KR101794320B1 - Crosslinker for ion exchangable polymer for vanadium redox flow battery, ion exchangable-crosslinked polymer for vanadium redox flow battery crosslinked by the crosslinker and use thereof - Google Patents

Abstract

The present invention relates to a crosslinking agent for an ion-exchange polymer having an electron-withdrawing group, an ion-conducting crosslinking polymer crosslinked by the crosslinking agent, and a use thereof, and more particularly to a method for forming an ion-exchange functional group as a primary or secondary amine crosslinking agent It is possible to prevent the change of the membrane shape by suppressing the rapid crosslinking reaction at the time of film formation due to the presence of the electron attracting moiety. In particular, the dimensional stability due to crosslinking stability, mechanical stability, and ease of control of anion exchange groups, an ionically conductive crosslinked polymer crosslinked by the crosslinking agent, and a use thereof.

Description

Technical Field [0001] The present invention relates to a crosslinking agent for an ion-exchange polymer for a vanadium redox flow cell, an ion-conductive crosslinking polymer for a vanadium redox flow-type crosslinked by the crosslinking agent, and a use thereof for a crosslinkable polymer for vanadium redox flow battery crosslinked by the crosslinker and use thereof.

The present invention relates to a crosslinking agent for an ion-exchange polymer for a vanadium redox flow cell having an electron-attracting group, an ion-conductive crosslinking polymer for a vanadium redox flow battery crosslinked by the crosslinking agent, and a use thereof.

Efforts are being made to save fossil fuels or to apply renewable energy to more fields by improving the use efficiency to solve problems of depletion of fossil fuels and environmental pollution.

As one of them, a rechargeable battery provides a simple and efficient electric storage method, so that it is miniaturized to increase the mobility, and efforts to utilize it as an auxiliary power source for an intermittent auxiliary power or a power source of a small household appliance such as a laptop, a tablet PC, . In particular, a redox flow battery (RFB) is a secondary battery which can store and use energy for a long period of time by repeatedly charging and discharging by an electrochemical reversible reaction of an electrolyte. And the electrolytic tanks are independent of each other. Therefore, the battery design is free and the installation space is limited.

The ion conductive polymer membrane for new and renewable energy used in such a secondary battery is not only dependent on the core chemical material of the system or the whole amount of the system, but is also very expensive, so localization is necessary.

The presently used ion-exchange material is Nafion, a perfluorocyte cation exchange material. Nafion has excellent initial performance and durability, but at a very high price and a high crossover of active material, There is a difficulty. In particular, in the case of Vanadium Redox Flow Battery (VRFB), which has a higher ratio of ion-exchange materials in total system price than energy conversion systems such as fuel cells, It is the most important factor. Further, the continuous degradation of the performance due to the crossover of the vanadium ion causes a problem of causing not only the deterioration of the system life but also the additional cost for regenerating the active material. Therefore, the development of low-cost, low-crossover separator materials is considered to be urgently needed to commercialize VRFB.

Accordingly, the present inventors have made intensive studies to find a low-cost ion-exchange material using a hydrocarbon-based polymer. As a result, they have found that by improving the dimensional stability using an amine-based crosslinking agent having excellent reactivity and a simple crosslinking process, the crossover of the active material can be reduced And that the permeability of the cationic active material can be lowered by introducing an anion exchange group into the ion exchange group, and the present invention has been completed.

It is an object of the present invention to provide a crosslinking agent for an ion exchangeable polymer for a vanadium redox flow cell which can only crosslink without formation of an ion exchangeable functional group and inhibit a rapid crosslinking reaction during film formation to prevent a change in the shape of the membrane, And an ion conductive crosslinked polymer for use in the vanadium redox flow battery.

A first aspect of the present invention provides a crosslinker composition for an ion-exchange crosslinked polymer for a vanadium redox flow battery comprising a compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D and D 'are each independently -NH ₂ or -NHR, wherein R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

a and b are each independently 0 or an integer of 1 to 100;

The second aspect of the present invention provides an ionically conductive crosslinked polymer for a vanadium redox flow cell, wherein the ion conductive polymer is crosslinked through a crosslinking unit represented by the following formula (2)

(2)

In Formula 2,

E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or -NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, an alkyl group , An aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;

G and G 'are a single bond, or -O-, -S-, -NH- or NR ₄₇ - as an electron donor, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;

R ₉ to R ₁₆ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

또는

이고;Ar

or

ego;

J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

and x is an integer of 1 to 10000.

A third aspect of the present invention provides a compound comprising a repeating unit represented by the following formula (4) or (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)

E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, Or an aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;

G and G 'are a single bond, or -O-, -S-, -NH- or NR ₄₇ - as an electron donor, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;

W ₁ to W ₈ each independently represent a hydrogen atom; A chlorinated alkyl group, a brominated alkyl group or an iodinated alkyl group represented by (CH ₂ ) _h X ( ₁ ? _H ? 12); Or an alkyl chloride group, brominated alkyl group or iodinated alkyl group containing an ether group and an ester group, X is a halogen atom;

R ₂₉ to R ₄₆ and R ₃₅ 'to R ₄₆ ' each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group , A C ₂ to C ₁₂ allyl group, a cyano group (-CN), a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, at least one oxygen, A perfluoroalkylaryl group, a perfluoroaryl group or an -O-perfluoroaryl group;

또는

이고;Ar

or

ego;

J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D " and D "'are each independently NH or -NR, wherein R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

x 'is an integer from 1 to 10000;

a and b are each independently 0 or an integer of 1 to 100;

c, d, e and f are each independently an integer of 1 to 10000.

