KR102091904B1 - Polymer separator comprising inorganic particles - Google Patents

Abstract

The present specification relates to a polymer separation membrane containing inorganic particles and a membrane electrode assembly including the same, a fuel cell and a redox flow battery.

Description

Polymer separation membrane containing inorganic particles {POLYMER SEPARATOR COMPRISING INORGANIC PARTICLES}

The present specification relates to a polymer separation membrane containing inorganic particles and a membrane electrode assembly including the same, a fuel cell and a redox flow battery.

A fuel cell is an energy conversion device that directly converts chemical energy of fuel into electrical energy. That is, a fuel cell is a power generation method that uses fuel gas and an oxidizing agent, and generates electricity using electrons generated during their redox reaction. The membrane electrode assembly (MEA) of a fuel cell is a part where an electrochemical reaction between hydrogen and oxygen occurs, and is composed of a cathode, an anode, and a separator, that is, an ion conductive separator.

Redox flow battery (oxidation-reduction 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 unit cell includes an electrode, an electrolyte, and an ion exchange membrane (separation 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 emission of pollutants.

The most important components in fuel cells and redox flow cells are polymer separation membranes capable of cation exchange, 1) excellent proton conductivity, 2) prevention of electrolyte crossover, 3) strong chemical resistance, 4) mechanical It is good to have properties of strengthening properties and / or 4) low swelling ratio. Polymeric membranes are classified into fluorine-based, partially fluorine-based, and hydrocarbon-based membranes. In the case of partially-fluorine-based polymer membranes, they have a fluorine-based main chain, which has excellent physical and chemical stability and high thermal stability. In addition, the partial fluorine-based polymer separation membrane has the advantages of a hydrocarbon-based polymer separation membrane and a fluorine-based polymer separation membrane at the same time as the cation transfer functional group is attached to the end of the fluorine-based chain, like the fluorine-based polymer separation membrane.

However, the partial fluorine-based polymer separation membrane has a problem in that cation conductivity is relatively low because the fine phase separation of the cation transfer functional group and the control of aggregation are not effectively performed. Therefore, research has been conducted in the direction of securing high cation conductivity through control of the distribution of sulfonic acid groups and separation of fine phases.

United States Patent Application Publication No. 2008-0241626

The present specification provides a polymer separation membrane containing inorganic particles, a membrane electrode assembly, and a fuel cell or redox flow battery including the same.

The present specification is a polymer comprising a unit derived from a compound represented by Formula 1; And it provides a polymer separator comprising inorganic particles:

[Formula 1]

In Chemical Formula 1,

R1 and R2 are the same as or different from each other, and each independently a halogen group,

A is O or NR4,

Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R3 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 ) _q SO ₃ H, ―O (CF ₂ ) _q SO ₃ ^- M ⁺ , ―O (CF ₂ ) _q COOH, ―O (CF ₂ ) _q COO ^- M ⁺ , ―O (CF _{2 ) q PO 3 H 2, -O} (CF 2) q PO 3 H - M +, -O (CF 2) q PO 3 2 - 2M + or to be represented by the formula (2),

q is an integer from 1 to 6,

M is a group 1 element,

R4 is H, CH ₃ , (CF ₂ ) _o SO ₃ H or (CF ₂ ) _p CO ₂ H,

n, o and p are each independently an integer of 1 to 10, and when n is 2 or more, structures in parentheses are the same or different from each other,

[Formula 2]

In Chemical Formula 2,

Z3 and Z4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R5 is SO ₃ H or CO ₂ H,

m is an integer of 1 to 10, and when m is an integer of 2 or more, structures in parentheses are the same or different from each other.

In addition, the present specification is an anode; Cathode; And it provides a membrane electrode assembly comprising a polymer separation membrane according to the above-described embodiment of the present specification provided between the anode and the cathode.

In addition, the present specification is an anode cell comprising an anode and a cathode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer separation membrane according to the above-described exemplary embodiment of the present specification provided between the anode cell and the cathode cell.

The unit derived from the compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification has high reactivity in the polymerization process, and may increase process efficiency. In addition, the polymer separation membrane prepared using the unit derived from the compound can easily form a hydrophilic-hydrophobic phase separation structure. In addition, the polymer separation membrane comprising a unit derived from the compound according to an exemplary embodiment of the present specification can efficiently form a hydrophilic channel in the polymer separation membrane by controlling the phase separation structure. In addition, the polymer separation membrane comprising a unit derived from the compound has excellent ion conductivity. In addition, the units derived from the compounds are thermally and chemically stable.

Polymer membranes comprising units derived from compounds according to one embodiment of the present specification may have equivalent ionic conductivity at a low ion exchange capacity (IEC) compared to polymer membranes containing hydrocarbon-based compounds, resulting in less water absorption It can maintain excellent ionic conductivity.

In addition, the polymer separation membrane according to one embodiment of the present specification further includes inorganic particles, thereby preventing swelling due to a solvent, and increasing mechanical properties and an increase in chemical stability.

In addition, in the case of a polymer electrolyte fuel cell (PEMFC) including the polymer separator according to an exemplary embodiment of the present specification, gas crossover can be prevented, and ion conductivity can be improved even in a low-humidity condition. have.

In addition, the redox flow battery including the polymer separation membrane according to an exemplary embodiment of the present specification may prevent crossover of vanadium ions.

In addition, the fuel cell including the polymer separation membrane according to an exemplary embodiment of the present specification is excellent in durability and efficiency.

1 is a schematic view showing the principle of electricity generation in a fuel cell.
2 is a view schematically showing an embodiment of a redox flow battery.
3 is a view schematically showing an embodiment of a fuel cell.

Hereinafter, the present specification will be described in more detail.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present specification, "derived" means that a bond of a compound is broken or a new bond occurs when a substituent is removed, and a unit derived from the compound may mean a unit connected to the main chain of the polymer. The unit may be included in the main chain in the polymer to constitute the polymer.

In the present specification, "unit" is a structure in which a monomer is included in a polymer and repeated, and refers to a structure in which the monomer is bonded to the polymer by polymerization.

In the present specification, the meaning of “comprising units” means being included in the main chain in the polymer.

In the present specification, "separation membrane" is a membrane capable of exchanging ions, such as a membrane, an ion exchange membrane, an ion transport membrane, an ion conducting membrane, an ion exchange membrane, an ion transfer membrane, an ion conducting membrane, an ion exchange electrolyte membrane, an ion transfer membrane Electrolyte membranes, or ion conductive electrolyte membranes.

In this specification, the term "substituted or unsubstituted" deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And substituted or unsubstituted heterocyclic groups, or substituted with one or more substituents selected from the group consisting of, or substituted with two or more substituents among the exemplified substituents, or having no substituents. For example, "substituents connected to two or more substituents" are alkyl groups substituted with halogen groups, aryl groups substituted with alkyl groups, aryl groups substituted with aryl groups, aryl groups substituted with heteroaryl groups, aryl groups substituted with silyl groups, and alkyl groups substituted A silyl group, a heteroaryl group substituted with an alkyl group, a heteroaryl group substituted with an aryl group, a heteroaryl group substituted with a heteroaryl group, but is not limited thereto.

