CN103762375B - Politef interlayer protection ion exchange membrane, its preparation method and flow battery - Google Patents
Politef interlayer protection ion exchange membrane, its preparation method and flow battery Download PDFInfo
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- CN103762375B CN103762375B CN201410013122.4A CN201410013122A CN103762375B CN 103762375 B CN103762375 B CN 103762375B CN 201410013122 A CN201410013122 A CN 201410013122A CN 103762375 B CN103762375 B CN 103762375B
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- ion exchange
- exchange membrane
- flow battery
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- 239000011229 interlayer Substances 0.000 title claims abstract description 57
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 52
- 229950000845 politef Drugs 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 38
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 210000004379 membrane Anatomy 0.000 claims abstract description 15
- 239000004809 Teflon Substances 0.000 claims abstract description 12
- 229920006362 Teflon® Polymers 0.000 claims abstract description 12
- 230000002146 bilateral effect Effects 0.000 claims abstract description 9
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 36
- 229920002530 polyetherether ketone Polymers 0.000 claims description 36
- 238000006277 sulfonation reaction Methods 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920005649 polyetherethersulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000010408 film Substances 0.000 description 89
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 description 28
- 230000004087 circulation Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 238000007599 discharging Methods 0.000 description 12
- 239000012982 microporous membrane Substances 0.000 description 10
- 229920000557 Nafion® Polymers 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of politef interlayer protection ion exchange membrane, including sulphonated polymers ion exchange membrane basement membrane, also include one side or the microporous teflon membran of bilateral being fitted in described basement membrane as interlayer protection film.Also disclose the preparation method of described politef interlayer protection ion exchange membrane and use the flow battery of described politef interlayer protection ion exchange membrane.The politef interlayer protection ion exchange membrane of the present invention can meet the requirement of macroion selectivity and high stability simultaneously, can significantly improve efficiency and the cycle life of its flow battery applied particularly all-vanadium flow battery.
Description
Technical field
The present invention relates to flow battery, particularly relate to a kind of politef interlayer protection ion exchange
Film, the preparation method of this ion exchange membrane and use the flow battery of this ion exchange membrane.
Background technology
The energy and environment are always the key factor of human society survival and development.In order to solve current energy
Source consumption and the contradiction of environmental pollution, it is achieved the sustainable development of national economy, people start exploitation and
Utilize regenerative resource, such as solar energy, wind energy, tide energy etc., but the sending out of these regenerative resources
Electricity has unstability and discontinuity.In order to realize the stable and continuous of subsequent power generation, exploitation is efficiently
Excellent scale energy storage technology is particularly important.Flow battery (flow battery) because its capacitance of storage is big,
Have extended cycle life, environmental friendliness, addressing freely, quickly response, easily realize scale, can the degree of depth
The advantages such as electric discharge and become the ideal form of extensive energy storage, be widely used in renewable energy power generation storage
The aspects such as energy, peak load regulation network, intelligent grid, uninterrupted power source.Wherein, all-vanadium flow battery
(Vanadium redox flow battery is called for short VRB or vanadium cell) have energy conversion efficiency high,
The advantages such as simple in construction, system design (power and capacity) are flexibly, maintenance cost is low it is considered to be
It is easiest to realize a kind of flow battery of scale application and great potential.
Ion exchange membrane is one of critical material of restriction flow battery development, mainly has two works
With: separate both positive and negative polarity and conduction ion.Preferably ion exchange membrane should have characteristics that high from
Sub-selectivity (the highest ionic conductivity and relatively low active substance permeability), good chemistry and
Electrochemical stability, good mechanical strength, relatively low cost etc..Flow battery film is main at present
There are two classes: perfluor type sulfonate film with the Nafion series membranes of du pont company as representative and with sulfonation
Polyether-ether-ketone (sulfonated poly ether ether ketone, be called for short SPEEK) be representative non-entirely
Fluorine-type sulfonate film.Nafion membrane has that higher proton conductivity, chemical stability be high, heat stability
The advantage such as good, but expensive, active substance permeability high and preparation process has pollution to environment.