In a fourth aspect of the present invention, there is provided a method for producing an ionically conductive crosslinked polymer for a vanadium redox flow battery according to the second aspect,

A first step of preparing a halogenated polymer;

A second step of adding a cross-linking agent represented by the following formula (1) to the halogenated polymer to form a cross-linked polymer by a cross-linking reaction between the halogenated polymers at some halogen functional sites of the halogenated polymer; And

And a third step of replacing the residual halogen functionality of the crosslinking polymer with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group.

[Chemical Formula 1]

In Formula 1,

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D and D 'are each independently -NH ₂ or -NHR, wherein R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

a and b are each independently 0 or an integer of 1 to 100;

A fifth aspect of the present invention provides a film comprising an ionically conductive crosslinked polymer for a vanadium redox flow battery according to the second aspect.

Hereinafter, the present invention will be described in detail.

In the present invention, a primary or secondary amine cross-linking agent can be used as the amine-based cross-linking agent to perform crosslinking only without forming an ion-exchange functional group. In particular, it has an advantage that it improves the dimensional stability and mechanical stability due to crosslinking without affecting the functions of membranes such as water uptake and conductivity, and is easy to control the anion exchange function.

In particular, in the present invention, by using an aromatic primary or secondary amine crosslinking agent having an electron-withdrawing group at the "A" position as a compound represented by the following formula (1), it is possible to suppress the rapid crosslinking reaction during film formation,

[Chemical Formula 1]

Preferably, A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of the foregoing electron withdrawing groups, especially a compound having - (C = O) - as A, with an amine for the preparation of an ion exchange cross- Can be used as a crosslinking agent.

Specifically, in the examples of the present invention, when an ion-exchange membrane was prepared using various amine-based crosslinking agents and subjected to a screening test, the aromatic and alicyclic amines as crosslinking agents were much longer in retention time than aliphatic groups, ", It was found that the retention time was significantly increased in the case of the electron withdrawing group, and it was confirmed that the effect of preventing the change of the film shape due to the rapid crosslinking reaction during the film formation was confirmed. In addition, when the primary or secondary amine group of -NH ₂ or -NHR is located in the above "D" and "D '" and the compound represented by the above-mentioned formula (1) is used only as a crosslinking agent Lt; / RTI >

The ion exchangeable and / or ionically conductive crosslinked polymer of the present invention can be used for preparing an ion exchange membrane for a vanadium redox flow battery.

The present invention can provide an ionically conductive crosslinked polymer for a vanadium redox flow cell crosslinked by the crosslinking agent represented by the above formula (1).

As used herein, the term "ionically conductive polymer" refers to a polymer having ionic conductivity, which is a polymer provided as a polymer backbone before crosslinking.

The term "ionically conductive crosslinked polymer" used in the present invention may mean an ion conductive polymer crosslinked by the crosslinking agent represented by the general formula (1). In this case, the crosslinking may occur between the main chain portions of the ion conductive polymer and may occur at the side chain portions connected to the main chain of the ion conductive polymer.

The ion conductive crosslinked polymer according to the present invention is characterized in that the ion conductive polymer is crosslinked through a crosslinking unit represented by the following formula (2).

(2)

In Formula 2,

E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or -NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, an alkyl group , An aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;

G and G 'are a single bond, or -O-, -S-, -NH- or NR ₄₇ - as an electron donor, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;

R ₉ to R ₁₆ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

또는

이고;Ar

or

ego;

J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

and x is an integer of 1 to 10000.

Preferably, x is an integer of 5 to 500.

The ionically conductive crosslinked polymer according to the present invention may be formed by crosslinking a halogenated polymer at a halogen functional site in the halogenated polymer.

In the present invention, the ion conductive polymer may have an anion-exchangeable functional group, a cation-exchangeable functional group or an amphoteric ion-exchange functional group.

In the present invention, the anion exchangeable functional group is a salt-like anion exchange functional group derived from a pyridyl group, a carbazolyl group or an imidazolyl group, or an anion exchange functional group derived from -N ⁺ H ₃ L ^- , -N ⁺ R'H ₂ L ^- , -N _{^{+ R '2 HL -, -N}} + R' 3 L -, -P + R '3 L -, -S + R' 2 L - or C ₅ H ₅ N ⁺ HL ^- and (R 'is C _{1- 4} alkyl or C _6-12 aryl, L ^- is a hydroxide anion, bicarbonate anion, chloride anion, bromide anion, iodide or sulfate anion Im), a cation-exchange functional groups are -SO ₃ ^-, -COO ^-, -PO ₃ ^2- , -PO ₃ H ^- or -C ₆ H ₄ 0 ^- , and the amphoteric ion-exchange functional group may be betaine or sulfobetaine.

In one embodiment, the ionically conductive crosslinked polymer for a vanadium redox flow battery according to the present invention may have a skeleton containing a repeating unit represented by the following formula (3).