In the present specification, the term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited if the position at which the hydrogen atom is substituted, that is, the substituent is substitutable, 2 In the case of abnormal substitution, two or more substituents may be the same or different from each other.

In the present specification, "hydrocarbon-based" refers to an organic compound composed only of carbon and hydrogen, and includes straight-chain, branched-chain, and cyclic hydrocarbons, 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.

In the present specification, "fluorine-based binder" means that some or all of the carbon-hydrogen bonds in the hydrocarbon system are substituted with fluorine.

In the present specification, the halogen group may be F, Cl, Br, I, and the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 50 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but may be 6 to 50 carbon atoms, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The monocyclic aryl group may be a phenyl group, a biphenyl group, and a terphenyl group, but is not limited thereto. The polycyclic aryl group is a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perillynyl group, fluoranthenyl group, triphenylenyl group, phenenyl group, chrysenyl group, fluorenyl group, benzofluore It may be a nil group, a spirobifluorenyl group, a triphenylene group, and a spirobenzoanthracenefluorenyl group, but is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms include atoms selected from the group consisting of N, P, O, S, Se, Ge, and Si. It may contain 1 or more. The number of carbon atoms is not particularly limited, and preferably has 2 to 50 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms in the heteroaryl group is 2 to 30 carbon atoms. According to another exemplary embodiment, the heteroaryl group has 2 to 20 carbon atoms. The heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, isooxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, Triazinyl group, triazolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyra Ginopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzo Furanyl group, dibenzofuranyl group, naphthobenzofuranyl group, phenanthroline group, thiadiazolyl group, phenothiazinyl group, acenaphthoquinoxalyl group, indenoquinazolyl group, indenoisoquinolyl Group, indenoquinolyl group, pteridinyl group, phenoxazinyl group, benzoquinazolyl group, inda Group, benzo Perry MIDI quinolyl group, a benzo group and Perry media include, but RY Loa acridine fluorenyl group, and the like.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 50 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, and the like. no.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 50. 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, styrenyl group, etc., but are not limited to this no.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine groups; N-alkylarylamine group; Arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine groups and heteroarylamine groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methylanthracenylamine group, Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenyl Naphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group , N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, and the like, but is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group simultaneously. For example, the aryl group in the arylamine group can be applied to the description of the aryl group described above.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group simultaneously. For example, the description of the heteroaryl group in the heteroarylamine group described above may be applied.

In the present specification, the N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted for N of the amine group.

In the present specification, the N-aryl heteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, examples of the heteroaryl group in the N-aryl heteroarylamine group and the N-alkylheteroarylamine group may be applied to the description of the aforementioned heteroaryl group.

In the present specification, the aryl group in the arylamine group, the aryloxy group, the aralkyl group, and the alkylaryl group may be applied to the aryl group described above.

In the present specification, the alkyl group of the haloalkyl group, the alkylamine group, the alkylsilyl group, the alkoxy group, the aralkyl group and the alkylaryl group, the description of the aforementioned alkyl group may be applied.

In the present specification, as the aryloxy group, a phenoxy group, p-tolyloxy group, m-toryloxy group, 3,5-dimethylphenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryl Oxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like.

In the present specification, the hydrocarbon ring is a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic ring composed of only carbon and hydrogen.

In the present specification, the hetero ring may be an aliphatic hetero ring or an aromatic hetero ring, and selected from the group consisting of hetero atoms such as N, P, O, S, Se, Ge and Si in place of the carbon atom in the hydrocarbon ring. It means a structure containing one or more atoms.

In the present specification, the aromatic ring may be a substituted or unsubstituted aromatic hydrocarbon ring or an aromatic hetero ring, and may be monocyclic or polycyclic.

In the present specification, the description of the aryl group may be applied to the aromatic hydrocarbon ring.

In the present specification, the aromatic hetero ring has a structure containing at least one atom selected from the group consisting of hetero atoms such as N, P, O, S, Se, Ge and Si in the aromatic hydrocarbon ring instead of carbon atoms. Meaning, the description of the heteroaryl group may be applied.

In the present specification, the aliphatic ring may be a substituted or unsubstituted aliphatic hydrocarbon ring or an aliphatic hetero ring, and may be monocyclic or polycyclic.

In the present specification, the description of the cycloalkyl group may be applied to the aliphatic hydrocarbon ring.

In the present specification, the aliphatic hetero ring has a structure containing at least one atom selected from the group consisting of hetero atoms such as N, P, O, S, Se, Ge and Si in the aliphatic hydrocarbon ring instead of carbon atoms. it means.

In this specification, "organic group" includes an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and a heteroaryl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom. Further, the organic group may be either linear, branched or cyclic.

In the present specification, the term "trivalent organic group" means a trivalent group having three binding positions in an organic compound.

In addition, in the present specification, the organic group may form a cyclic structure, and may form a bond including a hetero atom as long as the effect of the invention is not impaired. Specifically, bonds containing heteroatoms, such as an oxygen atom, a nitrogen atom, and a silicon atom, are mentioned. As a specific example, ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N = C (-B)-, -C (= NB) -: B represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like, but is not limited thereto.

In the present specification, the cyclic structure may include the aforementioned aromatic ring, aliphatic ring, etc., and may be monocyclic or polycyclic.

In the present specification, the particle diameter of the inorganic particles was measured by dynamic light scattering.

According to an exemplary embodiment of the present specification, the inorganic particles are inorganic; Hetero polyacid; And one or two or more types from the group consisting of inorganic acids.

According to one embodiment of the present specification, the inorganic material is BaTiO ₃ , Pb (Zr _x Ti _1-x ) O ₃ (PZT, 0 <x <1), Pb _{1 - x} La _x Zr _{1 - y} Ti _y O ₃ (PLZT, 0 <x <1, 0 <y <1), (1-x) Pb (Mg _1/3 Nb _2/3 ) O ₃ -xPbTiO ₃ (PMN-PT, 0 <x <1), half Ni (HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZnO ₂ , ZrO ₂ , SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC, TiO ₂ , Tetraethyl Lead (Tetraethyl orthosilicate: TEOS), montmorillonite (MMT) and (P ₂ O ₅ ) ₄ (ZrO ₂ ) ₃ , P ₂ O ₅ -ZrO ₂ -SiO ₂ and the like, but is not limited thereto.

In addition, the inorganic acid is CsDSO ₄ , CsHSO ₄ and the like, but is not limited thereto.

Further, the hetero poly acid _{α-Zr (O 3 PCH 2} OH) 1 .27 (O 3 PC 6 H 4 SO 3 H) 0.73 · zH 2 O (1 <z <10), γ-Zr (PO 4) (H ₂ PO ₄ ) _{0 .54} (HO ₃ PC ₆ H ₄ SO ₃ H) _0.46 zH2O (1 <z <10), Zr (O ₃ PCH ₂ OH) _1.27 Y _0.73 zH ₂ O (1 <z <10), α-Zr (O ₃ PC ₆ H ₄ SO ₃ H) · 3.6H ₂ O, α-Zr (O ₃ POH) · H ₂ O, β-Cs ₃ (HSO ₄ ) ₂ (H _x ( P, S) O ₄ ), α-Cs ₃ (HSO ₄ ) ₂ (H ₂ PO ₄ ), phosphotungstic acid, silicocotungstic acid and molybdophosphoric acid (H) ₃ PO ₄ · 12MoO ₃ · zH ₂ O) (1 <z <10), but is not limited thereto.

