CN105789657A - Modified PES (polyether sulfones)-PVP (polyvinylpyrrolidone) hybrid anion exchange membrane for vanadium redox battery and preparation method of modified PES-PVP hybrid anion exchange membrane - Google Patents

Abstract

The invention discloses a modified PES (polyether sulfones)-PVP (polyvinylpyrrolidone) hybrid anion exchange membrane for a vanadium redox battery. The modified PES-PVP hybrid anion exchange membrane for the vanadium redox battery is prepared by blending of quaternization modified PES and PVP, wherein the quaternization modified PES is a mixture of quaternary ammonium base type quaternization modified PES and imidazole type quaternization modified PES. By blending of the quaternary ammonium base type quaternization modified PES, the imidazole type quaternization modified PES and the PVP, superior properties of the three are combined. In application to all-vanadium redox flow batteries, the modified PES-PVP hybrid anion exchange membrane has excellent vanadium resistance and ion selection performances and has advantages of high stability, superior mechanical properties, high coulombic efficiency and long service life.

Description

A kind of modified PES-PVP for vanadium cell is blended anion exchange membrane and preparation method thereof

Technical field

The invention belongs to electrochemical material field, be specifically related to a kind of modified PES-PVP for vanadium cell common Mixed anion exchange membrane and preparation method thereof.

Background technology

Vanadium cell full name is that (Vanadium Redox Battery, is abbreviated as vanadium redox battery VRB), be a kind of active substance in circulating the redox cell of liquid, be utilize different valence state vanadium from Redox reaction between son realizes the conversion of the energy, participate in the active substance of reaction be liquid vanadium from Son, vanadium cell be a kind of efficiently, environmental protection, Large Copacity, can high current charge-discharge, the liquid stream of deep discharge Energy-storage battery.

Vanadium cell is mainly made up of electrode material, electrolyte and ion exchange membrane.Wherein, ion exchange membrane is made One of core component for vanadium cell, how to obtain high selectivity, low resistance and enough chemical stability every Film is the key factor of restriction vanadium cell performance.Preferably diaphragm material should have differential permeability, both allowed Carrier, by ensureing high electrical conductivity, reduces the interior loss of energy of battery, stops again electrolyte ion to pass through The infiltration of barrier film, reduces the loss of the battery capacity thereby resulted in.Fixed group due to cation exchange membrane For azochlorosulfonate acid anion, attractive to the vanadium ion in VRB solution, although by modified to film Reason can reduce the permeability of vanadium ion to a certain extent, but can not fundamentally stop the infiltration of vanadium ion. Comparatively speaking, the fixed group of anion exchange membrane is with positive charge ion, due to Donan effect vanadium ion Infiltration will be restricted, thus ion selectivity is higher.At present, the Nafion of commercialization vanadium cell it is applied to Although film has good chemical stability and relatively low surface resistance, but it is expensive, and to vanadium ion Barrier poor, self-discharge of battery phenomenon is serious, affects battery efficiency.

Summary of the invention

For the deficiencies in the prior art, an object of the present invention is to provide a kind of modification for vanadium cell PES-PVP is blended anion exchange membrane, has good resistance vanadium performance, ion selects performance, has excellent Stability and mechanical performance, coulombic efficiency is high, and service life is long.

For reaching this purpose, the present invention by the following technical solutions:

A kind of modified PES-PVP for vanadium cell is blended anion exchange membrane, by quaternised modified PES and Being prepared from after PVP is blended, described quaternised modified PES is the quaternised modified PES of quaternary ammonium base and imidazoles The mixture of the quaternised modified PES of class.

Anion exchange membrane contains basic activated group, can intercept passing through of cation through anion, cloudy Ion exchange membrane due to positive charge and vanadium ion have repelling effect, the transmembrane movement of vanadium ion can be stoped, It is thus able to be effectively improved the coulombic efficiency of battery and energy efficiency.Anion exchange membrane is utilized to have Effect reduces vanadium ion permeability in film, but the increase having again resulted in impedance makes voltage efficiency Decline, and the chemical stability of anion exchange membrane is low, water migrates height, need anion exchange membrane is made Go out modification.Due to the less stable of anion exchange membrane, the property of film can be effectively improved by blending and modifying Energy.