(3)

In Formula 3,

E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, Or an aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;

G and G 'are -O-, -S-, -NH- or NR ₄₇ - as a single bond or electron donor group, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;

Z ₁ to Z ₆ each independently represent a hydrogen atom, (CH ₂ ) _h M (1 ≦ _h ≦ 12) or (CH ₂ ) _h M containing an ether group and an ester group (1 ≦ _h ≦ 12) Is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;

R ₃₅ to R ₄₆ and R ₃₅ 'to R _46' each independently represent a hydrogen atom (-H), halogen atoms (-X), C ₁ to alkyl, substituted by halogen, alkyl of C _12, C ₂ to C ₁₂ of an allyl group, a cyan group (-CN), C ₆ to C ₁₀ aryl group, a nitro group (-NO _2), a perfluoroalkyl containing perfluoro oxygen, nitrogen or sulfur atom, an alkyl group, one or more of alkyl aryl , A perfluoroaryl group or an -O-perfluoroaryl group;

또는

이고;Ar

or

ego;

J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D " and D '" are each independently NH or -NR, and R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a halogen substituted alkyl group, a C ₂ to C ₁₂ allyl group, CN, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a perfluoroaryl group or - O-perfluoroaryl group;

a and b are each independently 0 or an integer of 1 to 100;

c, d, e and f are each independently an integer of 1 to 10000. E is -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or -NR ₄₉ - as a single bond or electron donor group, and each of R ₄₈ and R ₄₈ ' independently represents a hydrogen atom, an alkyl group, Group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;

G and G 'are -O-, -S-, -NH- or NR ₄₇ - as a single bond or electron donor group, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;

Z ₁ to Z ₆ each independently represents a hydrogen atom or (CH ₂ ) _h M (1 ≦ _h ≦ 12) containing (CH ₂ ) _h M (1 ≦ _h ≦ 12) or an ether group and an ester group, Is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;

R ₃₅ to R ₄₆ and R ₃₅ 'to R ₄₆ ' each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group , A C ₂ to C ₁₂ allyl group, a cyano group (-CN), a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, optionally one or more oxygen, A perfluoroalkylaryl group containing a sulfur atom, a perfluoroaryl group or an -O-perfluoroaryl group;

또는

이고;Ar

or

ego;

J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D " and D "'are each independently NH or -NR, wherein R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

a and b are each independently 0 or an integer of 1 to 100;

c, d, e and f are each independently an integer of 1 to 10000.

Preferably, c, d, e and f are each independently an integer of 5 to 500.

The ionically conductive crosslinked polymer having a skeleton containing the repeating unit represented by Formula 3 may be prepared by reacting a halogen functional group of a crosslinked polymer having a skeleton containing a repeating unit represented by Formula 5 with an anion exchange functional group, Lt; RTI ID = 0.0 > ion-exchangeable < / RTI > functional groups.

[Chemical Formula 5]

In Formula 5,

E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or -NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, an alkyl group , An aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;

G and G 'are -O-, -S-, -NH- or NR ₄₇ - as a single bond or electron donor group, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;

W ₃ to W ₈ each independently represent a hydrogen atom; A chlorinated alkyl group, a brominated alkyl group or an iodinated alkyl group represented by (CH ₂ ) _h X ( ₁ ? _H ? 12); Or an alkyl chloride group, brominated alkyl group or iodinated alkyl group containing an ether group and an ester group, X is a halogen atom;

R ₃₅ to R ₄₆ and R ₃₅ 'to R _46' each independently represent a hydrogen atom (-H), halogen atoms (-X), C ₁ to alkyl, substituted by halogen, alkyl of C _12, C ₂ to C ₁₂ of an allyl group, a cyan group (-CN), C ₆ to C ₁₀ aryl group, a nitro group (-NO _2), a perfluoroalkyl containing perfluoro oxygen, nitrogen or sulfur atom, an alkyl group, one or more of alkyl aryl , A perfluoroaryl group or an -O-perfluoroaryl group;

또는

이고;Ar

or

ego;

J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D " and D "'are each independently NH or -NR, wherein R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;

a and b are each independently 0 or an integer of 1 to 100;

c, d, e and f are each independently an integer of 1 to 10000.

Preferably, c, d, e and f are each independently an integer of 5 to 500.

Within each repeating unit in the ion-conducting crosslinked polymer according to the invention _{R 35, R 36, R 37} , R 38, R 39, R 40, R 41, R 42, R 43, R 44, R 45, R 46, R _{35 ', R 36', R} 37 ', R 38', R 39 ', R 40', R 41 ', R 42', R 43 ', R 44', R 45 ' and R _46' are the same or another Can be different. Accordingly, in the ionically conductive crosslinked polymer according to the present invention, each repeating unit may be composed of the same repeating units or different repeating units may form a certain block to form a block copolymer, May be randomly connected to form a random copolymer.

The ionically conductive crosslinked polymer according to the present invention may have Mn (number-average molecular weight) of 10,000 to 1,000,000 or molecular weight of Mw (weight-average molecular weight) of 10,000 to 10,000,000. When the molecular weight is low, for example, when Mn and Mw are less than 10,000, film formation is difficult, the moisture content is increased, and it is easily decomposed by the attack of radical, so that conductivity and durability may be decreased. On the other hand, when the molecular weight is high, for example, when the Mn is more than 1,000,000 or the Mw is more than 10,000,000, the production of the polymer solution and molding into a film become difficult due to the rapidly increased viscosity, and the film manufacturing process may become impossible.

Since the weight average molecular weight and the viscosity average molecular weight are similar to each other, the intrinsic viscosity of the polymer is measured to predict the molecular weight in the specific examples of the present invention. GPC (gel permeation chromatography) can be used to measure the molecular weight. However, in the case of a polymer substituted with a sulfonic acid group, the molecular weight can be estimated by measuring viscosity since it is difficult to trust data due to interaction between sulfonic acid groups.