The ion selectivity of sulfonated polyether-ether-ketone film is high, low cost, and the efficiency of flow battery is high, but it is mechanical
Strength and stability is poor, causes battery life the longest.Therefore, macroion selectivity, high stability,
The developmental research of the ion exchange membrane of low cost, to promoting flow battery particularly all-vanadium flow battery
Large-scale application is significant.
In all-vanadium flow battery, the ion selectivity of ion exchange membrane and stability be two contrary
Aspect, when traditional ion exchange polymer film ion selectivity after generally optimizing is higher, it is stable
Property is poor.
Summary of the invention
Present invention aim to overcome that the existing flow battery preferable ion exchange membrane of ion selectivity
The problem of the less stable existed, it is provided that one meets macroion selectivity simultaneously and high stability is wanted
The politef interlayer asked is protected ion exchange membrane, its preparation method and uses this ion exchange membrane
Flow battery.
For achieving the above object, the present invention is by the following technical solutions:
A kind of politef interlayer protection ion exchange membrane, including sulphonated polymers ion exchange membrane
Basement membrane and be fitted in one side or the politef micropore of bilateral of described basement membrane as interlayer protection film
Film.
Preferably:
Described sulphonated polymers is perfluorinated sulfonic resin, sulfonated polyether ketone, sulfonated polyether-ether-ketone, sulphur
Change polyether ether ketone ketone, SPSF, sulfonated polyether sulfone, sulfonated polyether ether sulfone, sulfonated polyethylene sulfone,
Sulfonate polybenzimidazole, sulfonated polyimide, sulfonated polystyrene, sulfonated polytrifluorostyrene, sulphur
Change poly-(4-phenoxy benzonitrile acyl group-1,4-Asia benzene), sulfonation poly, sulfonated poly (phenylene oxide), sulfonated polyphenyl
One or two or more kinds in thioether.
The ion exchange capacity of described sulphonated polymers is 0.1～5mmol g-1。
The porosity of described microporous teflon membran is 1%～99%, and pore-size distribution is 5nm～50
μm, the thickness of described microporous teflon membran is 5 μm～1000 μm.
The thickness of described sulphonated polymers ion exchange membrane is 5 μm～500 μm.
The preparation method of a kind of politef interlayer protection ion exchange membrane, comprises the following steps:
(1) above-mentioned sulphonated polymers is pressed mass volume ratio 0.1～0.5g mL-1Join organic molten
In agent, abundant ultrasonic disperse, magnetic agitation 0.5～make mixed solution in 48 hours at 20～100 DEG C；
(2) mixed solution step (1) prepared removes bubble and impurity, utilizes the tape casting, painting
Mixed solution is uniformly spread out film forming on substrate by slurry processes, successively 40～120 DEG C be dried 2～48 hours,
40～140 DEG C are vacuum dried 2～48 hours, and demoulding the most in deionized water prepares sulfonated
Ion exchange polymer film basement membrane；
(3) microporous teflon membran is placed in the sulphonated polymers ion prepared by step (2)
The one side of exchange membrane basement membrane or bilateral compress and fit.
Preferably:
Described substrate is silicon plate, glass plate, plastic plate, metallic plate, ceramic wafer.
Described organic solvent is DMF (DMF), N,N-dimethylacetamide
(DMAC), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), oxolane
(THF) one or two or more kinds in.
The thickness of described microporous teflon membran is 5 μm～1000 μm.
The thickness of described sulphonated polymers ion exchange membrane is 5 μm～500 μm.
A kind of flow battery, has described politef interlayer protection ion exchange membrane.
Described flow battery can be all-vanadium flow battery, zinc/bromine flow battery, ferrum/chrome liquor galvanic battery,
Sodium polysulfide/bromine redox flow cell, vanadium/bromine flow battery, zinc/cerium flow battery, ferrum/vanadium flow battery or
Vanadium/air redox flow battery.
