), so that the A functional groups in the polymer are easily phase-separated to facilitate ion phase separation Can be formed. Therefore, the effect of improving the ionic conductivity of the polymer electrolyte membrane can be expected.
  • the content of the first monomer represented by Chemical Formula 1 in the polymer is 1 mol% to 99 mol% based on the total content of the polymer, and different from each other with the first monomer, fluorine ;
  • the content of the second monomer having at least one of the trifluoroalkyl groups is 1 mol% to 99 mol% based on the total content of the polymer.
  • the content of the first monomer represented by Chemical Formula 1 in the polymer is 50 mol% to 99 mol%, different from the first monomer, and different from fluorine; And the content of the second monomer having at least one of the trifluoroalkyl groups is 1 mol% to 50 mol% based on the total content of the polymer.
  • the first monomer of the polymer according to one embodiment of the present specification serves to increase the ionic conductivity
  • the second monomer serves to reduce the crossover.
  • those skilled in the art can adjust the contents of the first and second monomers to achieve the desired ion conductivity and at the same time prevent crossover.
  • the polymer includes a hydrophilic block and a hydrophobic block
  • the hydrophilic block is a block polymer including a first monomer represented by Chemical Formula 1.
  • the hydrophilic block and the hydrophobic block are included in the block polymer at a molar ratio of 1: 0.1 to 1:10. In one embodiment of the present specification, the hydrophilic block and the hydrophobic block are included in the block polymer in a molar ratio of 1: 0.1 to 1: 2. In another exemplary embodiment, the hydrophilic block and the hydrophobic block are included in the block polymer at a molar ratio of 1: 0.8 to 1: 1.2. In this case, the ion transport ability of the block polymer can be raised.
  • the monomer represented by Chemical Formula 1 in the hydrophilic block is contained in an amount of 0.01 mol% to 100 mol% based on the hydrophilic block.
  • the number average molecular weight of the hydrophilic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.
  • the number average molecular weight of the hydrophobic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.
  • the partition and division of the hydrophilic block and the hydrophobic block are clear, so that phase separation is easy, and ion transfer may be easy.
  • the hydrophilic block and the hydrophobic block are more clearly distinguished, and thus the ion transfer effect may be superior to that of the conventional polymer.
  • the block polymer refers to a polymer in which one block and one or more blocks different from the block are connected to each other by a main chain of the polymer.
  • the block polymer may include a hydrophilic block and a hydrophobic block.
  • the block polymer may include a hydrophilic block and a hydrophobic block including the monomer represented by Chemical Formula 1.
  • the first monomer and different from each other fluorine; And a second monomer having at least one of trifluoroalkyl groups is included in the hydrophobic block.
  • hydrophilic block herein is meant a block having an ion exchange group as a functional group.
  • the functional groups are -SO 3 H, -SO 3 - M +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M +, -PO 3 2- 2M +, -O (CF 2 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 may be at least one selected from the group consisting of 2M + -) m PO 3 H 2, -O (CF 2) m PO 3 H - m +, -O (CF 2) m PO 3 2.
  • M may be a metallic element. That is, the functional group may be hydrophilic.
  • block having an ion exchange group means a block containing an average of 0.5 or more represented by the number of ion exchange groups per structural monomer constituting the block, and an average of 1.0 or more ions per structural monomer. It is more preferable to have an exchanger.
  • hydrophobic block herein is meant the polymer block which is substantially free of ion exchange groups.
  • block having substantially no ion exchange group in the present specification means a block having an average of less than 0.1 represented by the number of ion exchange groups per structural monomer constituting the block, and more preferably 0.05 or less on average. It is more preferable if it is a block which does not have an ion exchange group at all.
  • the present disclosure provides a polymer electrolyte membrane including the polymer described above.
  • a polymer including a monomer derived from the compound according to an exemplary embodiment of the present specification it has high mechanical strength and high ionic conductivity, and may facilitate phase separation of the electrolyte membrane.
  • electrolyte membrane is a membrane capable of exchanging ions, such as membrane, ion exchange membrane, ion transfer membrane, ion conductive membrane, separator, ion exchange membrane, ion transfer membrane, ion conductive separator, ion exchange electrolyte membrane, ion And a transfer electrolyte membrane or an ion conductive electrolyte membrane.
  • the polymer electrolyte membrane according to one embodiment of the present specification may be prepared using materials and / or methods known in the art, except for including a polymer including a monomer derived from the compound.
  • the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.5 S / cm or less. In another exemplary embodiment, the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.3 S / cm or less.
  • the ionic conductivity of the polymer electrolyte membrane may be measured under humidification conditions.
  • the humidification condition may mean 10% to 100% relative humidity (RH).
  • the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5.0 mmol / g.
  • IEC ion exchange capacity
  • the thickness of the polymer electrolyte membrane is 1 ⁇ m to 500 ⁇ m.