In the present invention, the ion conductive polymer preferably has a halogen functional group, and at the halogen functional group position, the compound represented by the general formula (1), that is, the crosslinking agent according to the present invention, The ion-conductive crosslinked polymer according to the present invention can be formed.

As described above, the ion conductive polymer as a main chain of the ion conductive crosslinked polymer according to the present invention may be a random copolymer, a cross-copolymer or a block copolymer. That is, the ion conductive polymer constituting the backbone itself may be various types of polymers such as random copolymers, cross-linked copolymers, and block copolymers. In the functional groups capable of causing a cross-linking reaction in the polymer, Crosslinked by a compound, polymers having various forms such as random copolymers, cross-linked copolymers, and block copolymers can be crosslinked to form ionically-crosslinked polymers (FIG. 1). The functional group capable of causing the crosslinking reaction is preferably a halogen element. Examples of the halogen element include F (fluorine), Cl (chlorine), Br (bromine) and I (iodine). The halogen element is a substituent that is widely introduced for the reaction such as condensation and substitution because it is excellent in reactivity when it is introduced as a substituent to an organic compound due to high electronegativity due to high effective nuclear charge. More preferably, the halogen element may be a chlorine atom.

As described above, the method for producing an ionically conductive crosslinked polymer for a vanadium redox flow battery according to the second aspect,

A first step of preparing a halogenated polymer;

A second step of adding a cross-linking agent represented by the following formula (1) to the halogenated polymer to form a cross-linked polymer by a cross-linking reaction between the halogenated polymers at some halogen functional sites of the halogenated polymer; And

And a third step of replacing the residual halogen functionality of the crosslinking polymer with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group.

[Chemical Formula 1]

In Formula 1,

A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;

D and D 'are each independently -NH ₂ or -NHR, wherein R is a C ₁ to C ₁₂ alkyl group;

R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a halogen substituted alkyl group, a C ₂ to C ₁₂ allyl group, CN, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a perfluoroaryl group or - O-perfluoroaryl group;

a and b are each independently 0 or an integer of 1 to 100;

The first step is a step of preparing a polymer to which a halogen functional group is introduced as a reactive functional group capable of causing a crosslinking reaction.

The term " degree of halogenation "used in the present invention is a value obtained by dividing the number of halogen functional groups produced in the whole polymer by the halogenation reaction divided by the total number of repeating units. I. E., The number of halogen functional groups per repeating unit. Similarly, for example, "degree of bromination" is a value obtained by dividing the number of bromine functional groups produced in the entire polymer by the number of all repeating units through the bromination reaction, and "degree of chloromethylation " "Is a value obtained by dividing the number of bromine functional groups produced in the entire polymer by the number of all repeating units through chloromethylation reaction.

In the present invention, the degree of halogenation of the halogenated polymer is 1 to 150% (0.01 to 1.5), such as 10 to 120% (0.1 to 1.2), 10 to 30% (0.1 to 0.3), 30 to 50% (0.3 to 0.5) 80 to 100% (0.8 to 1), and the like.

In the present invention, a halogenated polymer can be used by obtaining a commercially available one, or by directly halogenating a non-halogenated polymer. Also, in the present invention, the halogenated polymer may be prepared by using a monomer as a desired polymer by directly polymerizing and halogenating the monomer.

The halogenation can be carried out using various known methods. For example, the bromination of poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) can be carried out as described in Hsin-I Chang et al. Methyl-brominated PPO synthesis method of Reactive & Functional Polymers, 70, (2010) 944-950 and X. Tongwen, Y. Weihua (Journal of Membrane Science, 190, (2001) 159-166) . The desired degree of bromination can be controlled according to the molar ratio of NBS (N-bromosuccinimide). In addition, chloromethylation of polyphenylsulfone and polysulfone can be carried out by referring to a process for producing an anion conductor-containing solution of Korean Patent No. 10-1284009. The desired degree of chloromethylation can be controlled by the molar ratio of chloromethyl methyl ether.

The reaction temperature, the reaction time, the stirring conditions, and the halogen element used in the halogenation are not particularly limited, but may be appropriately selected depending on the size, performance characteristics, quality and other properties of the resultant ion exchange membrane. The halogen atom is not particularly limited, but includes fluorine, chlorine, bromine and iodine in particular.

The halogenation reaction temperature is selected, for example, preferably in the range of 0 to 300 占 폚, more preferably in the range of 20 to 200 占 폚. The halogenation reaction time can be appropriately selected depending on other conditions, and is preferably 1 to 10 hours. Under stirring conditions at the time of halogenation, a stirring speed in a usual halogenation reaction may be used. The reaction initiator used may be water-soluble or lipophilic and, in normal use, its peroxide or azo initiator may be used. For additives, conventional stabilizers and others may be used. Other reaction conditions are not specifically limited.

In the second step, a cross-linking agent represented by the general formula (1) is added to a halogenated polymer to form a cross-linked polymer by cross-linking reaction between halogenated polymers at a halogen functional site of the halogenated polymer.

