CN105789657B - Anion-exchange membrane and preparation method thereof is blended in a kind of modified PES-PVP for vanadium cell - Google Patents
Anion-exchange membrane and preparation method thereof is blended in a kind of modified PES-PVP for vanadium cell Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of modified PES PVP for vanadium cell, and anion-exchange membrane is blended.Anion-exchange membrane is blended in a kind of modified PES PVP for vanadium cell of the present invention, by quaternised modified PES and PVP it is blended after be prepared, quaternised modified PES for the quaternised modified PES of quaternary ammonium base and the quaternised modified PES of imidazoles mixture；After the quaternised modified PES anion-exchange membranes of quaternary ammonium base, the quaternised modified PES anion-exchange membranes of imidazoles and PVP are blended, the excellent performance of three is combined.Anion-exchange membrane is blended when applied to vanadium redox battery in the modified PES PVP that the present invention is prepared, and has good resistance vanadium performance, ion selectivity energy, has excellent stability and mechanical performance, and coulombic efficiency is high, and service life is long.
Description
Technical field
The invention belongs to electrochemical material fields, and in particular to a kind of modified PES-PVP for vanadium cell be blended it is cloudy from
Proton exchange and preparation method thereof.
Background technology
Vanadium cell full name is vanadium redox battery (Vanadium Redox Battery, be abbreviated as VRB), is
A kind of active material is in the redox cell for circulating liquid, is anti-using the redox between different valence state vanadium ion
Should realize the conversion of the energy, the active material of participating in reaction is the vanadium ion of liquid, vanadium cell be it is a kind of efficiently, it is environmental protection, big
Capacity, can high current charge-discharge, deep discharge liquid flow energy storage battery.
Vanadium cell is mainly made of electrode material, electrolyte and amberplex.Wherein, amberplex is as vanadium cell
One of core component, how to obtain the diaphragm of highly selective, low resistance and enough chemical stabilities is to restrict vanadium cell performance
Key factor.Ideal diaphragm material should have differential permeability, both allowed carrier by ensureing high conductivity, and subtracted
The interior loss of energy of baby battery, and infiltration of the electrolyte ion by diaphragm is prevented, reduce the loss of the battery capacity thereby resulted in.
It is attractive to the vanadium ion in VRB solution since the fixed group of cation-exchange membrane is azochlorosulfonate acid anion, although logical
The permeability of vanadium ion can be reduced to a certain extent by crossing the modification to film, but cannot fundamentally prevent oozing for vanadium ion
Thoroughly.In contrast, the fixed group of anion-exchange membrane carries positive charge ion, since the infiltration of Donan effect vanadium ions will
It is restricted, thus ion selectivity is higher.Currently, although the Nafion membrane applied to commercialization vanadium cell has goodization
Stability and lower surface resistance are learned, but it is expensive, and poor to the barrier property of vanadium ion, self-discharge of battery phenomenon is tight
Weight, influences battery efficiency.
Invention content
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of modified PESs-for vanadium cell
Anion-exchange membrane is blended in PVP, has good resistance vanadium performance, ion selectivity energy, has excellent stability and mechanicalness
Can, coulombic efficiency is high, and service life is long.
For this purpose, the present invention uses following technical scheme：
Anion-exchange membrane is blended in a kind of modified PES-PVP (polyether sulfone-polyvinylpyrrolidone) for vanadium cell, by
It is prepared after quaternised modified PES and PVP are blended, the quaternised modified PES is the quaternised modified PES of quaternary ammonium base and miaow
The mixture of the quaternised modified PES of azole.
Anion-exchange membrane contains basic activated group, and passing through for cation can be obstructed through anion, and anion is handed over
Change film due to positive charge and vanadium ion have repelling effect, the transmembrane movement of vanadium ion can be prevented, it is thus possible to effectively
Improve the coulombic efficiency and energy efficiency of battery.Infiltration of the vanadium ion in film can be effectively reduced using anion-exchange membrane
Rate, but the increase for having also resulted in impedance makes voltage efficiency be declined, and the chemical stability of anion-exchange membrane
Low, water migration height, needs to make modification to anion-exchange membrane.Since the stability of anion-exchange membrane is poor, pass through blending
The modified performance that can effectively improve film.