Polyether sulfone (PES) is a kind of chemically inert engineering thermoplasties, has the mechanical performance of excellence, It is modified that polyether sulfone carries out quaternary amine, introduces quaternary ammonium group；With preparation the moon after amine reagent functionalization after chloromethylation Ion exchange membrane, wherein, utilizes trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine etc. as amination reagent Quaternary ammonium base quaternised modified PES anion exchange membrane has reasonable ion selectivity and higher energy dose-effect Rate, but ionic conductance is low, heat stability and poor chemical stability；Utilize 1-Methylimidazole. etc. as amine The imidazoles quaternised modified PES anion exchange membrane changing reagent has preferable heat stability and chemically stable Property, fixedness and high ionic conductance, by quaternised modified for quaternary ammonium base PES, imidazoles is quaternized changes Property PES be blended with polyvinylpyrrolidone (PVP), PVP is a kind of water-soluble polymer, has Good film property and stability, the carbonyl in PVP and quaternary ammonium group have strong interaction, by three The blend of kind material is prepared modified PES-PVP and anion exchange membrane is blended, for vanadium redox Field of batteries, has good resistance vanadium performance, ion selects performance, has excellent stability and mechanicalness Can, coulombic efficiency is high, and service life is long.

Wherein, the mass ratio of described quaternised modified PES and described PVP is 1:(1～5), such as 1:1, 1:2、1:3、1:4、1:5。

Wherein, the mass ratio of the quaternised modified PES of described quaternary ammonium base and the quaternised modified PES of described imidazoles For 1:(1～3), such as 1:1,1:1.5,1:2,1:2.5,1:3.

Wherein, described quaternised modified PES by PES through chloromethylation reagents chloromethylation, amination reagent season Prepare after ammonium.

Wherein, described chloromethylation reagents is chloromethyl alkyl ether；Preferably, described chloromethyl alkyl ether choosing One in chloromethyl methyl ether, chloromethyl ether, chloromethyl butyl ether, chloromethyl octyl ether or at least two.

Wherein, in the quaternised modified PES of described quaternary ammonium base, described amination reagent selected from trimethylamine, triethylamine, One in tripropyl amine (TPA), tri-n-butylamine or at least two；In the quaternised modified PES of described imidazoles, described amine Changing reagent is 1-Methylimidazole..

The two of the purpose of the present invention are that providing a kind of modified PES-PVP for vanadium cell that anion is blended hands over Change the preparation method of film, comprise the steps:

1) by proportioning, quaternised modified for quaternary ammonium base PES, quaternised modified PES with PVP of imidazoles are blended After, join in DMF (DMF) solution and stir, obtain blended liquid；

2) by step 1) blended liquid prepared is applied on substrate, prepares altogether after drying, peeling off Mixed anion exchange membrane；

3) by step 2) the blended anion exchange membrane prepared soaks in sulfuric acid solution, prepares modification PES-PVP is blended anion exchange membrane.

Modified PES-the PVP for vanadium cell of the present invention is blended the preparation method of anion exchange membrane, quaternary ammonium Change modified PES and PVP is mutually shifted in DMF solvent and is wound around, form a kind of homogeneous phase, and use The post processing that sulfuric acid solution soaks makes the film prepared have more preferable hydrophilic.

Preferably, step 1) in, the time of described stirring is 5～8h, and the temperature of described DMF solution is 40℃；The mass ratio of described quaternised modified PES and described PVP is 1:(1～5), described quaternary ammonium base season Ammonium modified PES is 1:(1～3 with the mass ratio of the quaternised modified PES of described imidazoles)；

Step 2) in, the temperature of described drying is 60～90 DEG C, and described substrate is glass plate or coating machine, The process of described stripping is, after the substrate ultrasonic humidifier after drying humidifies, blended anion is handed over Change film to peel off from substrate；The purpose dried is to remove the solvent DMF in solution, uses ultrasonic humidifier After process, can peel off more convenient for film from substrate；

Step 3) in, the concentration of described sulfuric acid solution is 1～3M, and the time of described immersion is 36～80h； Soak as post processing with sulfuric acid solution so that film has more preferable hydrophilicity.