Specifically, according to an exemplary embodiment of the present specification, the inorganic particles are BaTiO ₃ , Pb (Zr _x , Ti _1-x ) O ₃ (PZT, 0 <x <1), Pb _{1 - x} La _x Zr _{1 - y} Ti _y O ₃ (PLZT, 0 <x <1, 0 <y <1), (1-x) Pb (Mg _1/3 Nb _2/3 ) O _{3 -x} PbTiO ₃ (PMN-PT, 0 <x <1), hafnia (HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZnO ₂ , ZrO ₂ , SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC, TiO ₂ , Tetraethyl orthosilicate (TEOS), Montmorillonite (MMT), (P ₂ O ₅ ) ₄ (ZrO ₂ ) ₃ , P ₂ O ₅ -ZrO ₂ -SiO ₂ , CsDSO ₄ , CsHSO ₄ , α -Zn (O ₃ PCH ₂ OH) _{1 .27} (O ₃ PC ₆ H ₄ SO ₃ H) _0.73 zH ₂ O (1 <z <10), γ-Zr (PO ₄ ) (H ₂ PO ₄ ) _0.54 (HO ₃ PC ₆ H ₄ SO ₃ H) _0.46 zH ₂ O (1 <z <10), Zr (O ₃ PCH ₂ OH) _{1 . 27 Y 0 .73 · zH 2 O} (1 <z <10), α-Zr (O 3 PC 6 H 4 SO 3 H) · 3.6H 2 O, α-Zr (O 3 POH) H 2 O, β -Cs ₃ (HSO ₄ ) ₂ (H _x (P, S) O ₄ ), α-Cs ₃ (HSO ₄ ) ₂ (H ₂ PO ₄ ), phosphotungstic acid, silicocotungstic acid) and molybdophosphoric acid (molybdophosphoric acid: H ₃ PO ₄ 12MoO ₃ · zH ₂ O) (1 <z <10) may be selected from the group consisting of one or two or more, but is not limited thereto. .

According to an exemplary embodiment of the present specification, the inorganic particles are SiO ₂ .

According to an exemplary embodiment of the present specification, the inorganic particles are provided in a form dispersed in the polymer separation membrane.

According to an exemplary embodiment of the present specification, the content of the inorganic particles based on the total content of the solid content of the polymer separator is 0.5% to 10% by weight, the content of the polymer is 90% to 99.5% by weight.

According to the exemplary embodiment of the present specification, the solid content of the polymer separation membrane means a solute or solid material excluding the solvent from the total mass of the solution.

According to the exemplary embodiment of the present specification, when the inorganic particles in the above range are included, heat resistance of the polymer membrane and water uptake at high temperature may be increased by the introduced inorganic particles, and high temperature swelling ( Swelling) can prevent the reduction of mechanical properties. In addition, within the above range, it is possible to contribute to an improvement in hydrogen ion conductivity due to a decrease in moisture content at a high temperature by inorganic particles.

According to an exemplary embodiment of the present specification, the content of the polymer in the composition for forming a polymer separator is preferably 3% by weight to 30% by weight, more preferably 5% by weight to 15% by weight.

According to the exemplary embodiment of the present specification, the composition for forming a polymer separator includes a solvent, and is preferable in terms of viscosity when the polymer content in the composition is within the above range.

According to an exemplary embodiment of the present specification, the polymer contained in the polymer separation membrane includes a unit derived from the compound represented by the formula (1).

According to an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a halogen group. Specifically, R1 and R2 may be each independently selected from the group consisting of F, Cl, Br and I.

According to an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently F or Cl.

According to an exemplary embodiment of the present specification, each of R1 and R2 is F.

According to an exemplary embodiment of the present specification, A is O or NR4.

According to an exemplary embodiment of the present specification, R3 may be represented by -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H or the formula (2).

According to an exemplary embodiment of the present specification, R3 may be represented by -SO ₃ H, -SO ₃ ^- M ⁺ or the formula (2).

According to another exemplary embodiment of the present specification, R3 may be represented by —SO ₃ H or Chemical Formula 2.

According to an exemplary embodiment of the present specification, when R3 in the formula (1) is represented by -SO ₃ H, -SO ₃ ^- M ⁺ or the formula (2), it is possible to form a chemically stable polymer.

According to an exemplary embodiment of the present specification, M is a group 1 element.

According to an exemplary embodiment of the present specification, the group 1 element is Li, Na or K.

According to an exemplary embodiment of the present specification, R4 is H, CH ₃ , (CF ₂ ) _o SO ₃ H or (CF ₂ ) _p CO ₂ H.

According to an exemplary embodiment of the present specification, Z1 to Z4 are the same as or different from each other, and may be independently selected from the group consisting of F, Cl, Br, and I.

According to one embodiment of the present specification, Z1 to Z4 are the same as or different from each other, and each independently a halogen group.

According to an exemplary embodiment of the present specification, each of Z1 to Z4 is F.

According to an exemplary embodiment of the present specification, when the Z1 to Z4 are each independently a halogen element (F, Cl, Br, I), it is possible to facilitate the movement of hydrogen ions by attracting electrons well, and the structure of the polymer separation membrane. It has the advantage of being strong. Specifically, according to an exemplary embodiment of the present specification, when the Z1 to Z4 are each F, the advantage may be maximized.

According to an exemplary embodiment of the present specification, n in the formula 1 is an integer of 0 or more and 5 or less.

According to an exemplary embodiment of the present specification, o in the formula 1 is an integer of 0 or more and 5 or less.

According to the exemplary embodiment of the present specification, p in Chemical Formula 1 is an integer of 0 or more and 5 or less.

According to an exemplary embodiment of the present specification, when n in the formula (1) is an integer of 2 or more, structures in parentheses of 2 or more are the same or different from each other.

According to the exemplary embodiment of the present specification, m in Chemical Formula 2 is an integer of 0 or more and 5 or less.

According to the exemplary embodiment of the present specification, when m in Formula 2 is an integer of 2 or more, structures in parentheses of 2 or more are the same or different from each other.

According to an exemplary embodiment of the present specification, the chain consisting of carbon and oxygen of the formula (2) may serve to facilitate the phase separation phenomenon of the polymer membrane. In addition, the chain consisting of carbon and oxygen of Chemical Formula 2 may serve to facilitate the movement of hydrogen ions of the polymer separator.

In the present specification, when O or NR4 is used as a linker between a-[CZ1Z2] n-R3 structure and a benzene ring in Chemical Formula 1, O or NR4 is relatively electron donating character, but O or By-[CZ1Z2] n-R3 connected to NR4, it has an electron withdrawing character. Therefore, when the position in the benzene ring is connected to the polymer by 1 or 3 based on O or NR4 is improved, the polymerizability is improved, and it is easy to form a high molecular weight polymer, and has the advantage of providing a stable polymer. have.