Polyether sulfone (PES) is a kind of chemically inert engineering thermoplasties, have excellent mechanical performance, polyether sulfone into
Row quaternary amine is modified, and introduces quaternary ammonium group；With preparing anion-exchange membrane after amine reagent functionalization after chloromethylation, wherein profit
The quaternised modified PES anion-exchange membranes of quaternary ammonium base for using trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine etc. as amination reagent
With relatively good ion selectivity and higher energy efficiency, but ionic conductivity is low, thermal stability and chemical stability
Difference；There is preferable heat using 1- methylimidazoles etc. as the quaternised modified PES anion-exchange membranes of the imidazoles of amination reagent
Stability and chemical stability, fixedness and high ionic conductivity, by the quaternised modified PES of quaternary ammonium base, imidazoles quaternary ammonium
Change modified PES to be blended with polyvinylpyrrolidone (PVP), PVP is a kind of water-soluble polymer, has good film forming
With stability, the carbonyl in PVP has strong interaction with quaternary ammonium group, is prepared and be modified by the blend of three kinds of substances
Anion-exchange membrane is blended in PES-PVP, is used for vanadium redox battery field, has good resistance vanadium performance, ion
Performance is selected, there is excellent stability and mechanical performance, coulombic efficiency is high, and service life is long.
Wherein, the mass ratio of the quaternised modified PES and 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 the quaternary ammonium base and quaternised modified PES of the imidazoles is 1：(1~
, such as 1 3):1、1:1.5、1:2、1:2.5、1:3.
Wherein, the quaternised modified PES is made by PES after chloromethylation reagents chloromethylation, amination reagent are quaternized
It is standby to obtain.
Wherein, the chloromethylation reagents are chloromethyl alkyl ether；Preferably, the chloromethyl alkyl ether is selected from chloromethyl
Methyl ether, chloromethyl ether, chloromethyl butyl ether, one kind in chloromethyl octyl ether or at least two.
Wherein, in the quaternised modified PES of the quaternary ammonium base, the amination reagent be selected from trimethylamine, triethylamine, tripropyl amine (TPA),
One kind in tri-n-butylamine or at least two；In the quaternised modified PES of imidazoles, the amination reagent is 1- methylimidazoles.
The second object of the present invention is to provide a kind of modified PES-PVP for vanadium cell and anion-exchange membrane is blended
Preparation method includes the following steps：
1) after the quaternised modified PES of quaternary ammonium base, the quaternised modified PES of imidazoles being blended with PVP according to the ratio, it is added to N,
It is stirred in dinethylformamide (DMF) solution, obtains blended liquid；
2) blended liquid prepared by step 1) is applied on substrate, blending anion is prepared after drying, removing
Exchange membrane；
3) blending anion-exchange membrane prepared by step 2) is impregnated in sulfuric acid solution, modified PES-PVP is prepared
Anion-exchange membrane is blended.
The preparation method that anion-exchange membrane is blended for the modified PES-PVP of vanadium cell of the present invention, it is quaternised modified
PES and PVP is mutually shifted and winds in DMF solvent, forms a kind of homogeneous phase, and made with the post-processing that sulfuric acid solution impregnates
Film obtained has better hydrophily.
Preferably, in step 1), the time of the stirring is 5~8h, and the temperature of the DMF solution is 40 DEG C；The season
The mass ratio of ammonium modified PES and the PVP are 1：(1~5), the quaternised modified PES of quaternary ammonium base and the imidazoles season
The mass ratio of ammonium modified PES is 1：(1~3)；
In step 2), the temperature of the drying is 60~90 DEG C, and the substrate is glass plate or coating machine, the stripping
Process be, after the substrate after drying is humidified with ultrasonic humidifier, by be blended anion-exchange membrane removed from substrate；It dries
Dry purpose is to remove the solvent DMF in solution, after being handled with ultrasonic humidifier, can be more convenient to shell from substrate by film
From；
In step 3), the time of a concentration of 1~3M of the sulfuric acid solution, the immersion are 36~80h；Use sulfuric acid solution
It impregnates as post-processing so that film has better hydrophilicity.