In the second step, the film formation can be performed simultaneously with the crosslinking reaction. Specifically, the resin composition obtained by adding the crosslinking agent represented by the general formula (1) to the halogenated polymer can be formed into a molded article in the form of fiber or film by any method such as casting, extrusion, spinning or rolling. The resin composition may further contain various additives such as an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a cross-linking agent, a defoaming agent, and a dispersant, if necessary.

The reaction temperature, the reaction time, and the stirring conditions during the crosslinking in the second step are not specifically limited, but may be appropriately selected depending on the size, performance characteristics, quality and other properties of the resultant ion exchange membrane. The reaction temperature is, for example, preferably selected within the range of -10 to 400 占 폚, more preferably 0 to 200 占 폚. The reaction time can be appropriately selected depending on other conditions, and is preferably within 100 hours. In the stirring condition, the stirring speed in the ordinary crosslinking reaction can be used. Other reaction conditions are not specifically limited.

For example, a resin composition obtained by adding a crosslinking agent represented by the general formula (1) to a halogenated polymer may be molded to prepare an ion exchange membrane. Specifically, the halogenated polymer and the crosslinking agent represented by the formula (1) are dissolved in an organic solvent, the solution is poured into a molding mold such as a silicone mold, and the temperature is elevated from room temperature to 40 to 100 ° C stepwise to cause a crosslinking reaction. To obtain a film having a thickness of several to several hundreds of 탆, preferably 10 to 200 탆, more preferably 50 to 150 탆, and then desorbing from the molding mold. Examples of the organic solvent include, but are not limited to, saturated chain hydrocarbons such as pentane, (n-) hexane and heptane; Alicyclic hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; Or a general-purpose solvent such as chloroform, dimethylsulfoxide, dimethylacetamide, dimethylformamide, chlorobenzene, N-methyl-2-pyrrolidinone and the like. Among the above-mentioned organic solvents, chloroform and N-methyl-2-pyrrolidinone are more preferable. The above-mentioned solvent is only illustrative, and the scope of the present invention is not limited thereto. Conventional organic solvents may be used as long as they dissolve the polymer and can be evaporated under the drying condition. Specifically, the same organic solvent as that used in the preparation of the polymer may be used.

According to a specific embodiment of the present invention, poly (2,6-dimethyl-1,4-phenylene bromide), chloromethylated polyphenylsulfone or chloromethylated polysulfone as a halogenated polymer are used as crosslinking agents, Minobenzophenone dissolved in a solvent and poured into a silicone mold having a predetermined size, and dried at 60 to 100 ° C., preferably 70 to 90 ° C., for 12 to 36 hours, preferably 18 to 30 hours to obtain a film.

The third step is a step in which the residual halogen functional group of the crosslinkable polymer is substituted with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group to impart ionic conductivity.

The ion exchangeable functional group substitution can be carried out by various known substitution methods. For example, in the second step, the crosslinked polymer may be immersed in a solution in which an aqueous solution of a compound having various ion exchangeable functional groups such as trimethylamine is diluted in acetone for a predetermined time, and then immersed in distilled water for a predetermined time.

The present invention can provide a film containing the ionically conductive crosslinked polymer. The membrane may be an ion exchange membrane. Further, the film may be a water treatment film.

The anion which can be exchanged by using the ion exchange membrane comprising the ion conductive crosslinked polymer according to the present invention is an organic anion or an inorganic anion, which means an anion generated by loss of one or more hydrogen ions from an organic acid or an inorganic acid.

As inorganic anions, there may be mentioned, for example, sulfates, phosphonates, borates, cyanides, carbonates, hydrogen carbonates, thiocyanates, thiosulfates, sulfites, hydrogen sulfites, nitrates, cyanates, phosphates, (E.g. molybdate, tungstate, metavanadate, pyrovanadate, hydrogen pyrovanadate, niobate, tantalate, perrhenate, etc.), tetrafluoroaluminate, tetrafluoroborate, hexa Fluorophosphate and tetrachloroaluminate, and Al ₂ Cl ₇ ^- ions.

Organic anions include sulfonates, formates, oxalates, acetates, (meth) acrylates, trifluoroacetates, tropluoromethane sulfonates and bis (trifluoromethanesulfonate) amides, (CF ₃ SO ₂ ) ₃ Cl ^- anion, and the like.

The amine-based crosslinking agent according to the present invention can be crosslinked only without forming an ion-exchange functional group as a primary or secondary amine crosslinking agent, and can inhibit the rapid crosslinking reaction at the time of film formation by preventing electron- it has an advantage that it improves the dimensional stability and mechanical stability due to crosslinking without affecting the function of the membrane such as water uptake and conductivity and is easy to control the anion exchange function.

In order to improve the performance of the vanadium redox flow battery, it is necessary to have not only a low film resistance but also a low level of dimensional change characteristics in order to prevent crossover of the active material. In the polymer ion conductor using a diamine type crosslinking agent having an electron- Has a great advantage in producing a separator for a vanadium redox flow battery because it has excellent film forming properties and can effectively improve dimensional stability while controlling ion exchange capacity.