  • the polymer electrolyte membrane having the above range thickness lowers an electrical short and a cross over of an electrolyte material, and may exhibit excellent cation conductivity characteristics.
  • the substrate In one embodiment of the present specification, the substrate; And it provides a reinforcing film comprising the polymer described above.
  • the 'reinforcement membrane' is an electrolyte membrane including a substrate that is a reinforcing material, and a membrane capable of exchanging ions, and includes a substrate, an ion exchange membrane, an ion transfer membrane, and an ion conductive membrane.
  • Separator ion exchange membrane, ion transfer membrane, ion conductive separator, ion exchange electrolyte membrane, ion transfer electrolyte membrane or ion conductive electrolyte membrane and the like.
  • the substrate may mean a support having a three-dimensional network structure
  • the reinforcing film including the substrate and the polymer may include one surface of the polymer, a surface facing the surface, and a pore region inside the substrate. It may mean that it is included in at least part of. That is, the reinforcing film of the present specification may be provided in a form in which the polymer is impregnated into the substrate.
  • the polymer is the same as described above.
  • the reinforcing membrane according to the exemplary embodiment of the present specification includes a polymer including the unit represented by Chemical Formula 1, has high mechanical strength and high ionic conductivity, and may facilitate phase separation of the reinforcing membrane.
  • the reinforcing film according to the exemplary embodiment of the present specification may include a substrate, thereby increasing chemical resistance and durability, and thus improving the life of the device.
  • the substrate is one or two species in the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), polyethylene (PE) and polyvinylidene difluoride (PVDF) Is selected.
  • PP polypropylene
  • PTFE polytetrafluoroethylene
  • PE polyethylene
  • PVDF polyvinylidene difluoride
  • the content of the polymer is 10 parts by weight to 99 parts by weight with respect to 100 parts by weight of the reinforcing film.
  • the polymer content is 10 parts by weight to 99 parts by weight with respect to 100 parts by weight of the reinforcing film, and the content of the substrate is 1 part by weight to 90 parts by weight.
  • the crossover of vanadium ions may be reduced, and as the content of the polymer increases, the performance of the battery may be improved.
  • the ion conductivity of the reinforcing film is 0.001 S / cm or more and 0.5 S / cm or less. In another exemplary embodiment, the ion conductivity of the reinforcing film is 0.001 S / cm or more and 0.3 S / cm or less.
  • the ion conductivity may be measured under the same conditions as the aforementioned method.
  • the ion exchange capacity (IEC) value of the reinforcing membrane is 0.01 mmol / g to 5.0 mmol / g.
  • IEC ion exchange capacity
  • the thickness of the reinforcement film is 0.01 ⁇ m to 10,000 ⁇ m.
  • the thickness of the reinforcement film may reduce the electric short and the crossover of the electrolyte material, and may exhibit excellent cationic conductivity characteristics.
  • the present disclosure also provides a method for preparing a substrate; And it provides a method for producing a strengthening film comprising the step of impregnating the substrate with a polymer comprising a unit represented by the formula (1).
  • Impregnation in the present specification means that the polymer permeates into the substrate.
  • the impregnation may be performed by dipping the substrate into the polymer, using a slot dye coating, bar casting, or the like.
  • immersion may be expressed in terms such as dip coating or dipping method.
  • the reinforcing film may have a directionality.
  • the substrate may be manufactured by uniaxial stretching or biaxial stretching, and the orientation of the substrate by the stretching may determine the orientation of the reinforcing film. Therefore, the reinforcing film according to the exemplary embodiment of the present specification may have a directionality of the machine direction (MD) and the vertical direction of the machine direction (MD), and the reinforcing film may be stressed and elongated according to the direction.
  • MD machine direction
  • MD vertical direction of the machine direction
  • the physical properties of can represent a difference.
  • the present disclosure also provides a method for preparing a substrate; And it provides a method for producing a reinforcing film comprising the step of immersing the substrate in the polymer.
  • the substrate and the polymer are as described above.
  • the present specification also relates to an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.
  • the present specification also relates to an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described reinforcement film provided between the anode and the cathode.
  • Membrane-electrode assembly is an electrode (cathode and anode) in which the electrochemical catalysis of fuel and air occurs and a polymer membrane in which hydrogen ions are transferred.
  • the electrode (cathode and anode) and the electrolyte membrane are bonded together. It is a single unitary unit.
  • the membrane-electrode assembly of the present specification is a form in which the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane, and may be prepared according to conventional methods known in the art.
  • the cathode; Anode; And it may be prepared by thermocompression bonding at 100 °C to 400 °C in a state in which the electrolyte membrane located between the cathode and the anode in close contact.
  • 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 microporous 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 further include a cathode microporous layer and a cathode electrode substrate.