Wherein, the preparation process of the quaternised modified PES of the quaternary ammonium base is：
1) PES of 1~5g is dissolved in the concentrated sulfuric acid of 10~30ml, is added in the chloromethyl alkyl ether of 8~15ml, reaction
White solid is precipitated after 5~8h, is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；
2) the chloromethylation PES that step 1) obtains is soaked in 24~48h in amination reagent, be washed with deionized water into
Property, the quaternized PES of quaternary ammonium base is obtained after drying；Wherein, the amination reagent is in trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine
One kind or at least two.
Wherein, the preparation process of the quaternised modified PES of the imidazoles is：
1) PES of 1~5g is dissolved in the concentrated sulfuric acid of 10~30ml, is added in the chloromethyl alkyl ether of 8~15ml, reaction
White solid is precipitated after 5~8h, is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；
2) the chloromethylation PES that step 1) obtains is soaked in 24~48h in 1- methylimidazoles, be washed with deionized water into
Property, the quaternized PES of imidazoles is obtained after drying.
Compared with prior art, beneficial effects of the present invention are：A kind of modified PES-PVP for vanadium cell of the present invention
Be blended anion-exchange membrane, by quaternised modified PES and PVP it is blended after be prepared, the quaternised modified PES be quaternary ammonium
The mixture of the quaternised modified PES of alkali and the quaternised modified PES of imidazoles；The quaternised modified PES anion-exchange membranes of quaternary ammonium base
With excellent ion selectivity and higher energy efficiency, the quaternised modified PES anion-exchange membranes of imidazoles have excellent
Thermal stability and chemical stability, fixedness and high ionic conductivity, PES is quaternised modified by quaternary ammonium base respectively
With imidazoles it is quaternised modified after, the advantages of both combining, by the quaternised modified PES of quaternary ammonium base and imidazoles are quaternized changes
After property PES is blended with PVP, further combined with the good film formings of PVP and stability, carbonyl and quaternary ammonium group in PVP
It interacts so that anion-exchange membrane is blended applied to whole vanadium oxide reduction liquid in the modified PES-PVP being prepared
When galvanic battery, there is good resistance vanadium performance, ion selectivity energy, there is excellent stability and mechanical performance, coulombic efficiency
Height, service life are long.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field
It obtains.
Embodiment 1
1) PES of 1g is dissolved in the concentrated sulfuric acid of 10ml, is added in the chloromethyl methyl ether of 8ml, white is precipitated after reacting 5h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in trimethylamine
In for 24 hours, be washed with deionized water to neutrality, the quaternized PES of quaternary ammonium base obtained after drying；
2) PES of 1g is dissolved in the concentrated sulfuric acid of 10ml, is added in the chloromethyl methyl ether of 8ml, white is precipitated after reacting 5h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in 1- methyl
In imidazoles for 24 hours, it is washed with deionized water to neutrality, the quaternized PES of imidazoles is obtained after drying；
3) it is 1 in mass ratio：The quaternised modified PES of quaternary ammonium base, imidazoles quaternised modified PES and PVP are total to by 1 proportioning
After mixed, the mass ratio of the quaternised modified PES and PVP is 1：2, it is added to the N that temperature is 40 DEG C, N- dimethyl formyls
5h is stirred in amine (DMF) solution, obtains blended liquid；
4) blended liquid of preparation is applied on glass panel substrate, is dried by 60 DEG C, by the substrate ultrasound after drying
After wave humidifier humidifies, anion-exchange membrane will be blended and removed from substrate；By the blending anion-exchange membrane of preparation in 2M sulphur
36h is impregnated in acid solution, modified PES-PVP is prepared, anion-exchange membrane is blended.