1 is a ¹ H-NMR spectrum of a chloromethylated polysulfone synthesized in Example 1 of the present invention.
2 compares the FT-IR of the crosslinked membrane (PSf-x) prepared in Example 1 of the present invention.
3 shows a state of the ion exchange membrane manufactured in Example 1 of the present invention.
4 compares FT-IR before and after ion exchange of the crosslinked membrane prepared in Example 1 of the present invention.
5 is a graph comparing the ionic conductivities of the ion exchange membranes prepared in Example 1 of the present invention.
6 compares the VRFB efficiency of the ion exchange membrane prepared in Example 1 of the present invention.
7 compares the charge-discharge capacity retention ratio of the ion exchange membrane prepared in Example 1 of the present invention with Nafion 115. FIG.
FIG. 8 is a graph comparing the change of the capacity versus voltage according to the charging cycle of the ion exchange membrane prepared in Example 1 of the present invention.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Example 1

A crosslinked polysulfone-based anion exchange membrane was prepared according to the following Reaction Scheme 1.

[Reaction Scheme 1]

Step 1: Chloromethylation reaction step

The chloromethylation process of the polysulfone was carried out as follows, with reference to the process for preparing an anion conductor-containing solution of Korean Patent No. 10-1284009.

Polysulfone ^{(UDEL ® Polysulfone, P-3500} LCD MB, Solvay Advanced Polymers) was a dried for 100 ℃ 24 hours in a vacuum oven to 34g, the dried polysulfone mechanical stirrer, a constant temperature water bath for a gas inlet, condenser and a temperature setting, Lt; RTI ID = 0.0 > 1L < / RTI > Then, it was completely dissolved in 140 ml of 1,1,2,2-tetrachloroethane, 2.97 g of zinc chloride (ZnCl ₂ ) was added, and the mixture was stirred for about 30 minutes. Thereafter, 23 ml of chloromethyl methyl ether (CMME) was dropped through a dropping funnel. The amount of CMME added was 6 times 6 times the number of moles of CMME reacted per mole of polysulfone repeating units (G / mol) × (molecular weight of chloromethyl methyl ether) (g / mol), and the mixture was added dropwise to the reactor. The inert gas, which had been dried through the gas inlet, was vigorously stirred, The reaction product was precipitated in an excess amount of methanol and washed several times with methanol and tertiary distilled water. The washed chloromethylated polysulfone was vacuum-dried at 80 DEG C for 24 hours.

When analyzed by ¹ H-NMR spectroscopy, chloromethyl functional groups were observed at 4.5 ppm, and the chloromethylation degree of the polysulfone in this example was 0.956.

Step 2: Cross-linking reaction and film-forming step

The chloromethylated poly-N, N of the sulfone 1g 10㎖ - dimethylacetamide as a cross-linking agent was then dissolved in (N, N -dimethylacetamide) 4,4- diamino benzophenone-chloromethyl-functional groups to (4,4'-diaminobenzophenone) , 0, 1, 2.5, 5, 10, and 15 mol%, respectively, and then completely dissolved by stirring. The solution was filled in a 10x10 cm 2 silicone mold and heated from 25 캜 to 40 캜 for 1 hour, maintained at 40 캜 for 2 hours, heated from 40 캜 to 60 캜 for 1 hour, maintained at 60 캜 for 2 hours, The temperature was raised for 1 hour and then kept at 80 DEG C for 12 hours. Immediately after the crosslinking and film formation, the dried film had a thickness of 70 to 110 탆. This is named APSf-x, where x represents the ratio of crosslinking agent. When analyzed by FT-IR spectroscopy, PSf-2.5 versus PSf-0 and C = O 1642 cm- ¹ of 4,4'-diaminobenzophenone were observed in PSf-10.

Step 3: Ion exchange step

The anion exchangeable functional group substitution of the residual chloromethyl functional group of the crosslinked membrane was performed as follows.

The crosslinked membrane was supported on a mixed solution obtained by diluting trimethylamine in 1 M of acetone and ethanol having a volume ratio of 1: 1 for 24 hours, washed with tertiary distilled water, A crosslinked polysulfone-based anion exchange membrane was prepared. At this time, a ~45 wt% aqueous solution of trimethylamine was used. Anion-exchangeable functional group Substituted crosslinked membrane is referred to as APSf-x. When analyzed by FT-IR spectroscopy, the absorption of 730-980 cm- ¹ chloromethyl functional group in APSf-x versus the absorption of a wide range of trimethylamine salt (-N ⁺ (CH ₃ ) ₃ ) around 3500 cm ^-1 was observed .

[Chemical Formula 6]

Hereinafter, the performance of the crosslinked polysulfone-based anion exchange membrane prepared in Example 1 was analyzed.

Experimental Example 1: IEC and dimensional stability analysis

IEC and dimensional stability of the ion exchange membrane prepared in Example 1 were analyzed.

At room temperature, the ion exchange membrane to the IEC analysis for 24 hours by immersion in 1M NaOH aqueous solution of ^{Cl-transformed} into ion form ^- the form of ion OH. OH ^- ion form were each stirred in 0.01 M aqueous HCl solution for 24 hours, and then acid-base titrated with 0.01 M NaOH aqueous solution. The results are shown in Table 1 below.

The weight, length, thickness, and volume change of the ion exchange membrane in the wet state and the completely dried state were measured at room temperature and 80 ° C for the dimensional stability analysis, and the results are shown in Table 1 below.

[Table 1]

It can be seen from Table 1 that the cross-linking degree of IEC can be controlled by the amount of cross-linking agent, as the amount of cross-linking agent increases with increasing amount of cross-linking agent.

In addition, it was found that the dimensional stability increases with increasing crosslinking degree, and the dimensional change due to temperature increase also tends to decrease. The dimensional stability of APSf-0 at 80 ° C was not measurable because the film morphology disappeared. The crosslinked ion exchange membranes except for APSf-1 showed similar or higher dimensional stability than the general anion exchange membranes.