According to an exemplary embodiment of the present specification, the unit derived from the compound represented by Formula 1 may be represented by any one of the following Formula 1-1 to Formula 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Chemical Formulas 1-1 to 1-4,

R6 is H, CH ₃ , (CF ₂ ) _o SO ₃ H or (CF ₂ ) _p CO ₂ H,

n, o and p are as defined above.

는 인접한 치환기 또는 중합체의 주쇄와 결합함을 의미한다.According to an exemplary embodiment of the present specification,

Means that it bonds with an adjacent substituent or the main chain of the polymer.

According to an exemplary embodiment of the present specification, the polymer includes only the unit derived from the compound represented by the formula (1).

According to another exemplary embodiment of the present specification, the polymer may further include a second unit other than the unit derived from the compound represented by Chemical Formula 1.

According to one embodiment of the present specification, the unit derived from the compound represented by Chemical Formula 1 and the second unit may be polycondensed.

According to the exemplary embodiment of the present specification, the second unit may be a dithiol monomer or a diol monomer, but is not limited thereto.

According to an exemplary embodiment of the present specification, the second unit may include a compound represented by the following formula 5 or 6.

[Formula 5]

[Formula 6]

In Chemical Formulas 5 and 6,

Y is a substituted or unsubstituted alkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, y is an integer of 1 to 10, and when y is an integer of 2 or more, 2 or more Y is the same or different from each other.

According to an exemplary embodiment of the present specification, Y is an arylene group.

According to an exemplary embodiment of the present specification, Y is a phenylene group; Biphenylene group; Or a terphenylene group.

According to an exemplary embodiment of the present specification, Y is a phenylene group, y is 2.

According to an exemplary embodiment of the present specification, when the polymer further comprises a second unit, the content of the unit derived from the compound represented by Formula 1 is 5 mol% to 50 mol based on the total content of the polymer solid content %. As described above, the desired ion exchange capacity (IEC) can be adjusted according to the purpose of use by controlling the content of the unit derived from the compound represented by Formula 1, that is, a membrane electrode assembly or a redox flow battery.

According to an exemplary embodiment of the present specification, the "total content of the polymer solid content" means the content of the solute or solids excluding the solvent in the total mass of the solution.

According to an exemplary embodiment of the present specification, the unit derived from the compound represented by the formula (1) serves to control the ionic conductivity of the polymer membrane.

According to the exemplary embodiment of the present specification, the second unit may be selected from units that improve the mechanical strength of the polymer, and if the unit is capable of improving the mechanical strength, its type is not limited.

According to one embodiment of the present specification, the weight average molecular weight of the polymer is 500 g / mol to 2,000,000 g / mol. When the weight average molecular weight of the polymer is within the above range, the mechanical properties of the polymer separator containing the polymer are not deteriorated, and solubility of the appropriate polymer is maintained, so that the separator can be easily prepared.

According to an exemplary embodiment of the present specification, the polymer containing a unit derived from the compound represented by Formula 1 is a random polymer or a block polymer.

According to one embodiment of the present specification, the unit derived from the compound represented by Chemical Formula 1 and the second unit may constitute a random polymer.

According to an exemplary embodiment of the present specification, the polymer may be a block polymer. More specifically, the block polymer includes a hydrophilic block and a hydrophobic block, and the hydrophilic block may include a unit derived from the compound represented by Chemical Formula 1.

According to an exemplary embodiment of the present specification, the hydrophilic block and the hydrophobic block in the block polymer is included in a molar ratio of 1: 0.1 to 1:10. According to one embodiment of the present specification, the hydrophilic block and the hydrophobic block in the block polymer are included in a molar ratio of 1: 0.1 to 1: 2. According to another exemplary embodiment of the present specification, the hydrophilic block and the hydrophobic block in the block polymer are included in a molar ratio of 1: 0.8 to 1: 1.2. In this case, the ion transfer ability of the block polymer can be increased.

According to an exemplary embodiment of the present specification, the unit derived from the compound represented by the formula (1) in the hydrophilic block is included from 0.01 mol% to 100 mol% based on the hydrophilic block.

According to one embodiment of the present specification, the number average molecular weight of the hydrophilic block is 1,000 g / mol to 300,000 g / mol. According to a specific embodiment, it is 2,000 g / mol to 100,000 g / mol. According to another exemplary embodiment, it is 2,500 g / mol to 50,000 g / mol.

According to an exemplary embodiment of the present specification, the number average molecular weight of the hydrophobic block is 1,000 g / mol to 300,000 g / mol. According to a specific embodiment, it is 2,000 g / mol to 100,000 g / mol. According to another exemplary embodiment, it is 2,500 g / mol to 50,000 g / mol.

According to the exemplary embodiment of the present specification, in the case of a block polymer, the separation and division of the hydrophilic block and the hydrophobic block are clear, so phase separation is easy, and ion transfer may be facilitated.

According to the exemplary embodiment of the present specification, when the unit derived from the compound represented by Chemical Formula 1 is included, the distinction between the hydrophilic block and the hydrophobic block becomes more clear, and the ion transfer effect may be superior to that of the conventional polymer. .

According to an exemplary embodiment of the present specification, the block polymer means a polymer composed of one block and one or two or more blocks different from the block connected to each other by a main chain of a polymer.

As used herein, "hydrophilic block" means a block having an ion exchange group as a functional group. Wherein 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 ) _w SO ₃ H, ―O (CF ₂ ) _w SO ₃ ^- M ⁺ , ―O (CF ₂ ) _w COOH, ―O (CF ₂ ) _w COO ^- M ⁺ , ―O (CF ₂ may be at least one selected from the group consisting of _{^{2M + -) w PO 3 H}} 2, -O (CF 2) w PO 3 H - M + , and _{-O (CF 2) w PO 3} 2. Here, M is a metallic element, and w may have a range of 1 <w <10. That is, the functional group can be hydrophilic.

In the present specification, "block having an ion exchange group" means a block represented by the average number of ion exchange groups per one structural monomer constituting the block and 0.5 or more, and an average of 1.0 or more per structural monomer. It is more preferable to have an ion exchange group.

As used herein, "hydrophobic block" refers to the polymer block that is substantially free of ion exchange groups.

In the present specification, "a block having substantially no ion exchange group" means a block having an average of less than 0.1, expressed as the number of ion exchange groups per structural monomer constituting the block, and is preferably 0.05 or less. , It is more preferable if it is a block having no ion exchange groups.

In the present specification, "brancher (Brancher)" serves to link or crosslink the polymer chain.

According to one embodiment of the present specification, the polymer further includes a brancher.

According to the exemplary embodiment of the present specification, in the case of the polymer further comprising the brancher, the brancher can directly constitute the main chain of the polymer, and improve the mechanical density of the thin film. For example, the branched polymers of the present invention are post-treated sulfonated by polymerizing branched hydrophobic blocks that do not contain acid substituents and branched hydrophilic blocks that contain acid substituents. Without performing a post-sulfonation or cross-linking of a sulfonated polymer, the brancher directly constitutes the polymer main chain and maintains the mechanical density of the thin film. Hydrophobic blocks and hydrophilic blocks that impart ionic conductivity to thin films may alternately lead to chemical bonding.

According to one embodiment of the present specification, the polymer further includes a brancher represented by the following Chemical Formula 3 or 4.