Embodiment 2
1) PES of 2g is dissolved in the concentrated sulfuric acid of 20ml, is added in the chloromethyl ether of 10ml, white is precipitated after reacting 7h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in triethylamine
Middle 36h is washed with deionized water to neutrality, and the quaternized PES of quaternary ammonium base is obtained after drying；
2) PES of 2g is dissolved in the concentrated sulfuric acid of 20ml, is added in the chloromethyl ether of 10ml, white is precipitated after reacting 7h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in 1- methyl
36h in imidazoles is washed with deionized water to neutrality, and the quaternized PES of imidazoles is obtained after drying；
3) it is 1 in mass ratio：The quaternised modified PES of quaternary ammonium base, imidazoles quaternised modified PES and PVP are total to by 3 proportioning
After mixed, the mass ratio of the quaternised modified PES and PVP is 1：3, it is added to the N that temperature is 40 DEG C, N- dimethyl formyls
7h is stirred in amine (DMF) solution, obtains blended liquid；
4) blended liquid of preparation is applied on glass panel substrate, is dried by 80 DEG C, by the substrate ultrasound after drying
After wave humidifier humidifies, anion-exchange membrane will be blended and removed from substrate；By the blending anion-exchange membrane of preparation in 1M sulphur
48h is impregnated in acid solution, modified PES-PVP is prepared, anion-exchange membrane is blended.
Embodiment 3
1) PES of 3g is dissolved in the concentrated sulfuric acid of 30ml, is added in the chloromethyl butyl ether of 12ml, white is precipitated after reacting 8h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in triethylamine
Middle 48h is washed with deionized water to neutrality, and the quaternized PES of quaternary ammonium base is obtained after drying；
2) PES of 3g is dissolved in the concentrated sulfuric acid of 30ml, is added in the chloromethyl butyl ether of 12ml, white is precipitated after reacting 8h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in 1- methyl
48h in imidazoles is washed with deionized water to neutrality, and the quaternized PES of imidazoles is obtained after drying；
3) it is 1 in mass ratio：The quaternised modified PES of quaternary ammonium base, imidazoles quaternised modified PES and PVP are total to by 2 proportioning
After mixed, the mass ratio of the quaternised modified PES and PVP is 1：4, it is added to the N that temperature is 40 DEG C, N- dimethyl formyls
8h is stirred in amine (DMF) solution, obtains blended liquid；
4) blended liquid of preparation is applied on glass panel substrate, is dried by 85 DEG C, the substrate after drying is ultrasonic
After wave humidifier humidifies, anion-exchange membrane will be blended and removed from substrate；By the blending anion-exchange membrane of preparation in 2M sulphur
48h is impregnated in acid solution, modified PES-PVP is prepared, anion-exchange membrane is blended.
Embodiment 4
1) PES of 5g is dissolved in the concentrated sulfuric acid of 25ml, is added in the chloromethyl octyl ether of 15ml, white is precipitated after reacting 7h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in tri-n-butylamine
Middle 48h is washed with deionized water to neutrality, and the quaternized PES of quaternary ammonium base is obtained after drying；
2) PES of 5g is dissolved in the concentrated sulfuric acid of 25ml, is added in the chloromethyl octyl ether of 15ml, white is precipitated after reacting 7h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in 1- methyl
48h in imidazoles is washed with deionized water to neutrality, and the quaternized PES of imidazoles is obtained after drying；
3) it is 1 in mass ratio：2.5 proportioning is by the quaternised modified PES of quaternary ammonium base, imidazoles quaternised modified PES and PVP
After blending, the mass ratio of the quaternised modified PES and PVP is 1：4, it is added to the N that temperature is 40 DEG C, N- dimethyl methyls
6h is stirred in amide (DMF) solution, obtains blended liquid；
4) blended liquid of preparation is applied on coating machine substrate, is dried by 90 DEG C, by the substrate ultrasound after drying
After wave humidifier humidifies, anion-exchange membrane will be blended and removed from substrate；By the blending anion-exchange membrane of preparation in 3M sulphur
80h is impregnated in acid solution, modified PES-PVP is prepared, anion-exchange membrane is blended.