Wherein, the preparation process of the quaternised modified PES of described quaternary ammonium base is:

1) PES of 1～5g is dissolved in the concentrated sulphuric acid of 10～30ml, adds the chloromethyl alkane of 8～15ml In base ether, separate out white solid after reaction 5～8h, be washed with deionized water to neutrality, after drying, obtain chloromethane Base PES；

2) by step 1) the chloromethylation PES that obtains is soaked in amination reagent 24～48h, uses deionization It is washed to neutrality, after drying, obtains the quaternized PES of quaternary ammonium base；Wherein, described amination reagent be trimethylamine, One in triethylamine, tripropyl amine (TPA), tri-n-butylamine or at least two.

Wherein, the preparation process of the quaternised modified PES of described imidazoles is:

1) PES of 1～5g is dissolved in the concentrated sulphuric acid of 10～30ml, adds the chloromethyl alkane of 8～15ml In base ether, separate out white solid after reaction 5～8h, be washed with deionized water to neutrality, after drying, obtain chloromethane Base PES；

2) by step 1) the chloromethylation PES that obtains is soaked in 1-Methylimidazole. 24～48h, spend from Son is washed to neutrality, obtains the quaternized PES of imidazoles after drying.

Compared with prior art, the invention have the benefit that a kind of modification for vanadium cell of the present invention PES-PVP is blended anion exchange membrane, by quaternised modified PES and PVP blended after be prepared from, institute State the mixing that quaternised modified PES is the quaternised modified PES of quaternary ammonium base and the quaternised modified PES of imidazoles Thing；Quaternary ammonium base quaternised modified PES anion exchange membrane has excellent ion selectivity and higher energy Efficiency, imidazoles quaternised modified PES anion exchange membrane have excellent heat stability and chemical stability, Fixedness and high ionic conductance, by quaternised modified by quaternary ammonium base respectively for PES and imidazoles quaternary ammonium Change after modification, the advantage combining both, by quaternised modified for quaternary ammonium base PES with imidazoles is quaternized changes Property PES Yu PVP be blended after, the film property good further combined with PVP and stability, in PVP Carbonyl interact with quaternary ammonium group so that the modified PES-PVP prepared be blended anion hand over Change film when being applied to vanadium redox battery, there is good resistance vanadium performance, ion selects performance, Having excellent stability and mechanical performance, coulombic efficiency is high, and service life is long.

Detailed description of the invention

Technical scheme is further illustrated below by detailed description of the invention.

As no specific instructions, the various raw materials of the present invention are the most commercially available to be buied, or the routine side according to this area Method prepares.

Embodiment 1

1) PES of 1g is dissolved in the concentrated sulphuric acid of 10ml, adds in the chloromethyl methyl ether of 8ml, reaction Separate out white solid after 5h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 24h in trimethylamine, be washed with deionized water to neutrality, after drying, obtain quaternary ammonium The quaternized PES of alkali；

2) PES of 1g is dissolved in the concentrated sulphuric acid of 10ml, adds in the chloromethyl methyl ether of 8ml, reaction Separate out white solid after 5h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 24h in 1-Methylimidazole., be washed with deionized water to neutrality, obtain after drying The quaternized PES of imidazoles；

3) it is that the proportioning of 1:1 is by quaternised modified to quaternised modified for quaternary ammonium base PES, imidazoles in mass ratio After PES Yu PVP is blended, the mass ratio of described quaternised modified PES and described PVP is 1:2, adds In DMF (DMF) solution that temperature is 40 DEG C, stir 5h, obtain blended liquid；

4) blended liquid of preparation is applied on glass panel substrate, through 60 DEG C of drying, the base after drying After plate humidifies with ultrasonic humidifier, blended anion exchange membrane is peeled off from substrate；Being blended preparation Anion exchange membrane soaks 36h in 2M sulfuric acid solution, prepares modified PES-PVP and anion is blended Exchange membrane.