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

X is S; O; CO; SO; SO ₂ ; NR; Hydrocarbon-based or fluorine-based conjugates,

l is an integer from 0 to 100, and when l is 2 or more, 2 or more Xs are the same or different from each other,

Y1 and Y2 are the same as or different from each other, and each independently an aromatic ring substituted by 1 or 2 or more with a substituent selected from the group consisting of a hydroxy group and a halogen group; An aliphatic ring substituted by 1 or 2 or more with a substituent selected from the group consisting of a hydroxy group and a halogen group; Or an amine group represented by NR'R ",

R, R 'and R "are aromatic rings substituted with halogen groups; or aliphatic rings substituted with halogen groups,

Z is a trivalent organic group.

According to an exemplary embodiment of the present specification, the brancher derived from the compound of Formula 3 is an aromatic ring substituted with each of the halogen groups of Y1 and Y2; Or an aliphatic ring substituted with a halogen group; Alternatively, the halogen group in the amine group represented by NR'R "may be separated from the aromatic ring or the aliphatic ring, and function as a branch.

According to an exemplary embodiment of the present specification, l is 3 or more.

According to an exemplary embodiment of the present specification, X is S.

According to another exemplary embodiment of the present specification, X is a haloalkylene group.

According to another exemplary embodiment of the present specification, X is NR.

According to the exemplary embodiment of the present specification, Y1 and Y2 are the same or different from each other, and are each independently an aromatic ring substituted with a halogen group.

According to the exemplary embodiment of the present specification, Y1 and Y2 are the same or different from each other, and each independently is an aromatic hydrocarbon ring substituted with F.

According to one embodiment of the present specification, Y1 and Y2 are the same or different from each other, and each is an amine group represented by NR'R ".

According to another exemplary embodiment of the present specification, Y1 and Y2 are each a fluorine-substituted phenyl group. Specifically, 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl, and the like, but are not limited thereto.

According to the exemplary embodiment of the present specification, the brancher represented by Chemical Formula 3 may be represented by any one of the following structures.

In the above structure, X, l, R 'and R "are the same as defined in the formula (3).

According to one embodiment of the present specification, Z in Chemical Formula 4 may be represented by any one of the following Chemical Formulas 4-1 to 4-4.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Chemical Formulas 4-1 to 4-4,

L1 To L7 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; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a, b, c, f, h, i and j are each an integer from 1 to 4,

d, e, g and k are each an integer from 1 to 3,

When a, b, c, d, e, f, g, h, i, j and k are each integers of 2 or more, structures in parentheses of 2 or more are the same or different from each other.

According to an exemplary embodiment of the present specification, L1 is CO.

According to one embodiment of the present specification, L1 is SO ₂ .

According to an exemplary embodiment of the present specification, L1 is S.

According to an exemplary embodiment of the present specification, L2 is CO.

According to one embodiment of the present specification, L2 is SO ₂ .

According to an exemplary embodiment of the present specification, L2 is S.

According to an exemplary embodiment of the present specification, L3 is CO.

According to one embodiment of the present specification, L3 is SO ₂ .

According to an exemplary embodiment of the present specification, L3 is S.

According to an exemplary embodiment of the present specification, L4 is CO.

According to one embodiment of the present specification, L4 is SO ₂ .

According to an exemplary embodiment of the present specification, L5 is a direct bond.

According to an exemplary embodiment of the present specification, L6 is a direct bond.

According to an exemplary embodiment of the present specification, L7 is a direct bond.

According to an exemplary embodiment of the present specification, each of R10 to R20 is hydrogen.

According to an exemplary embodiment of the present specification, the R10 to R15, and R17 to R20 are each hydrogen.

According to an exemplary embodiment of the present specification, R16 is a halogen group.

According to an exemplary embodiment of the present specification, R16 is fluorine.

According to the exemplary embodiment of the present specification, the brancher represented by Chemical Formula 4 may be represented by any one of the following structures.

The present specification provides a polymer separation membrane comprising a polymer derived from a compound represented by the formula (1) and inorganic particles.

According to an exemplary embodiment of the present specification, when including a polymer containing a unit derived from the compound represented by the formula (1), it has a high mechanical strength and high ionic conductivity, it is possible to facilitate the phase separation phenomenon of the polymer membrane have.

According to one embodiment of the present specification, the polymer separation membrane uses materials and / or methods known in the art, except that it includes polymers and inorganic particles comprising units derived from the compound represented by Formula 1 Can be manufactured. For example, it may be performed by applying a solution containing the polymer, and drying and / or curing.

According to the exemplary embodiment of the present specification, the coating may be a method such as a tape casting method, a dip coating method, a spray coating method, a spin coating method, or the like. have.

According to an exemplary embodiment of the present specification, the solvent used in the preparation of the polymer membrane is N, N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N, N- Dimethylpyrrolidone (N, N-dimethylpyrollidone (NMP)), diphenylsulfone, N, N-dimethylformamide (DMF), etc. may be used, but is not limited to these. no.

According to one embodiment of the present specification, the curing may be performed by heating.

According to an exemplary embodiment of the present specification, the heating means curing through heating.

According to one embodiment of the present specification, the heating temperature may be 30 ° C or more and 200 ° C or less, specifically 50 ° C or more and 150 ° C or less.

According to one embodiment of the present specification, the heating time may be 1 hour or more and 46 hours or less, specifically 5 hours or more and 20 hours or less.

According to an exemplary embodiment of the present specification, the method of manufacturing the polymer separator may further include adding an acid solution to the solution containing the polymer.

According to an exemplary embodiment of the present specification, when the acid solution is added to the solution containing the polymer, A of Formula 1 is -SO ₃ , -M ⁺ , -COO ^- M ⁺ , -PO ₃ H ^- M ⁺ , or- instead of the metal M PO ₃ ^2- 2M ⁺ a copolymer which may be substituted with H (hydrogen).

According to one embodiment of the present specification, the heating is preheated at 50 ° C to 70 ° C for 2 to 6 hours, dried at 100 ° C for at least 12 hours, and finally dried at 100 ° C in a vacuum oven for at least 12 hours. can do.

According to an exemplary embodiment of the present specification, the ion conductivity of the polymer separation membrane is 0.01 S / cm to 0.5 S / cm. According to another exemplary embodiment, the ionic conductivity of the polymer separation membrane is 0.01 S / cm to 0.3 S / cm.

According to an exemplary embodiment of the present specification, the ion conductivity of the polymer separation membrane can be measured under humidifying conditions. In the present specification, the humidification condition may mean relative humidity (RH) 10% to 100%.

According to an exemplary embodiment of the present specification, the ion exchange capacity (IEC) value of the polymer separation membrane is 0.01 mmol / g to 5.0 mmol / g. When the ion exchange capacity value is in the range, an ion channel is formed in the polymer separation membrane, and the polymer may exhibit excellent ion conductivity.

According to an exemplary embodiment of the present specification, the thickness of the polymer separator is 1 ㎛ to 500 ㎛. The polymer membrane having a thickness in the above range may reduce electric short and cross over of the electrolyte material, and exhibit excellent cationic conductivity characteristics.

According to an exemplary embodiment of the present specification, the polymer separation membrane is a polymer comprising a unit derived from the compound represented by Formula 1; And inorganic particles.