Embodiment 5
1) PES of 5g is dissolved in the concentrated sulfuric acid of 30ml, is added in the chloromethyl methyl ether of 15ml, white is precipitated after reacting 8h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in trimethylamine
Middle 48h is washed with deionized water to neutrality, and the quaternized PES of quaternary ammonium base is obtained after drying；
2) PES of 5g is dissolved in the concentrated sulfuric acid of 30ml, is added in the chloromethyl methyl ether of 15ml, white is precipitated after reacting 8h
Solid is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；Obtained chloromethylation PES is soaked in 1- methyl
36h in imidazoles is washed with deionized water to neutrality, and the quaternized PES of imidazoles is obtained after drying；
3) it is 1 in mass ratio：The quaternised modified PES of quaternary ammonium base, imidazoles quaternised modified PES and PVP are total to by 3 proportioning
After mixed, the mass ratio of the quaternised modified PES and PVP is 1：5, it is added to the N that temperature is 40 DEG C, N- dimethyl formyls
7h is stirred in amine (DMF) solution, obtains blended liquid；
4) blended liquid of preparation is applied on glass panel substrate, is dried by 80 DEG C, the substrate after drying is ultrasonic
After wave humidifier humidifies, anion-exchange membrane will be blended and removed from substrate；By the blending anion-exchange membrane of preparation in 2M sulphur
48h is impregnated in acid solution, modified PES-PVP is prepared, anion-exchange membrane is blended.
Anion-exchange membrane is blended in the modified PES-PVP that Examples 1 to 5 is prepared and carries out performance survey as diaphragm
Examination, performance characterization include：Water imbibition, surface resistance (R, Ω cm2) and stability.Wherein, the water imbibition of diaphragm is measured with reference to weight
Amount method evaporates DMF at 80 DEG C, then at 25 DEG C, until weight remains unchanged, obtains the dry weight of film, then will
Film impregnates 3 days, after impregnation in distilled water, wipes the moisture on surface, the moist weight of film is measured, by the dry weight of film
The water absorption of film is measured with moist weight；Modified PES-PVP blending the anion-exchange membranes being prepared, which are clipped in two, includes
Between the half-cell of graphite plate electrode, the measurement of surface resistance is the H in 25 DEG C of 2.0MD2SO4In solution, electrochemical workstation is used
Impedance methodologies (exchange 1kHz) are measured, diaphragm has low surface resistance, can be used for whole vanadium oxide reduction battery, 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 water absorption that anion-exchange membrane is blended in the modified PES-PVP that prepared by the present invention is small, swelling
The small satisfactory mechanical property for making film；Surface resistance is low, close to surface resistance (the 0.95 Ω cm of Nafion membrane2), and far below more
The surface resistance of kind commercialization amberplex.Lower surface resistance allows modified PES-PVP blending anion-exchange membranes to apply
In whole vanadium oxide reduction battery.In addition, high coulombic efficiency is also to hinder the good factor of vanadium performance.
Anion-exchange membrane is blended in modified PES-PVP prepared by embodiment 1 to be placed in strong oxidizing property acidity solution, 25
DEG C 1M (VO2)2SO4With the H of 2M2SO4It is impregnated 30 days in mixed solution, the H of 2M is used after immersion2SO4Solution washing is multiple, leads to
Cross and measure the transport number of vanadium ion to measure the stability of film, and using the vanadium ion transport number of Nafion cation-exchange membranes as
Comparative example, experimental result are shown in Table 2.It is being soaked simultaneously by the transport number of the thickness of measurement film, surface resistance, anion to characterize diaphragm
The front and back performance change of bubble, experimental result are shown in Table 3.