The Advantageous Effects of the present invention:
The present invention is by using poly-four in the one side of sulphonated polymers ion exchange membrane basement membrane or bilateral
Fluoride microporous film is protected, by the chemical stability sour high, resistance to of microporous teflon membran
The erosion property characteristic such as strong, intensity is high, even aperture distribution, significantly improve ion exchange membrane stability and
Ion selectivity, makes ion exchange membrane meet both sides requirement simultaneously.By sulphonated polymers-poly-four
Fluorothene interlayer protection ion exchange membrane is applied in flow battery particularly all-vanadium flow battery, permissible
Obtain more stable battery performance and longer battery cycle life.
Lower cost for material, preparation process used by the present invention are simple, operating procedure is easy, easily real
Existing large area, large-scale production, be conducive to promoting the industry of flow battery especially all-vanadium flow battery
Change and large-scale development.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b is the signal of the sulphonated polymers in embodiment 1-politef interlayer film
Figure.
Fig. 2 is with embodiment 1～7 and the battery performance ratio of all-vanadium flow battery that assembles of comparative example 1～4
Relatively scheme.
Fig. 3 is the all-vanadium flow electricity assembled with embodiment 1,2,3,4,7 and comparative example 1,3,4
The charging capacity conservation rate in pond-charge and discharge cycles number of times figure.
Fig. 4 is the current efficiency-discharge and recharge of the all-vanadium flow battery assembled with embodiment 1 and comparative example 1
Cycle-index figure.
Fig. 5 is the current efficiency-discharge and recharge of the all-vanadium flow battery assembled with embodiment 6 and comparative example 2
Cycle-index figure.
Fig. 6 be with embodiment 8 assemble all-vanadium flow battery circulation 10000 circle current efficiency-
Charge and discharge cycles number of times figure.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated.State under it is emphasized that
Bright that be merely exemplary rather than in order to limit the scope of the present invention and application thereof.
Embodiment 1
(1) it is 1.80mmol g by 1.5g ion exchange capacity-1, sulfonation time is 3h, sulfonation degree
Be 0.61 sulfonated polyether-ether-ketone (SPEEK) to join the DMF of 10mL molten
In agent (DMF), at 25 DEG C, abundant ultrasonic disperse, magnetic agitation make SPEEK in 24 hours
Homogeneous solution.
(2) homogeneous solution of SPEEK step (1) prepared removes bubble and impurity, at water
Utilize the tape casting film forming on flat cleaned glass plate, successively 60 DEG C be dried 12 hours, 100 DEG C true
Empty dry 12 hours, demoulding the most in deionized water, sulfonated polyether-ether-ketone ion exchange membrane can be prepared
Basement membrane.In the present embodiment, the ion exchange membrane basement membrane thickness obtained is 70 μm.
(3) being 30 μm by required thickness, pore size is the politef of 0.45 μm
(PTFE) microporous membrane is cut into required size, respectively puts a politef in SPEEK film 1 both sides
Microporous membrane 2, compresses laminating, the P of gained30(0.45)-S3-P30(0.45) the concrete preparation process of interlayer film
As illustrated in figs. ia and ib.
Utilize P30(0.45)-S3-P30(0.45) interlayer film assembles the monocell of all-vanadium flow battery, and electrode is
Activated Graphite felt, end plate is graphite cake, and the effective area of film is 25cm2, both positive and negative polarity electrolyte volume
It is 50mL, wherein vanadium ion concentration 2mol L-1, sulfuric acid concentration 2mol L-1.Charge-discharge test
In, battery charging and discharging electric current density is 80mA cm-2, the current efficiency of monocell is 98.7%,
Voltage efficiency is 85.0%, energy efficiency be 83.9%(as shown in Figure 2).Cycle charge discharge electric life is real
In testing, battery charging and discharging electric current density is 80mA cm-2, current efficiency is sufficiently stable and battery fills
Capacitance fall-off is slow, and after 620 circle circulations complete, charging capacity retention rate is 60%(such as Fig. 3
Shown in), in 1000 circle circulations, current efficiency is always maintained at stable, the most undamped (such as Fig. 4
Shown in).