Experimental Example 2: Ionic Conductivity Analysis

Ion exchange membranes prepared in Example 1 were analyzed for ionic conductivity. Pt electrode cell was used for ion conductivity analysis and impedance was measured by 4-probe electrochemical impedance spectroscopy (Solatron 1280). The ion exchange membranes were loaded on 1M NaCl aqueous solution, 1M Na ₂ SO ₄ aqueous solution and 1M NaOH aqueous solution for 24 hours, respectively, and the conductivity of Cl ^- , SO ₄ ^2- and OH ^- ions were measured. The ionic conductivities at 25 ° C, 40 ° C, 60 ° C, 70 ° C and 80 ° C were measured at 100% relative humidity and the results are shown in Table 2 below.

[Table 2]

As shown in Table 2, ionic conductivity of all membranes increased with increasing temperature. This is because the ion migration rate increases with increasing temperature. The ionic conductivity decreased in the order of OH ^- , Cl ^- , SO ₄ ^{2 -} due to the difference in ion size and migration rate. The OH ^- conductivity of APSf-0 and APSf-1 at 80 ° C was not measurable due to impairment of membrane morphology.

Experimental Example 3: Evaluation of membrane resistance, vanadium ion permeability and vanadium redox flow battery unit cell performance

The ion-exchange membrane prepared in Example 1 was immersed in 0.5M H ₂ SO ₄ aqueous solution for 24 hours at room temperature, and the membrane resistance was measured. A 0.5 M H ₂ SO ₄ aqueous solution was used as an electrolyte between the Pt electrodes having a diameter of 0.5 cm and the resistance was measured with a resistance meter (Hioki 3560) under the electrolyte solution. The results are shown in Table 3 below. The resistance of the commercially available cation exchange membrane Nafion 115 (Dupont, USA) as a reference was measured under the same conditions.

The ion exchange membrane prepared in Example 1 was immersed in a 1M Na ₂ SO ₄ aqueous solution for 24 hours, dried, and then measured for vanadium ion permeability. H ₂ SO ₄ aqueous solution to a 3M to 2M solvent MgSO ₄ solution, and 3M H ₂ SO ₄ aqueous solution as a solvent for a 2M VOSO ₄ UV- the concentration of vanadium ions in time while circulating the solution with the ion exchange membrane between an aqueous solution visible spectroscopy (Agilent cary 8454). The results are shown in Table 3 below. At this time, APSf-1, APSf-2.5 and APSf-5 were measured for 72 hours, APSf-10, APSf-15 and Nafion 115 were measured for 24 hours. As a reference, Nafion 115 was immersed in a 1.5 M H ₂ SO ₄ aqueous solution for 24 hours, washed with a third distilled water and then dried and then dried.

The ion exchange membranes prepared in Example 1 were loaded in a ₁ M Na ₂ SO ₄ aqueous solution for 24 hours and then dried. The cell performance was evaluated using a WonATech battery test system. The results are shown in Table 3 below. At this time, the effective area of the ion exchange membrane was 49 cm ² , the current density was 50 mA cm ^-2 , and the flow rate was 60 ml min ^-1 . As a reference, Nafion 115 was immersed in a 1.5 M H ₂ SO ₄ aqueous solution for 24 hours, washed with a third distilled water and then dried and then dried.

[Table 3]

(t _d is the discharge time, t _c is the charge time, V _d is the discharge voltage, and V _c is the charge voltage)

As shown in Table 3 above, irrespective of the degree of crosslinking, the anion exchange membranes prepared in Example 1 showed significantly lower vanadium ion permeability than Nafion 115. Also, the higher the degree of crosslinking, the lower the vanadium ion permeability, but APSf-10 and APSf-15 did not measure vanadium ion permeability for 120 hours.

In addition, the anion exchange membrane prepared in Example 1 exhibited a higher Coulombic efficiency (C.E.) than Nafion 115, which is due to the significantly lower vanadium ion permeability compared to Nafion 115. In addition, the voltage efficiency (V.E.) and the energy efficiency (E.E.) of APSf-1 and APSf-2.5 according to the present invention were found to be equal to or higher than Nafion 115. In addition, APSf-2.5, APSf-5 and APSf-10 according to the present invention exhibited better charge / discharge capacity retention than Nafion 115.

Claims (14)

delete delete An ion conductive crosslinking agent for a vanadium redox flow cell, wherein the ion conductive polymer is crosslinked through a crosslinking unit represented by the following formula (2), and the ion conductive polymer has an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group Polymers:
(2)