Wherein, hittorf method has been used to measure vanadium ion transport number.Cationic i penetrates the transport number such as formula (1) of diaphragm
It is shown：
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 cathode chamber
Volume, ni are the molal quantitys of cationic i, and Qtotal is electrolysis electricity, and I is electric current, and t is the duration of electrolysis, and F is faraday
Constant uses the value of formula (1) computation migration number.For V3+、VO2+And VO2 +Ion, through the transport number respectively under use of diaphragm
The formula in face is calculated, as shown in formula (2), (3), (4)：
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 |
| Impregnate 30 days films | 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 blending anion exchanges
Film, main transmission ion is hydrogen ion in Nafion cation-exchange membranes, and with the migration of H+ ions, vanadium ion is from anode chamber
It migrates to cathode chamber；Since the hydrogen ion in film can be replaced by other cations, in charging process, part tetravalence and pentavalent
Vanadium ion can move in electrolyte liquid from anode, then these ions reacted with divalent vanadium ion generate trivalent vanadium from
Son, it means that have lost the capacity of positive and negative anodes electroactive material.Equally, in discharge process, part divalent and trivalent vanadium from
Son is moved to from cathode in anode electrolyte, is reacted with pentavalent vanadium ion and is generated tetravalent vanadium ion.Vanadium is exchanged through Nafion membrane
Ion will lead to the reduction of energy content of battery efficiency.However, modified PES-PVP be blended anion-exchange membrane can prevent cation without
It is the cross contamination of anion, keeps the vanadium ion transport number that anion-exchange membrane is blended through modified PES-PVP far smaller than saturating
The number of Nafion membrane is crossed, it can thus be seen that the resistance vanadium performance that anion-exchange membrane is blended in modified PES-PVP is far superior to
Nafion membrane.
The Cl in anion-exchange membrane is blended in modified PES-PVP as can be seen from Table 3-And SO4 2-Transport number.In electric field
Under, modified PES-PVP is blended in anion-exchange membrane, along with SO4 2-Migrated from cathode chamber to anode chamber, minimal amount of vanadium from
Son is migrated from anode chamber to cathode chamber through anion-exchange membrane；Chemical stability of the diaphragm in strong oxidizing property electrolyte is complete
One of the main restricting factor in vanadium redox battery service life.Originally some commercialization diaphragms show good coulombic efficiency,
But chemical stability official post their restricted lifetimes in the battery.Table 2, table 3 statistics indicate that, modified PES-PVP is blended cloudy
It is still with good performance after amberplex impregnates 30 days in oxidative acidic solution, in whole vanadium oxide reduction battery
In show excellent chemical stability, extend the service life of film.
Anion-exchange membrane is blended in the modified PES-PVP of the present invention, and it is quaternised modified to combine quaternary ammonium base in modified PES
The advantages of PES and imidazoles quaternised modified PES and PVP, and by adjusting the proportioning of modified PES and PVP, and it is modified
The proportioning of the quaternised modified PES of quaternary ammonium base and the quaternised modified PES of imidazoles, have inquired into the performance of different films in PES, can be with
Find out, anion-exchange membrane, which is blended, in the modified PES-PVP that the present invention is prepared is applied to vanadium redox battery
When, there is good resistance vanadium performance, ion selectivity energy, there is excellent stability and mechanical performance, coulombic efficiency is high, uses
Long lifespan.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (7)
1. anion-exchange membrane is blended in a kind of modified PES-PVP for vanadium cell, which is characterized in that by quaternised modified PES
With PVP it is blended after be prepared, the quaternised modified PES is the quaternised modified PES of quaternary ammonium base and imidazoles are quaternized changes
The mixture of property PES；
The mass ratio of the quaternised modified PES and PVP is 1：(1~5)；
The mass ratio of the quaternised modified PES of the quaternary ammonium base and quaternised modified PES of the imidazoles is 1：(1~3).
2. anion-exchange membrane is blended in modified PES-PVP according to claim 1, which is characterized in that described quaternized to change
Property PES is prepared by PES after chloromethylation reagents chloromethylation, amination reagent are quaternized.
3. anion-exchange membrane is blended in modified PES-PVP according to claim 2, which is characterized in that the chloromethylation
Reagent is chloromethyl alkyl ether.