At P30(0.45)-S3-P30(0.45) during this title is write a Chinese character in simplified form, P30(0.45) aperture 0.45 μm is represented,
The PTFE microporous membrane of thickness 30 μm, S3 represents that the sulfonation time of SPEEK is 3h, other interlayers
The title of film is write a Chinese character in simplified form and in like manner can be obtained；Further, representing positive pole protection on the left of basement membrane, right side represents negative
Pole is protected, and "None" represents unprotected, and N represents Nafion117 film.
Embodiment 2
The same embodiment of preparation method of the sulfonated polyether-ether-ketone of the present embodiment 2-politef interlayer film
1, the thickness of the polytetrafluoroethylene (PTFE) thin film of employing is 60 μm, and pore size is 0.45 μm,
Prepare P60(0.45)-S3-P60(0.45) interlayer film.This interlayer film assembles the monocell of all-vanadium flow battery,
Other assembling conditions and test condition are with embodiment 1.The current efficiency of monocell is 98.5%, voltage
Efficiency is 85.3%, energy efficiency be 84.1%(as shown in Figure 2).In cycle charge discharge electrical endurance,
Battery charging and discharging electric current density is 80mA cm-2, current efficiency is sufficiently stable and battery charge capacity
Decay slowly, after 605 circle circulations complete, charging capacity conservation rate be 60%(as shown in Figure 3).
Embodiment 3
The same embodiment of preparation method of the sulfonated polyether-ether-ketone of the present embodiment 3-politef interlayer film
1, the thickness of the polytetrafluoroethylene (PTFE) thin film of employing is 15 μm, and pore size is 0.45 μm,
Prepare P15(0.45)-S3-P15(0.45) interlayer film.This interlayer film assembles the monocell of all-vanadium flow battery,
Other assembling conditions and test condition are with embodiment 1.The current efficiency of monocell is 98.6%, voltage
Efficiency is 85.4%, energy efficiency be 84.2%(as shown in Figure 2).In cycle charge discharge electrical endurance,
Battery charging and discharging electric current density is 80mA cm-2, current efficiency is sufficiently stable and battery charge capacity
Decay slowly, after 478 circle circulations complete, charging capacity conservation rate be 60%(as shown in Figure 3).
Embodiment 4
The same embodiment of preparation method of the sulfonated polyether-ether-ketone of the present embodiment 4-politef interlayer film
1, the thickness of the polytetrafluoroethylene (PTFE) thin film of employing is 30 μm, and pore size is 0.45 μm,
Only add PTFE microporous membrane to protect in sulfonated polyether-ether-ketone ion exchange membrane side, prepare respectively
Film P30(0.45)-S3-is without (the most only positive pole protection) with without-S3-P30(0.45) (the most only negative pole protection).This
Two kinds of films assemble the monocell of all-vanadium flow battery, and other assembling conditions and test condition are with embodiment 1.
Film P30 (0.45)-S3-without the current efficiency of monocell be 98.7%, voltage efficiency is 85.4%, energy
Efficiency be 84.4%(as shown in Figure 2).Film is without-S3-P30(0.45) current efficiency of monocell is
98.5%, voltage efficiency is 85.3%, energy efficiency be 84.4%(as shown in Figure 2).Fill in circulation
In discharge life experiment, battery charging and discharging electric current density is 80mA cm-2, two kinds of unilateral protecting film
Battery charge capacity decay more slow, positive pole protecting film P30(0.45)-S3-is without in 309 circle circulations
After completing, charging capacity conservation rate be 60%(as shown in Figure 3).Negative pole protecting film is without-S3-P30(0.45)
After at 231 circles, circulations complete, charging capacity conservation rate be 60%(as shown in Figure 3).