  • FIG. 1 schematically illustrates the principle of electricity generation of a fuel cell.
  • the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is an electrolyte membrane 100 and the electrolyte membrane 100. It consists of an anode (200a) and a cathode (200b) electrode formed on both sides of the.
  • MEA membrane electrode assembly
  • an anode 200a generates an oxidation reaction of a fuel such as hydrogen or a hydrocarbon such as methanol and butane to generate hydrogen ions (H +) and electrons (e ⁇ ). Hydrogen ions move to the cathode 200b through the electrolyte membrane 100.
  • water is generated by reacting hydrogen ions transferred through the electrolyte membrane 100 with an oxidant such as oxygen and electrons. This reaction causes the movement of electrons in the external circuit.
  • the catalyst layer of the anode electrode is where the oxidation reaction of the fuel occurs, the catalyst is selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum-transition metal alloy. Can be used.
  • the catalyst layer of the cathode electrode is where the reduction reaction of the oxidant occurs, platinum or platinum-transition metal alloy may be preferably used as a catalyst.
  • the catalysts can be used on their own as well as supported on a carbon-based carrier.
  • the introduction of the catalyst layer may be carried out by conventional methods known in the art, for example, the catalyst ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer.
  • the coating method of the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used.
  • Catalytic inks can typically consist of a catalyst, a polymer ionomer, and a solvent.
  • the gas diffusion layer serves as a passage for the reaction gas and water together with a role as a current conductor, and has a porous structure. Therefore, the gas diffusion layer may include a conductive substrate. As the conductive substrate, carbon paper, carbon cloth, or carbon felt may be preferably used.
  • the gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive substrate. The microporous layer may be used to improve the performance of the fuel cell in low-humidity conditions, and serves to reduce the amount of water flowing out of the gas diffusion layer so that the electrolyte membrane is in a sufficient wet state.
  • One embodiment of the present specification includes two or more membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
  • the membrane-electrode assembly includes the aforementioned polymer electrolyte membrane or includes a reinforcement membrane.
  • a fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy.
  • a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction.
  • the fuel cell can be manufactured according to conventional methods known in the art using the membrane-electrode assembly (MEA) described above.
  • MEA membrane-electrode assembly
  • it may be prepared by configuring a membrane electrode assembly (MEA) and a bipolar plate (bipolar plate) prepared above.
  • the fuel cell of the present specification includes a stack, a fuel supply unit and an oxidant supply unit.
  • FIG. 3 schematically illustrates the structure of a fuel cell, in which the fuel cell includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80.
  • the stack 60 includes one or two or more membrane electrode assemblies as described above, and includes two or more separators interposed therebetween when two or more membrane electrode assemblies are included.
  • the separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer fuel and oxidant supplied from the outside to the membrane electrode assembly.
  • the oxidant supply unit 70 serves to supply the oxidant to the stack 60.
  • Oxygen is typically used as the oxidizing agent, and may be used by injecting oxygen or air into the pump 70.
  • the fuel supply unit 80 serves to supply fuel to the stack 60, and to the fuel tank 81 storing fuel and the pump 82 supplying fuel stored in the fuel tank 81 to the stack 60.
  • fuel hydrogen or hydrocarbon fuel in gas or liquid state may be used.
  • hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.
  • the fuel cell may be 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, or a direct dimethyl ether fuel cell.
  • the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a fuel cell, the above-described effects can be obtained.
  • an exemplary embodiment of the present specification includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising a polymer electrolyte membrane according to one embodiment of the present specification provided between the cathode cell and the anode cell.
  • a positive electrode cell including a positive electrode and a positive electrode electrolyte;
  • a cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising a reinforcing film according to an embodiment of the present disclosure provided between the positive electrode and the negative electrode cell.
  • the redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of the active material directly as electrical energy as a system in which the active material contained in the electrolyte is redoxed and charged and discharged.
  • the redox flow battery uses a principle that charges and discharges are exchanged when electrons containing active materials having different oxidation states meet with an ion exchange membrane interposed therebetween.
  • a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occurs, and a circulation pump for circulating the electrolyte solution between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, an electrolyte, and an ion. Exchange membrane.
  • the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a redox flow battery, the above-described effects may be exhibited.
  • the redox flow battery of the present specification may be manufactured according to conventional methods known in the art, except for including the polymer electrolyte membrane according to one embodiment of the present specification.
  • the redox flow battery is divided into the positive electrode cell 32 and the negative electrode cell 33 by the electrolyte membrane 31.
  • the anode cell 32 and the cathode cell 33 include an anode and a cathode, respectively.
  • the anode cell 32 is connected to the anode tank 10 for supplying and discharging the anode electrolyte 41 through a pipe.
  • the cathode cell 33 is also connected to the cathode tank 20 for supplying and discharging the cathode electrolyte 42 through a pipe.