According to another exemplary embodiment of the present specification, the polymer separation membrane is a reinforced membrane further comprising a substrate.

This specification is described; A polymer comprising a unit derived from the compound represented by Formula 1; And it provides a reinforced film comprising inorganic particles.

According to an exemplary embodiment of the present specification, the "reinforced membrane" is a separation membrane containing a substrate that is a reinforcing material, a membrane capable of exchanging ions, a membrane including a substrate, an ion exchange membrane, an ion transport membrane, an ion conductive membrane, Separation membrane, ion exchange separation membrane, ion transfer separation membrane, ion conductive separation membrane, ion exchange electrolyte membrane, ion transfer electrolyte membrane, or ion conductive electrolyte membrane.

In the present specification, the substrate may mean a support having a three-dimensional network structure, and a reinforcement film comprising the substrate and the polymer may include one surface of the substrate, a surface facing the one surface, and inside the substrate. It may mean included in at least a part of the pore area. That is, the reinforcement film of the present specification may be provided in a form in which the polymer is impregnated into the substrate.

As used herein, "impregnation" means that polymer and inorganic particles are impregnated in the substrate.

According to an exemplary embodiment of the present specification, in the case of a hydrocarbon-based ion transport membrane, the ion-transporting ability is lower than that of the fluorine-based membrane, and there is a problem that chemical resistance is weak. Therefore, the reinforced film according to the exemplary embodiment of the present specification includes a polymer containing a unit derived from the compound represented by Chemical Formula 1, has high mechanical strength and high ionic conductivity, and can facilitate phase separation of the reinforced film. have.

In addition, the reinforcing film according to an exemplary embodiment of the present specification, including a substrate, can increase the chemical resistance and durability, thereby improving the life of the device.

According to an exemplary embodiment of the present specification, the substrate is one or two types in the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), polyethylene (PE) and polyvinylidene difluoride (PVDF) Is selected.

According to an exemplary embodiment of the present specification, the content of the polymer and the inorganic particles with respect to 100 parts by weight of the reinforced film is 10 parts by weight to 99 parts by weight.

According to another exemplary embodiment of the present specification, with respect to 100 parts by weight of the reinforced film, the content of the polymer and inorganic particles is 10 parts by weight to 99 parts by weight, and the content of the substrate is 1 part by weight to 90 parts by weight . As the content of the substrate increases, the crossover of vanadium ions may be reduced, and as the content of the polymer increases, the performance of the battery may be improved. Therefore, when the substrate, polymer, and inorganic particles according to an exemplary embodiment of the present specification are within the above range, it is possible to reduce the crossover of vanadium ions while maintaining the performance of the battery.

According to an exemplary embodiment of the present specification, the ion conductivity of the reinforced film is 0.001 S / cm to 0.5 S / cm. According to another exemplary embodiment, the ionic conductivity of the reinforced film is 0.001 S / cm to 0.3 S / cm.

In the present specification, the ion conductivity can be measured under the same conditions as the above method.

Further, according to an exemplary embodiment of the present specification, the ion exchange capacity (IEC) value of the reinforced membrane is 0.01 mmol / g to 5.0 mmol / g. When the ion exchange capacity value ranges, an ion channel is formed in the reinforced film, and the polymer may exhibit excellent ion conductivity.

According to an exemplary embodiment of the present specification, the thickness of the reinforced film is 0.01 ㎛ to 10,000 ㎛. The reinforcing film having the above-described thickness may reduce electric short and crossover of the electrolyte material, and exhibit excellent cationic conductivity characteristics.

The present specification also includes the steps of preparing a substrate; And impregnating the substrate with a mixed solution of the polymer and inorganic particles.

According to one embodiment of the present specification, the impregnation may be performed by dipping the substrate in a mixed solution of the polymer and inorganic particles, dipping, slot dye coating, bar casting, or the like. have.

In this specification, immersion may be expressed in terms such as dip coating or dipping method.

According to the exemplary embodiment of the present specification, the reinforced film may have directionality.

Specifically, according to an exemplary embodiment of the present specification, the substrate may be manufactured through uniaxial stretching or biaxial stretching, and the orientation of the substrate by the stretching may determine the orientation of the reinforcement film. Therefore, the reinforcing film according to an exemplary embodiment of the present specification may have a machine direction (MD) and a direction in the vertical direction of the machine direction, and the reinforcing film may include stress and elongation according to the direction. May have a difference in physical properties.

The present specification also includes the steps of preparing a substrate; And a polymer containing a unit derived from the compound represented by Chemical Formula 1 above. And immersing in a mixed solution containing inorganic particles.

In the present specification, the substrate, polymer and inorganic particles are as described above.

The present specification also includes an anode; Cathode; And it provides a membrane electrode assembly comprising the above-described polymer separation membrane provided between the anode and the cathode.

In the present specification, the term "membrane electrode assembly (MEA)" means an electrode (cathode and anode) where an electrochemical catalytic reaction of fuel and air occurs and a polymer separation membrane where hydrogen ion transfer occurs, and an electrode (cathode and cathode) Anode) and a single membrane-bonded unit.

According to an exemplary embodiment of the present specification, the membrane electrode assembly is in a form that the catalyst layer of the anode and the catalyst layer of the cathode contact the polymer separation membrane, it can be prepared according to a conventional method known in the art. In one example, the cathode; Anode; And it may be prepared by heat-pressing to 100 ℃ to 400 ℃ in a state in close contact with the polymer membrane positioned between the cathode and the anode.

According to one embodiment of the present specification, 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.

According to an exemplary embodiment of the present specification, 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 microporous layer and a cathode electrode substrate.

FIG. 1 schematically shows the principle of electricity generation in a fuel cell, and in a fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is a separator 100 and both sides of the separator 100 It is composed of an anode (200a) and a cathode (200b) formed on the electrode. Referring to Fig. Showing the electricity generating principle of a fuel cell 1, an anode (200a) in the hydrogen or methanol, up the oxidation reaction of fuel of hydrocarbon such as butane hydrogen ions (H ⁺⁾ and electron (e ^-) is generated and , Hydrogen ions move to the cathode 200b through the separation membrane 100. In the cathode 200b, hydrogen ions transferred through the separator 100 react with oxidizing agents such as oxygen and electrons to generate water. The reaction causes electron movement to occur in the external circuit.

The catalyst layer of the anode electrode is where the oxidation reaction of fuel occurs, and a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum-transition metal alloy is preferred. Can be used.

The catalyst layer of the cathode electrode is a place where a reduction reaction of an oxidizing agent occurs, and a platinum or platinum-transition metal alloy can be preferably used as a catalyst. The catalysts can be used by themselves as well as supported on a carbon-based carrier.

The process of introducing the catalyst layer may be performed by a conventional method known in the art, for example, the catalyst ink may be directly coated on a separator or a gas diffusion layer to form a catalyst layer. At this time, 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. The catalyst ink is typically made of a catalyst, a polymer ionomer, and a solvent.

The gas diffusion layer serves as a current conductor and serves as a passage for the reaction gas and water, and has a porous structure. Therefore, the gas diffusion layer may be formed of a conductive substrate. Carbon paper, carbon cloth or carbon felt may be preferably used as the conductive substrate.