Embodiment 5
The same embodiment of preparation method of the sulfonated polyether-ether-ketone of the present embodiment 5-politef interlayer film
1, the thickness of the polytetrafluoroethylene (PTFE) thin film of employing is 30 μm, and pore size is 0.25 μm,
Prepare P30(0.25)-S3-P30(0.25) interlayer film.This interlayer film assembles the monocell of all-vanadium flow battery,
In addition to not being circulated discharge and recharge life experiment, other assembling conditions and test condition are with embodiment 1.
P30(0.25)-S3-P30(0.25) current efficiency of the monocell that interlayer film assembles is 99.2%, voltage efficiency
Being 84.9%, energy efficiency is 84.2%.(as shown in Figure 2).
Embodiment 6
The same embodiment of preparation method of the sulfonated polyether-ether-ketone of the present embodiment 6-politef interlayer film
1, the ion exchange capacity of the sulfonated polyether-ether-ketone of employing is 2.10mmol g-1, sulfonation time is 4h,
Sulfonation degree is 0.75, and thickness is 70 μm, and the thickness of the polytetrafluoroethylene (PTFE) thin film of employing is
30 μm, pore size is 0.45 μm, prepares P30(0.45)-S4-P30(0.45) interlayer film.This interlayer film
Assembling the monocell of all-vanadium flow battery, other assembling conditions and test condition are with embodiment 1.
P30(0.45)-S4-P30(0.45) current efficiency of the monocell that interlayer film assembles is 94.8%, voltage efficiency
Being 87.5%, energy efficiency is 83.0%.In cycle charge discharge electrical endurance, battery charging and discharging electric current
Density is 80mA cm-2, in 1000 circle circulations, current efficiency keeps stable, the most undamped (as
Shown in Fig. 5).
Embodiment 7
The preparation method of the perfluorinated sulfonic acid polymer of the present embodiment 7-politef interlayer film is with implementing
Example 1, the perfluorinated sulfonic acid ion exchange membrane of this interlayer film is the Nafion117(ion exchange of E.I.Du Pont Company
Capacity is 0.85mmol g-1), thickness is 220 μm, uses preparation method same as in Example 1
Prepare the interlayer film P of the present embodiment30(0.45)-N-P30(0.45).The thickness of this interlayer film is 280 μm.
The monocell of all-vanadium flow battery, other assembling conditions and test condition is assembled with implementing with this interlayer film
Example 1.The current efficiency of monocell is 93.0%, and voltage efficiency is 85.9%, and energy efficiency is 80.1%
(as shown in Figure 2).In cycle charge discharge electrical endurance, battery charging and discharging electric current density is 80mA
cm-2, current efficiency is basicly stable, but battery charge capacity is decayed quickly, after 59 circle circulations complete,
Charging capacity conservation rate be 60%(as shown in Figure 3).
Embodiment 8
The preparation method of the sulfonated polyether-ether-ketone of the present embodiment 8-politef interlayer film is completely with real
Executing example 1, the thickness of the polytetrafluoroethylene (PTFE) thin film of employing is 30 μm, and pore size is 0.45
μm, prepares P30(0.45)-S3-P30(0.45) interlayer film.This interlayer film assembles the list of all-vanadium flow battery
Battery, other assembling conditions are with embodiment 1.It is real that this interlayer film carries out long period cycle charge discharge electric life
Testing, battery charging and discharging electric current density is 80mA cm-2, during full 1000 circle of every charge and discharge cycles, more
Change the fresh electrolyte of equivalent, keep test condition constant, then carry out next round 1000 and enclose discharge and recharge
Circulation, total test loop number of turns is 10000 circles.In the circulation of 10000 circles, the electricity of this interlayer film
Stream efficiency is sufficiently stable the most undamped, causes first circle current efficiency relatively except changing fresh electrolyte every time
Outside low, in other cyclic processes, current efficiency slightly fluctuates substantially between 98%～99%, illustrates this
The protective effect of microporous teflon membran has essence to the stability of sulfonated polyether-ether-ketone ion exchange membrane
Raising.