In Formula 2,
E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or -NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, an alkyl group , An aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;
G and G 'are a single bond, or -O-, -S-, -NH- or NR ₄₇ - as an electron donor, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;
R ₉ to R ₁₆ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;
Ar

or

ego;
J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;
R ₁₇ to R ₂₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a halogen substituted alkyl group, a C ₂ to C ₁₂ allyl group, CN, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a perfluoroaryl group or - O-perfluoroaryl group;
and x is an integer of 1 to 10000. [5] The ionically conductive crosslinked polymer of claim 3, wherein the ionically conductive crosslinked polymer is formed by crosslinking halogenated polymers at halogen functional sites in the halogenated polymer. delete 4. The method of claim 3 wherein the anion-exchange functional group is a pyridyl group, a carbazolyl group or an imidazole or an anion exchange functional group derived from the yeomsangtae pyridazinyl ^{_{group, -N + H 3 L -,}} -N + R'H 2 L - ^{_{, -N + R '2 HL -}} , -N + R' 3 L -, -P + R '3 L -, -S + R' 2 L - or C ₅ H ₅ N ⁺ HL ^-, and wherein R ' Is a C _1-4 alkyl or C _6-12 aryl and L ^- is a hydroxide anion, a bicarbonate anion, a chloride anion, a bromide anion, an iodide anion or a sulfate anion,
The cation-exchange functional groups are ^{_{-SO 3 -, -COO -, -PO}} 3 2-, -PO 3 H - or C ₆ H ₄ 0 ^-, and
Wherein the amphoteric ion-exchange functional group is betaine or sulfobetaine. ≪ RTI ID = 0.0 > 11. < / RTI > The ion conductive crosslinked polymer for a vanadium redox flow battery according to claim 3, which has a skeleton containing a repeating unit represented by the following formula (3): < EMI ID =
(3)

In Formula 3,
E is a single bond or an electron donor group -O-, -S-, -CR ₄₈ R ₄₈ '-, -NH- or NR ₄₉ -, and R ₄₈ and R ₄₈ ' each independently represent a hydrogen atom, Or an aryl group, and R ₄₉ is a C ₁ to C ₁₂ alkyl group;
G and G 'are -O-, -S-, -NH- or NR ₄₇ - as a single bond or electron donor group, and R ₄₇ is a C ₁ to C ₁₂ alkyl group;
Z ₁ to Z ₆ each independently represent a hydrogen atom, (CH ₂ ) _h M (1 ≦ _h ≦ 12) or (CH ₂ ) _h M containing an ether group and an ester group (1 ≦ _h ≦ 12) Is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;
R ₃₅ to R ₄₆ and R ₃₅ 'to R ₄₆ ' each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group , A C ₂ to C ₁₂ allyl group, a cyano group (-CN), a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, at least one oxygen, A perfluoroalkylaryl group, a perfluoroaryl group or an -O-perfluoroaryl group;
Ar

or

ego;
J is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _{5 -20} heteroaryl substituted by one or more of said electron withdrawing groups;
R ₁₇ to R ₂₈ each independently represents a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;
A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _{5 -20} heteroaryl substituted by one or more of said electron withdrawing groups;
D " and D '" are each independently NH or -NR, and R is a C ₁ to C ₁₂ alkyl group;
R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;
a and b are each independently 0 or an integer of 1 to 100;
c, d, e and f are each independently an integer of 1 to 10000. The method of claim 7, wherein the anion-exchange functional group is a pyridyl group, a carbazolyl group or an imidazole or an anion exchange functional group derived from the yeomsangtae pyridazinyl ^{_{group, -N + H 3 L -,}} -N + R'H 2 L - ^{_{, -N + R '2 HL -}} , -N + R' 3 L -, -P + R '3 L -, -S + R' 2 L - or C ₅ H ₅ N ⁺ HL ^-, and wherein R ' Is a C _1-4 alkyl or C _6-12 aryl and L ^- is a hydroxide anion, a bicarbonate anion, a chloride anion, a bromide anion, an iodide anion or a sulfate anion,
The cation-exchange functional groups are ^{_{-SO 3 -, -COO -, -PO}} 3 2-, -PO 3 H - or C ₆ H ₄ 0 ^-, and
Wherein the amphoteric ion-exchange functional group is betaine or sulfobetaine. ≪ RTI ID = 0.0 > 11. < / RTI > The method of claim 3, wherein the polymer has a molecular weight of Mw (number-average molecular weight) of 10,000 to 1,000,000 or Mw (weight-average molecular weight) of 10,000 to 10,000,000. Ion conductive crosslinked polymers for toxic flow batteries. The ionically conductive crosslinked polymer for a vanadium redox flow cell according to claim 3, wherein the ion conductive polymer is a random copolymer, a cross-copolymer or a block copolymer. delete 11. A process for producing an ion conductive crosslinked polymer for a vanadium redox flow battery according to any one of claims 3, 4 and 6 to 10,
A first step of preparing a halogenated polymer;
A second step of adding a cross-linking agent represented by the following formula (1) to the halogenated polymer to form a cross-linked polymer by a cross-linking reaction between the halogenated polymers at some halogen functional sites of the halogenated polymer; And
And a third step of replacing the residual halogen functionality of the crosslinking polymer with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group.
[Chemical Formula 1]

In Formula 1,
A is a single bond; As the electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -; Or C _6-20 aryl or C _5-20 heteroaryl substituted by one or more of said electron withdrawing groups;
D and D 'are each independently -NH ₂ , or -NHR, wherein R is a C ₁ to C ₁₂ alkyl group;
R ₁ to R ₈ each independently represent a hydrogen atom (-H), a halogen atom (-X), a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkyl group substituted with halogen, a C ₂ to C ₁₂ allyl A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom, a C ₆ to C ₁₀ aryl group, a nitro group (-NO ₂ ), a perfluoroalkyl group, A perfluoroaryl group or a -O-perfluoroaryl group;
a and b are each independently 0 or an integer of 1 to 100; A film comprising an ionically conductive crosslinked polymer for a vanadium redox flow cell according to any one of claims 3, 4, 14. The membrane of claim 13, wherein the membrane is an ion exchange membrane.

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