The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive substrate. The microporous layer can be used to improve the performance of the fuel cell under low-humidity conditions, and serves to keep the polymer membrane in a sufficiently wet state by reducing the amount of water passing out of the gas diffusion layer.

One embodiment of the present specification is two or more membrane electrode assembly; A stack including 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 oxidizing agent supply unit for supplying an oxidizing agent to the stack.

A fuel cell is an energy conversion device that directly converts chemical energy of fuel into electrical energy. That is, a fuel cell is a power generation method that uses fuel gas and an oxidizing agent, and generates electricity using electrons generated during their redox reaction.

The fuel cell can be manufactured according to conventional methods known in the art using the above-described membrane electrode assembly (MEA). For example, the membrane electrode assembly (MEA) and the bipolar plate (bipolar plate) prepared above may be manufactured.

In the present specification, the fuel cell includes a stack, a fuel supply unit, and an oxidizer supply unit.

3 schematically illustrates the structure of a fuel cell, and the fuel cell includes a stack 60, an oxidizing agent supply unit 70, and a fuel supply unit 80.

The stack 60 includes one or more of the above-described membrane electrode assemblies, and when two or more membrane electrode assemblies are included, includes a separator interposed therebetween. 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 oxidizing agent supply unit 70 serves to supply the oxidizing agent to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air may be injected into the pump 70 to be used.

The fuel supply unit 80 serves to supply fuel to the stack 60, and to a fuel tank 81 for storing fuel and a pump 82 for supplying fuel stored in the fuel tank 81 to the stack 60. Can be configured. As the fuel, gaseous or liquid hydrogen or hydrocarbon fuels may be used. Examples of 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.

According to one embodiment of the present specification, when the polymer separation membrane is used as the ion exchange membrane of the fuel cell, the above-described effect may be exhibited.

In addition, according to one embodiment of the present specification, an anode cell including an anode and an anode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And it provides a redox flow battery comprising the polymer separator provided between the anode cell and the cathode cell.

Redox flow battery (oxidation-reduction flow battery, Redox Flow Battery) is a system in which the active substance contained in the electrolyte is oxidized, reduced and charged and discharged. to be. Redox flow batteries use the principle of charging and discharging electrons when an electrolyte containing an active material having different oxidation states meets the ion exchange membrane. In general, a redox flow battery is composed of a tank containing electrolyte, a battery cell in which charging and discharging occurs, and a circulation pump for circulating the electrolyte between the tank and the battery cell, and the unit cells of the battery cell are electrodes, electrolytes and ions. Includes an exchange membrane.

According to one embodiment of the present specification, when the polymer separation membrane is used as the ion exchange membrane of the redox flow battery, the above-described effect may be exhibited.

According to the exemplary embodiment of the present specification, the redox flow battery may be manufactured according to a conventional method known in the art, except that the polymer separation membrane is included.

As shown in FIG. 2, the redox flow battery is divided into a positive electrode cell 32 and a negative electrode cell 33 by a separator 31. The positive electrode cell 32 and the negative electrode cell 33 include positive and negative electrodes, 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 a 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 (ie, a redox reaction) in which the oxidized water of ions is changed occurs, so that charging and discharging occur at the anode and cathode.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

< Manufacturing example  1> Synthesis of polymer

Using the above compound, a sulfonate-based compound according to an exemplary embodiment of the present specification was synthesized.

4,4'-Biphenol (4,4'-Biphenol) and 4,4'-difluorobenzophenone (4,4'-Difluorobenzophenone) and synthesized sulfonate compounds according to one embodiment of the present specification Polymerization was carried out at 140 ° C for 4 hours and at 180 ° C for 24 hours, and polymerization was performed using N-methyl-2-piperidone (NMP) as a solvent. After this, the mixture was sufficiently cooled at room temperature and precipitated in ethanol to obtain a polymer resin.

Ion transfer separators were prepared by making 20 wt% solution (solvent DMAc) of the synthesized resin and coating the solution, followed by drying in a vacuum oven at 110 ° C. for 24 hours. The ion transport membrane was immersed in a 10 wt / wt% sulfuric acid (H ₂ SO ₄ ) solution at 80 ° C. for 24 hours, and then rinsed several times with distilled water (DI water) to measure ion conductivity. The counterion of the sulfonic acid was replaced by H ⁺ rather than K ⁺ .

< Example  1> Composite membrane (Inorganic particles 0.5wt% )

The solution of silica nanoparticles (size: ~ 10 nm) in an ion transfer resin solution (viscosity 500 cP, IEC 2.3) containing a polymer synthesized by the method of Preparation Example 1 is based on the total content of the solid content of the polymer separator. The content was added to be 0.5 wt% (solvent NMP or DMAc), followed by stirring at room temperature for 4 hours.

After coating and drying on a glass substrate, a film having a size of about 20 μm was produced.

< Example  2> Composite membrane (Inorganic particles 5wt% )

A film was prepared in the same manner as in Example 1, except that the silica nanoparticle solution in Example 1 was added so that the content of the silica nanoparticles was 5 wt% based on the total content of the polymer separator solid content.

< Example  3> Composite membrane (Inorganic particles 10wt% )

A film was prepared in the same manner as in Example 1, except that the silica nanoparticle solution in Example 1 was added so that the content of the silica nanoparticles was 10 wt% based on the total content of the polymer separator solid content.

< Example  4> Composite membrane (Inorganic particles 0.1wt% )

A film was prepared in the same manner as in Example 1, except that the silica nanoparticle solution in Example 1 was added so that the content of the silica nanoparticle was 0.1 wt% based on the total content of the polymer separator solid content.

< Comparative example  1> Pure polymer separator

After coating and drying on a glass substrate with an ion transfer resin solution (viscosity 500 cP, IEC 2.3) containing a polymer synthesized by the method of Preparation Example 1, a film having a size of about 20 μm was produced.

The properties of the films prepared in Examples 1 to 4 and Comparative Example 1 were measured by the following method, and the results are shown in Table 1 below.

IEC stands for ion exchange capacity, and after precipitation for 24 hours in a saturated sodium chloride (NaCl) aqueous solution, the amount of released hydrogen ions (H ⁺ ) was measured by a method calculated through sodium hydroxide (NaOH) titration.

In addition, the water uptake was calculated by immersing the film in ultrapure water for 24 hours and then calculating the weight difference before and after immersion. The moisture content may be defined by Equation 1 below.

[Equation 1]

Swelling ratio (Swelling ratio) was calculated by the following equation 2 by measuring the thickness of the film before and after immersing the dried film in distilled water at room temperature for 24 hours.

[Equation 2]

The ion conductivity of the film was measured using a four-electrode cell with temperature and humidity control, and the humidity dependence was measured using an AC impedance method. After maintaining for more than 2 hours in the humidity section, the ion conductivity was measured after reaching a sufficiently parallel state.

Ionic conductivity 1 was measured by the method described above at a relative humidity (RH) of 100% and 25 ° C, and ion conductivity 2 was measured by the method described above at a relative humidity of 50% and 60 ° C.