Comparative example 1
Comparative example 1 is sulfonated polyether-ether-ketone film (sulfonation time is 3h, and sulfonation degree is 0.61), preparation
Method and component ratio are prepared with the basement membrane in embodiment 1.The thickness of this sulfonated polyether-ether-ketone film is 70
μm.The monocell of all-vanadium flow battery, other assembling conditions and survey is assembled with this sulfonated polyether-ether-ketone film
Strip part is with embodiment 1.The coulombic efficiency of monocell is 98.5%, and voltage efficiency is 85.6%, energy
Efficiency be 84.3%(as shown in Figure 2).In cycle charge discharge electrical endurance, battery charging and discharging electric current is close
Degree is 80mA cm-2, current efficiency is sufficiently stable, but battery charge capacity decay is very fast, 124
Circle is after circulation completes, charging capacity conservation rate be 60%(as shown in Figure 3)；When the circulation number of turns reaches
During 156 circle, SPEEK film is damaged (as shown in Figure 4), illustrates that sulfonated polyether-ether-ketone film is at full vanadium liquid
Instability in galvanic battery application.The reason of film breakage has: peracidity, the corruption of high oxidative V electrolyte
Erosion effect, the diapirism of graphite fibre in graphite felt, the pressure stresses effect etc. of cell sealing pad.
From embodiment 1,2,3 and comparative example 1, by same apertures, poly-the four of different-thickness
Fluorothene (PTFE) microporous membrane carries out bilateral protection system to sulfonated polyether-ether-ketone film (SPEEK3h)
Standby P-S-P interlayer film, substantially without affecting the current efficiency of SPEEK ion exchange membrane, voltage efficiency,
Energy efficiency, but significantly greater amplitude extend the cycle life of SPEEK ion exchange membrane,
Improve the stability of SPEEK ion exchange membrane.
From embodiment 4 and comparative example 1, by polytetrafluoroethylene (PTFE) microporous membrane to sulfonation
Polyether-ether-ketone film (SPEEK3h) carries out unilateral protection preparation P-S-without film (positive pole protection) with without-S-P
Film (negative pole protection), substantially without affecting the current efficiency of SPEEK ion exchange membrane, to a certain degree
Extend the cycle life of SPEEK ion exchange membrane, improve the steady of SPEEK ion exchange membrane
Qualitative.Contrasted from embodiment 1 and embodiment 4, by same apertures, poly-the four of same thickness
Fluorothene (PTFE) microporous membrane carries out bilateral protection to sulfonated polyether-ether-ketone film (SPEEK), and ratio is only
The effect carrying out unilateral protection becomes apparent from, and prepared interlayer film cycle life is longer, and stability is more preferable.
Comparative example 2
Comparative example 2 is that (sulfonation time is 4h, and sulfonation degree is for the sulfonated polyether-ether-ketone film of highly sulfonated
0.75), preparation method and component ratio are prepared with the basement membrane in embodiment 1.This sulfonated polyether-ether-ketone film
Thickness be 70 μm.The monocell of all-vanadium flow battery is assembled with this sulfonated polyether-ether-ketone film, other
Assembling condition and test condition are with embodiment 1.The current efficiency of monocell is 94.6%, voltage efficiency
Be 87.8%, energy efficiency be 83.1%(as shown in Figure 2).In cycle charge discharge electrical endurance, electricity
Pond charging and discharging currents density is 80mA cm-2, current efficiency is relatively stable, when the circulation number of turns reaches
During 83 circle, SPEEK4h film is damaged (as shown in Figure 5).Contrasted by comparative example 1 and comparative example 2
Understand, under identical assembling condition and test condition, the sulfonated polyether-ether-ketone film circulation of highly sulfonated
Life-span is shorter, and stability is worse.Reason is: the sulfonation degree of sulfonated polyether-ether-ketone film is the highest, the easiest
Swelling, even crack, mechanical strength and stability are the poorest.