Embodiment 2

1) PES of 2g is dissolved in the concentrated sulphuric acid of 20ml, adds in the chloromethyl ether of 10ml, reaction Separate out white solid after 7h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 36h in triethylamine, be washed with deionized water to neutrality, after drying, obtain quaternary ammonium The quaternized PES of alkali；

2) PES of 2g is dissolved in the concentrated sulphuric acid of 20ml, adds in the chloromethyl ether of 10ml, reaction Separate out white solid after 7h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 36h in 1-Methylimidazole., be washed with deionized water to neutrality, obtain after drying The quaternized PES of imidazoles；

3) it is that the proportioning of 1:3 is by quaternised modified to quaternised modified for quaternary ammonium base PES, imidazoles in mass ratio After PES Yu PVP is blended, the mass ratio of described quaternised modified PES and described PVP is 1:3, adds In DMF (DMF) solution that temperature is 40 DEG C, stir 7h, obtain blended liquid；

4) blended liquid of preparation is applied on glass panel substrate, through 80 DEG C of drying, the base after drying After plate humidifies with ultrasonic humidifier, blended anion exchange membrane is peeled off from substrate；Being blended preparation Anion exchange membrane soaks 48h in 1M sulfuric acid solution, prepares modified PES-PVP and anion is blended Exchange membrane.

Embodiment 3

1) PES of 3g is dissolved in the concentrated sulphuric acid of 30ml, adds in the chloromethyl butyl ether of 12ml, reaction Separate out white solid after 8h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 48h in triethylamine, be washed with deionized water to neutrality, after drying, obtain quaternary ammonium The quaternized PES of alkali；

2) PES of 3g is dissolved in the concentrated sulphuric acid of 30ml, adds in the chloromethyl butyl ether of 12ml, reaction Separate out white solid after 8h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 48h in 1-Methylimidazole., be washed with deionized water to neutrality, obtain after drying The quaternized PES of imidazoles；

3) it is that the proportioning of 1:2 is by quaternised modified to quaternised modified for quaternary ammonium base PES, imidazoles in mass ratio After PES Yu PVP is blended, the mass ratio of described quaternised modified PES and described PVP is 1:4, adds In DMF (DMF) solution that temperature is 40 DEG C, stir 8h, obtain blended liquid；

4) blended liquid of preparation is applied on glass panel substrate, through 85 DEG C of drying, will dry after base After plate humidifies with ultrasonic humidifier, blended anion exchange membrane is peeled off from substrate；Being blended preparation Anion exchange membrane soaks 48h in 2M sulfuric acid solution, prepares modified PES-PVP and anion is blended Exchange membrane.

Embodiment 4

1) PES of 5g is dissolved in the concentrated sulphuric acid of 25ml, adds in the chloromethyl octyl ether of 15ml, reaction Separate out white solid after 7h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 48h in tri-n-butylamine, be washed with deionized water to neutrality, after drying, obtain quaternary ammonium The quaternized PES of alkali；

2) PES of 5g is dissolved in the concentrated sulphuric acid of 25ml, adds in the chloromethyl octyl ether of 15ml, reaction Separate out white solid after 7h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 48h in 1-Methylimidazole., be washed with deionized water to neutrality, obtain after drying The quaternized PES of imidazoles；

3) in mass ratio for the proportioning of 1:2.5 by quaternised modified for quaternary ammonium base PES, imidazoles is quaternized changes Property after PES Yu PVP be blended, the mass ratio of described quaternised modified PES and described PVP is 1:4, adds Enter in DMF (DMF) solution that temperature is 40 DEG C stirring 6h, obtain blended liquid；

4) blended liquid of preparation is applied on coating machine substrate, through 90 DEG C of drying, the base after drying After plate humidifies with ultrasonic humidifier, blended anion exchange membrane is peeled off from substrate；Being blended preparation Anion exchange membrane soaks 80h in 3M sulfuric acid solution, prepares modified PES-PVP and anion is blended Exchange membrane.