Vanadium ion permeability is fixed by inserting a film prepared in a redox flow battery cell, and then dissolving 1M magnesium sulfate (MgSO ₄ ) in 2M sulfuric acid (H ₂ SO ₄ ) at the cathode, and 1M oxysulfuric acid at the anode. While circulating the solution in which vanadium (VOSO ₄ ) was dissolved in 2M sulfuric acid (H ₂ SO ₄ ), the concentration of vanadium ions at the cathode was measured over time, and the permeability was calculated by Equation 3 below.

The concentration of vanadium ions was converted by measuring absorbance at a quaternary ion wavelength of 767 nm using a UV spectrophotometer (Simadzu UV-1650PC).

[Equation 3]

In Equation 3,

V means the volume of sulfuric acid solution,

C _O means the initial concentration of vanadium ion in the magnesium sulfate tank,

C _t means the concentration of vanadium ions in the magnesium sulfate tank at time t,

S means the area of the film in contact with the sulfuric acid solution,

P means the permeability of vanadium ions,

L means the thickness of the film.

IEC
(meq / g) moisture
Absorption
(%) Swelling ratio
(%)
z-axis Ion conductivity 1
(S / cm)
@ RH100%, 25 ℃ Ion conductivity 2
(S / cm)
@ RH50%, 60 ℃ Vanadium ion permeability
(x10 ^-6 ㎠ / min) Example 1 1.988 80.5 26.47 0.12 0.05 2.03 Example 2 1.508 49.1 7.35 0.08 0.09 1.83 Example 3 1.231 12.4 2.92 0.04 0.04 1.02 Example 4 2.005 102.2 33.2 0.12 0.03 4.08 Comparative Example 1 2.057 119.9 35.3 0.12 0.03 5.84

As a result of Table 1, in the case of Comparative Example 1, which does not contain inorganic particles, it has excellent ionic conductivity in terms of application of a fuel cell or a redox flow cell, but has a high moisture absorption, swelling ratio, and high vanadium ion permeability. , It may adversely affect the application of the redox flow battery.

According to the exemplary embodiment of the present specification, in the case of a polymer separation membrane further comprising inorganic particles in addition to the polymer, the moisture-containing ability is excellent while maintaining ion conductivity for application to a fuel cell or a redox flow cell, and in a low-humidity condition. It can be confirmed that the ionic conductivity is excellent.

From the results, it was confirmed that the heat resistance of the polymer membrane and the water retention at high temperatures were increased by the introduced inorganic particles. However, when the content of the inorganic particles is more than 10 wt%, it can be seen that the ionic conductivity decreases, so that the problem of even dispersion can act as a major factor in performance.

In addition, it can be seen that the polymer separation membrane according to the exemplary embodiment of the present specification has excellent water absorption, swelling ratio, and vanadium ion permeability performance as compared to the case of not containing inorganic particles.

100: separator
200a: anode
200b: cathode
10, 20: Tank
11, 21: Pump
31: separator
32: anode cell
33: cathode cell
41: anode electrolyte
42: cathode electrolyte
60: stack
70: oxidizing agent supply unit
80: fuel supply
81: fuel tank
82: Pump

Claims (16)

Polymer comprising a unit derived from the compound represented by the formula (1); And
Polymer separation membrane comprising inorganic particles:
[Formula 1]

In Chemical Formula 1,
R1 and R2 are each characterized by being F,
A is O or NR4,
Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R3 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 ) _q SO ₃ H, ―O (CF ₂ ) _q SO ₃ ^- M ⁺ , ―O (CF ₂ ) _q COOH, ―O (CF ₂ ) _q COO ^- M ⁺ , ―O (CF ₂ ) _q PO ₃ H ₂ , ―O (CF ₂ ) _q PO ₃ H ^- M ⁺ , ―O (CF ₂ ) _q PO ₃ ^2- 2M ⁺ or represented by the following Chemical Formula 2,
q is an integer from 1 to 6,
M is a group 1 element,
R4 is H, CH ₃ , (CF ₂ ) _o SO ₃ H or (CF ₂ ) _p CO ₂ H,
n, o and p are each independently an integer of 1 to 10, and when n is 2 or more, structures in parentheses are the same or different from each other,
[Formula 2]

In Chemical Formula 2,
Z3 and Z4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R5 is SO ₃ H or CO ₂ H,
m is an integer of 1 to 10, and when m is an integer of 2 or more, structures in parentheses are the same or different from each other. delete The method according to claim 1,
The Z1 to Z4 are the same or different from each other, and each independently, F, Cl, Br and polymer separator characterized in that it is selected from the group consisting of I. The method according to claim 1,
The unit represented by Formula 1 is a polymer separation membrane characterized in that represented by any one of the following Formula 1-1 to Formula 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Chemical Formulas 1-1 to 1-4,
R6 is H, CH ₃ , (CF ₂ ) _o SO ₃ H or (CF ₂ ) _p CO ₂ H,
n, o and p are as defined in Formula 1. The method according to claim 1,
The particle diameter of the inorganic particles is 5 nm to 50 ㎛ polymer separation membrane. The method according to claim 1,
The inorganic particles are inorganic; Hetero polyacid; And one or two or more polymer separators from the group consisting of inorganic acids. The method according to claim 1,
The inorganic particle is a polymer separation membrane that is provided in a form dispersed in the polymer separation membrane. The method according to claim 1,
Based on the total content of solids in the polymer membrane
The content of the inorganic particles is 0.5% to 10% by weight,
The polymer content is 90 to 99.5% by weight of the polymer separator. The method according to claim 1,
The polymer is a polymer separator that is a random polymer or a block polymer. The method according to claim 1,
The polymer is a branch represented by the following formula (3); Or a polymer separator further comprising a brancher represented by the following formula (4):
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,
X is S; O; CO; SO; SO ₂ ; NR; Hydrocarbon-based or fluorine-based conjugates,
l is an integer from 0 to 100, and when l is 2 or more, 2 or more Xs are the same or different from each other,
Y1 and Y2 are the same as or different from each other, and each independently an aromatic ring substituted by 1 or 2 or more with a substituent selected from the group consisting of a hydroxy group and a halogen group; An aliphatic ring substituted by 1 or 2 or more with a substituent selected from the group consisting of a hydroxy group and a halogen group; Or an amine group represented by NR'R ",
R, R 'and R "are aromatic rings substituted with halogen groups; or aliphatic rings substituted with halogen groups,
Z is a trivalent organic group. The method according to claim 1,
The polymer separator has an ion conductivity of 0.01 S / cm to 0.5 S / cm. The method according to claim 1,
The polymer membrane has an ion exchange capacity (IEC) value of 0.01 mmol / g to 5 mmol / g. The method according to claim 1,
The polymer separator has a thickness of 1 μm to 500 μm. Anode; Cathode; And a polymer separation membrane according to any one of claims 1 and 3 to 13 provided between the anode and the cathode. A membrane electrode assembly according to claim 14 of 2 or more;
A stack including a bipolar plate provided between the membrane electrode assemblies;
A fuel supply unit supplying fuel to the stack; And
A polymer electrolyte fuel cell including an oxidizing agent supply unit for supplying an oxidizing agent to the stack. An anode cell comprising an anode and a cathode electrolyte;
A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And
Redox flow battery comprising the polymer separator of any one of claims 1 and 3 to 13 provided between the anode cell and the cathode cell.

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