  • the electrolyte is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) in which the oxidation number of ions changes occurs, thereby causing charge and discharge at the anode and the cathode.
  • an oxidation / reduction reaction that is, a redox reaction
  • 4,4-difluorobenzophenone (4,4-difluorobenzophenone) (3.82 g), 9,9-bis (hydroxyphenyl) fluorene (9,9-bis (hydroxyphenyl) fluorine) (6.4 g), carbonic acid Potassium (Potassium carbonate) (2.4g), dimethyl sulfoxide (DMSO), and benzene were further added thereto, followed by 4 hours of reaction at 140 ° C., followed by 24 hours of reaction at 180 ° C. to obtain a polyether ketone.
  • M means the final molecular weight of the polymer
  • M 0 means the initial molecular weight of the polymer
  • t means the number of elapsed cycles
  • T half-life (cycle).
  • Comparative Example 1 has a half-life of 50, whereas Example 1 has a half-life of 83.5 and an increase in half-life.
  • the half-life is the result of measuring charge and discharge in one cycle.
  • the ion conductivity is higher than the membrane of GCM, it can be confirmed that the transmittance of vanadium is lower.
  • the polymer electrolyte membrane including a polymer according to an exemplary embodiment of the present specification has a higher vanadium permeability than a polymer electrolyte membrane including a nafion in the prior art, and thus has a vanadium redox flow battery (VRFB).
  • VRFB vanadium redox flow battery
  • the polymer electrolyte membrane including the polymer according to one embodiment of the present specification has an excellent effect in terms of ionic conductivity and vanadium ion permeability.
  • Example 1 an experiment of obtaining a polymer with a 2,4-difluoro partial fluorine monomer, which is the first monomer represented by Formula 1, was performed, and a high molecular weight polymer was obtained.
  • a polymer with a 2,4-difluoro partial fluorine monomer which is the first monomer represented by Formula 1
  • attempts have been made to produce polymers using commonly used 2,5-difluoro partial fluorine-based monomers, but failed to obtain high molecular weight polymers under the same conditions.
  • the molecular weight of the polymer was measured by gel permeation chromatography (GPC: Gel Permeation Chromatography) to determine the molecular weight shown in Table 2 below.
  • N / A means not available, and it can be seen that the polymer is not formed.
  • the 2,4-difluoro halogenated compound according to an exemplary embodiment of the present specification has a characteristic in that the functional group of Formula 2, which is dependent on a pendant, exhibits the properties of electron drags as a whole.
  • the reactivity is greatly improved and it can be seen that there is an advantage in obtaining a high molecular weight polymer.
  • Example 1 As a result of Example 1 and Comparative Example 3, it can be seen that the compound containing the monomer represented by the formula (1) according to one embodiment of the present specification is chemically stable to facilitate the formation of a polymer.
  • Example 1 The polymer polymerized in Example 1 was dissolved in dimethyl sulfoxide (DMSO), immersed in a polytetrafluoroethylene (PTFE) substrate, and dried to prepare a reinforcing film. The dried reinforcing film was subjected to a single cell evaluation of a redox flow battery.
  • DMSO dimethyl sulfoxide
  • PTFE polytetrafluoroethylene
  • Table 2 shows the results of measuring ion conductivity and permeability of the electrolyte membranes prepared in Example 2 and Comparative Examples 4 and 5.
  • the ion conductivity is higher than that of the GCM, but it can be confirmed that the transmittance of vanadium ions is lower.
  • the reinforcing film according to one embodiment of the present specification has an excellent effect in terms of ion conductivity and transmittance of vanadium ions.
  • Example 4 is a view showing a single cell evaluation results of Example 2 of the present invention and Nafion.

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Abstract

La présente invention concerne un polymère présentant une résistance aux acides améliorée, une membrane électrolytique polymère en comprenant, un ensemble membrane-électrode comprenant la membrane électrolytique polymère, une pile à combustible comprenant l'ensemble membrane-électrode, et une batterie à flux redox comprenant la membrane électrolytique polymère.
PCT/KR2015/013206 2014-12-04 2015-12-04 Polymère et membrane électrolytique polymère en comprenant WO2016089154A1 (fr)

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CN201580066249.5A CN107001595B (zh) 2014-12-04 2015-12-04 聚合物和包含该聚合物的聚合物电解质膜
EP15865952.4A EP3228646B1 (fr) 2014-12-04 2015-12-04 Polymère et membrane électrolytique polymère en comprenant
US15/531,702 US10361447B2 (en) 2014-12-04 2015-12-04 Polymer and polymer electrolyte membrane comprising same

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KR10-2015-0134774 2015-09-23
KR1020150134774A KR20160067720A (ko) 2014-12-04 2015-09-23 중합체 및 이를 포함하는 고분자 전해질막

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