Embodiment 5

1) PES of 5g is dissolved in the concentrated sulphuric acid of 30ml, adds in the chloromethyl methyl ether of 15ml, reaction Separate out white solid after 8h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 48h in trimethylamine, be washed with deionized water to neutrality, after drying, obtain quaternary ammonium The quaternized PES of alkali；

2) PES of 5g is dissolved in the concentrated sulphuric acid of 30ml, adds in the chloromethyl methyl ether of 15ml, reaction Separate out white solid after 8h, be washed with deionized water to neutrality, after drying, obtain chloromethylation PES；To obtain Chloromethylation PES be soaked in 36h in 1-Methylimidazole., be washed with deionized water to neutrality, obtain after drying The quaternized PES of imidazoles；

3) it is that the proportioning of 1:3 is by quaternised modified to quaternised modified for quaternary ammonium base PES, imidazoles in mass ratio After PES Yu PVP is blended, the mass ratio of described quaternised modified PES and described PVP is 1:5, adds In DMF (DMF) solution that temperature is 40 DEG C, stir 7h, obtain blended liquid；

4) blended liquid of preparation is applied on glass panel substrate, through 80 DEG C of drying, will dry after base After plate humidifies with ultrasonic humidifier, blended anion exchange membrane is peeled off from substrate；Being blended preparation Anion exchange membrane soaks 48h in 2M sulfuric acid solution, prepares modified PES-PVP and anion is blended Exchange membrane.

Modified PES-the PVP that embodiment 1～5 prepares is blended anion exchange membrane carry out as barrier film Performance test, performance characterization includes: water absorption, surface resistance (R, Ω cm²) and stability.Wherein, every The water absorption of film measures referential weight method, evaporates DMF at 80 DEG C, then at 25 DEG C, until weight Amount keeps constant, obtains the dry weight of film, is then soaked in distilled water 3 days, after impregnation process by film, Wipe the moisture on surface, measure the moist weight of film, the dry weight of film and moist weight record the suction of film The water yield；Modified PES-the PVP prepared is blended anion exchange membrane be clipped in two and comprise graphite cake electrode Half-cell between, the measurement of surface resistance is the H at the 2.0MD of 25 DEG C₂SO₄In solution, use electrochemistry work Making station and measure impedance methodologies (exchange 1kHz), barrier film has low surface resistance, may be used for the oxidation of full vanadium also Galvanic element, experimental result is shown in Table 1.

Table 1

Embodiment	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						Water absorption (%)	30	25	24	27	23
Surface resistance (Ω cm2)	0.84	0.88	0.9	0.91	0.89
						Coulombic efficiency (%)	99.6	99.5	99.1	99.0	99.7

As can be seen from Table 1, the modified PES-PVP that prepared by the present invention is blended the water absorption of anion exchange membrane Little, the swelling little satisfactory mechanical property making film；Surface resistance is low, close to the surface resistance (0.95 of Nafion membrane Ω·cm²), and far below the surface resistance of multiple commercialization ion exchange membrane.Relatively low surface resistance makes modification PES-PVP is blended anion exchange membrane and can apply to whole vanadium oxide reduction battery.It addition, high coulomb effect Rate is also the factor that resistance vanadium performance is good.

Modified PES-PVP embodiment 1 prepared is blended anion exchange membrane and is placed in strong oxidizing property acidity solution In, at (the VO of the 1M of 25 DEG C₂)₂SO₄H with 2M₂SO₄Mixed solution soaks 30 days, soaks Afterwards with the H of 2M₂SO₄Solution washs repeatedly, measures the stability of film by measuring the transport number of vanadium ion, And with the vanadium ion transport number of Nafion cation exchange membrane as a comparison case, experimental result is shown in Table 2.Simultaneously Characterize barrier film performance before and after soaking become by the measurement thickness of film, surface resistance, the transport number of anion Changing, experimental result is shown in Table 3.

Wherein, employ hittorf method and measure vanadium ion transport number.Cation i is through the transport number of barrier film As shown in formula (1):

$t_i=\frac{Q_i}{Q_{total}}=\frac{z_i{n}_{i}F}{{\mathrm{\Σz}}_i{n}_{i}F}=\frac{z_i{C}_i{V}_{i}F}{It}---\left(1\right)$

Wherein zi is the valence mumber of metal cation i, and Ci is the concentration of metal cation in the cathodic compartment, and Vi is The volume of cathode chamber, ni is the molal quantity of cation i, and Qtotal is electrolysis electricity, and I is electric current, and t is electrolysis Persistent period, F is Faraday constant, use formula (1) computation migration number value.For V³⁺、VO²⁺ And VO₂ ⁺Ion, the transport number through barrier film uses equation below to calculate respectively, as formula (2), (3), (4) shown in:

$t_{V^{3+}}=\frac{z_{V^{3+}}{n}_{V^{3+}}F}{Q_{total}}=\frac{3n_{V^{3+}}F}{It}---\left(2\right)$

$t_{{\mathrm{VO}}^{2+}}=\frac{z_{{\mathrm{VO}}^{2+}}{n}_{{\mathrm{VO}}^{2+}}F}{Q_{total}}=\frac{2n_{{\mathrm{VO}}^{2+}}F}{It}---\left(3\right)$

$t_{{\mathrm{VO}}_2^{+}}=\frac{z_{{\mathrm{VO}}_2^{+}}{n}_{{\mathrm{VO}}_2^{+}}F}{Q_{total}}=\frac{n_{{\mathrm{VO}}_2^{+}}F}{It}---\left(4\right)$

Table 2

Table 3

Embodiment	Film thickness (μm)	Surface resistance (Ω cm2)	Cl-Transport number	SO4 2-Transport number
					Unsoaked film	70	0.84	0.951	0.913
Soak the film of 30 days	70	0.86	0.940	0.906

As can be seen from Table 2, the vanadium ion transport number of Nafion membrane is far longer than modified PES-PVP and the moon is blended Ion exchange membrane, transmission ion main in Nafion cation exchange membrane is hydrion, along with H+ ion Migrating, vanadium ion migrates to cathode chamber from anode chamber；Owing to the hydrion in film can be replaced by other cation Changing, in charging process, part tetravalence and pentavalent vanadium ion can move to electrolyte liquid from positive pole, Then these ions and divalent vanadium ion react generation trivalent vanadium ion, it means that have lost both positive and negative polarity electricity and live The capacity of property material.Equally, in discharge process, part bivalence and trivalent vanadium ion just move to from negative pole In the electrolyte of pole, react generation tetravalent vanadium ion with pentavalent vanadium ion.Will through Nafion membrane exchange vanadium ion Energy content of battery efficiency is caused to reduce.But, modified PES-PVP be blended anion exchange membrane be possible to prevent sun from Son rather than the cross-contamination of anion, make to be blended the vanadium ion of anion exchange membrane through modified PES-PVP Transport number is far smaller than the number through Nafion membrane, it can thus be seen that modified PES-PVP be blended cloudy from The resistance vanadium performance of proton exchange is far superior to Nafion membrane.

The Cl that modified PES-PVP is blended in anion exchange membrane as can be seen from Table 3^-And SO₄ ^2-Transport number. Under the electric field, modified PES-PVP is blended in anion exchange membrane, along with SO₄ ^2-Migrate to from cathode chamber Anode chamber, minimal amount of vanadium ion migrates to cathode chamber through anion exchange membrane from anode chamber；Barrier film is by force Chemical stability in oxidisability electrolyte is one of main restricting factor of whole vanadium oxide reduction battery life. Originally some commercialization barrier films show good coulombic efficiency, but chemical stability official post they at battery In restricted lifetime.Table 2, the data of table 3 show, modified PES-PVP is blended anion exchange membrane at oxygen After the property changed acid solution soaks 30 days, still there is good performance, table in whole vanadium oxide reduction battery Reveal the chemical stability of excellence, extend the service life of film.

Modified PES-the PVP of the present invention is blended anion exchange membrane, combines quaternary ammonium base quaternary ammonium in modified PES The advantage changing modified PES and quaternised modified PES and PVP of imidazoles, and by adjusting modified PES With the proportioning of PVP, and in modified PES, the quaternised modified PES of quaternary ammonium base is quaternised modified with imidazoles The proportioning of PES, has inquired into the performance of different films, it can be seen that the modification present invention prepared PES-PVP is blended anion exchange membrane when being applied to vanadium redox battery, has good resistance vanadium Performance, ion select performance, have excellent stability and mechanical performance, and coulombic efficiency is high, service life Long.

Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. one kind is blended anion exchange membrane for the modified PES-PVP of vanadium cell, it is characterised in that by Being prepared from after quaternised modified PES and PVP is blended, described quaternised modified PES is quaternary ammonium base season Ammonium modified PES and the mixture of the quaternised modified PES of imidazoles.

Modified PES-PVP the most according to claim 1 is blended anion exchange membrane, it is characterised in that The mass ratio of described quaternised modified PES and described PVP is 1:(1～5).

Modified PES-PVP the most according to claim 1 is blended anion exchange membrane, it is characterised in that The mass ratio of the quaternised modified PES of described quaternary ammonium base and the quaternised modified PES of described imidazoles be 1:(1～ 3)。

Modified PES-PVP the most according to claim 1 is blended anion exchange membrane, it is characterised in that Described quaternised modified PES is prepared after chloromethylation reagents chloromethylation, amination reagent are quaternized by PES Obtain.

Modified PES-PVP the most according to claim 4 is blended anion exchange membrane, it is characterised in that Described chloromethylation reagents is chloromethyl alkyl ether；

Preferably, described chloromethyl alkyl ether selected from chloromethyl methyl ether, chloromethyl ether, chloromethyl butyl ether, One in chloromethyl octyl ether or at least two.

Modified PES-PVP the most according to claim 4 is blended anion exchange membrane, it is characterised in that In the quaternised modified PES of described quaternary ammonium base, described amination reagent selected from trimethylamine, triethylamine, tripropyl amine (TPA), One in tri-n-butylamine or at least two；

In the quaternised modified PES of described imidazoles, described amination reagent is 1-Methylimidazole..

7. modified PES-PVP as claimed in claim 1 is blended a preparation method for anion exchange membrane, It is characterized in that, comprise the steps:

1) by proportioning, quaternised modified for quaternary ammonium base PES, quaternised modified PES with PVP of imidazoles are blended After, join in DMF solution and stir, obtain blended liquid；

2) by step 1) blended liquid prepared is applied on substrate, prepares altogether after drying, peeling off Mixed anion exchange membrane；

3) by step 2) the blended anion exchange membrane prepared soaks in sulfuric acid solution, prepares modification PES-PVP is blended anion exchange membrane.

Preparation method the most according to claim 7, it is characterised in that step 1) in, described stirring Time be 5～8h, the temperature of described DMF solution is 40 DEG C；Described quaternised modified PES is with described The mass ratio of PVP is 1:(1～5), the quaternised modified PES of described quaternary ammonium base is quaternized with described imidazoles The mass ratio of modified PES is 1:(1～3)；

Step 2) in, the temperature of described drying is 60～90 DEG C, and described substrate is glass plate or coating machine, The process of described stripping is, after the substrate ultrasonic humidifier after drying humidifies, blended anion is handed over Change film to peel off from substrate；

Step 3) in, the concentration of described sulfuric acid solution is 1～3M, and the time of described immersion is 36～80h.

Preparation method the most according to claim 7, it is characterised in that described quaternary ammonium base is quaternised modified The preparation process of PES is:

1) PES of 1～5g is dissolved in the concentrated sulphuric acid of 10～30ml, adds the chloromethyl alkane of 8～15ml In base ether, separate out white solid after reaction 5～8h, be washed with deionized water to neutrality, after drying, obtain chloromethane Base PES；

2) by step 1) the chloromethylation PES that obtains is soaked in amination reagent 24～48h, uses deionization It is washed to neutrality, after drying, obtains the quaternized PES of quaternary ammonium base；Wherein, described amination reagent be trimethylamine, One in triethylamine, tripropyl amine (TPA), tri-n-butylamine or at least two.

Preparation method the most according to claim 7, it is characterised in that described imidazoles is quaternized to be changed The preparation process of property PES is:

1) PES of 1～5g is dissolved in the concentrated sulphuric acid of 10～30ml, adds the chloromethyl alkane of 8～15ml In base ether, separate out white solid after reaction 5～8h, be washed with deionized water to neutrality, after drying, obtain chloromethane Base PES；

2) by step 1) the chloromethylation PES that obtains is soaked in 1-Methylimidazole. 24～48h, spend from Son is washed to neutrality, obtains the quaternized PES of imidazoles after drying.