4. anion-exchange membrane is blended in modified PES-PVP according to claim 3, which is characterized in that the chloromethyl alkane
The one kind or at least two of base ether in chloromethyl methyl ether, chloromethyl ether, chloromethyl butyl ether, chloromethyl octyl ether.
5. anion-exchange membrane is blended in modified PES-PVP according to claim 2, which is characterized in that the quaternary ammonium base season
In ammonium modified PES, the one kind or at least two of the amination reagent in trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine；
In the quaternised modified PES of imidazoles, the amination reagent is 1- methylimidazoles.
6. the preparation method of anion-exchange membrane is blended in a kind of modified PES-PVP as described in claim 1, which is characterized in that
Include the following steps：
1) after the quaternised modified PES of quaternary ammonium base, the quaternised modified PES of imidazoles being blended with PVP according to the ratio, it is molten to be added to DMF
It is stirred in liquid, obtains blended liquid；2) blended liquid prepared by step 1) is applied on substrate, is prepared into after drying, removing
To blending anion-exchange membrane；
3) blending anion-exchange membrane prepared by step 2) is impregnated in sulfuric acid solution, modified PES-PVP is prepared and is blended
Anion-exchange membrane；
Wherein, the preparation process of the quaternised modified PES of the quaternary ammonium base is：
1) PES of 1~5g is dissolved in the concentrated sulfuric acid of 10~30ml, is added in the chloromethyl alkyl ether of 8~15ml, reaction 5~
White solid is precipitated after 8h, is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；
2) the chloromethylation PES that step 1) obtains is soaked in 24~48h in amination reagent, is washed with deionized water to neutrality, dries
The quaternized PES of quaternary ammonium base is obtained after dry；Wherein, the amination reagent is one in trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine
Kind or at least two；
The preparation process of the quaternised modified PES of imidazoles is：
1) PES of 1~5g is dissolved in the concentrated sulfuric acid of 10~30ml, is added in the chloromethyl alkyl ether of 8~15ml, reaction 5~
White solid is precipitated after 8h, is washed with deionized water to neutrality, chloromethylation PES is obtained after drying；
2) the chloromethylation PES that step 1) obtains is soaked in 24~48h in 1- methylimidazoles, is washed with deionized water to neutrality,
The quaternized PES of imidazoles is obtained after drying.
7. preparation method according to claim 6, which is characterized in that in step 1), the time of the stirring is 5~8h,
The temperature of the DMF solution is 40 DEG C；The mass ratio of the quaternised modified PES and PVP is 1：(1~5), the quaternary ammonium
The mass ratio of the quaternised modified PES of the alkali and quaternised modified PES of the imidazoles is 1：(1~3)；
In step 2), the temperature of the drying is 60~90 DEG C, and the substrate is glass plate or coating machine, the mistake of the stripping
Cheng Wei after humidifying the substrate after drying with ultrasonic humidifier, will be blended anion-exchange membrane and be removed from substrate；
In step 3), the time of a concentration of 1~3M of the sulfuric acid solution, the immersion are 36~80h.
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| CN112290068A (en) * | 2020-09-21 | 2021-01-29 | 长春工业大学 | Two quaternary ammonium side chain type anion exchange membranes for fuel cell and preparation method thereof |
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| CN102049203A (en) * | 2010-11-04 | 2011-05-11 | 厦门大学 | Anion-exchange membrane in acid medium |
| CN104861167A (en) * | 2015-05-29 | 2015-08-26 | 常州大学 | Polyether sulphone containing plurality of quaternary ammonium salt phenyl side group structures and preparation method for polyether sulphone |
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| CN104861167A (en) * | 2015-05-29 | 2015-08-26 | 常州大学 | Polyether sulphone containing plurality of quaternary ammonium salt phenyl side group structures and preparation method for polyether sulphone |
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| "VRB用季铵化聚醚砜阴离子交换膜";张守海等;《电池》;20100630;第40卷(第3期);第137-139页 * |
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