Comparative example 3
(1) it is 1.80mmol g by 1.5g ion exchange capacity-1, sulfonation time is 3h, sulfonation degree
Be 0.61 sulfonated polyether-ether-ketone (SPEEK) to join the DMF of 10mL molten
In agent (DMF), at 25 DEG C, abundant ultrasonic disperse, magnetic agitation make SPEEK in 24 hours
Homogeneous solution.
(2) homogeneous solution step (1) prepared removes bubble and impurity, at the clean base of level
On plate, fixed thickness is 30 μm, and aperture is the polytetrafluoroethylene (PTFE) microporous membrane of 0.45 μm,
Utilize the tape casting that homogeneous solution is uniformly spread out film forming in PTFE film, be dried 12 at 60 DEG C successively
Hour, 100 DEG C be vacuum dried 12 hours, demoulding the most in deionized water, sulfonated polyether can be prepared
Ether ketone filled polytetrafluoroethylene film S3@P30(0.45).In this comparative example 3, prepared ion exchange
Film thickness is 100 μm.
Utilize S3@P30(0.45) filling film assembles the monocell of all-vanadium flow battery, other assembling conditions
And test condition is with embodiment 1.The current efficiency of monocell is 98.9%, and voltage efficiency is 75.8%,
Energy efficiency be 75%(as shown in Figure 2).In cycle charge discharge electrical endurance, battery charging and discharging electricity
Current density is 80mA cm-2, after at 158 circles, circulations complete, charging capacity conservation rate be 60%(such as
Shown in Fig. 3).
By embodiment 1, comparative example 1,3 understands, sulfonated polyether-ether-ketone-politef interlayer film and
Sulfonated polyether-ether-ketone filled polytetrafluoroethylene film can improve the stability of sulfonated polyether-ether-ketone film, prolongs
Long sulfonated polyether-ether-ketone film service life in all-vanadium flow battery.Contrast understands further, sulfonation
The protective effect of polyether-ether-ketone filled polytetrafluoroethylene film is less obvious, and prepared filling film is in circulation
In performance test, charging capacity decay is the most very fast.Reason is the aperture phase of microporous teflon membran
To less, the homogeneous solution of sulfonated polyether-ether-ketone is difficult to be uniformly impregnated with microporous teflon membran
In micropore, causing prepared filling ion exchange membrane uneven, therefore its protective effect is limited.
Comparative example 4
Comparative example 4 is Nafion 117 film of E.I.Du Pont Company, and thickness is 220 μm.Exchange with this ion
Film assembles the monocell of all-vanadium flow battery, and other assembling conditions and test condition are with embodiment 1.Single
The current efficiency of battery is 92.9%, and voltage efficiency is 85.7%, and energy efficiency is 79.6%(such as Fig. 2
Shown in).In cycle charge discharge electrical endurance, battery charging and discharging electric current density is 80mA cm-2, electricity
Pond charging capacity decay is very fast, and after the circulation of 45 circles, charging capacity conservation rate is 60%(such as Fig. 3
Shown in).
From embodiment 7 and comparative example 4, by polytetrafluoroethylene (PTFE) microporous membrane to Nafion
117 films carry out bilateral protection and prepare interlayer film P30(0.45)-N-P30(0.45), substantially without affecting Nafion
The current efficiency of 117 films, voltage efficiency, energy efficiency, also will not extend Nafion 117 film simultaneously
Cycle life, illustrate that this Nafion 117 film is the most stable, the therefore work of PTFE protective layer
With the faintest.
From embodiment 1～8, the monocell discharge and recharge data of the all-vanadium flow battery of comparative example 1～4,
The battery performance that microporous teflon membran protective layer not only will not reduce ion exchange membrane basement membrane is (the most former
This higher current efficiency, voltage efficiency, energy efficiency will not reduce), simultaneously can also be greatly
Extend the cycle life of ion exchange membrane basement membrane, be greatly improved interlayer film in all-vanadium flow battery is applied
Stability.
In sum, politef is used by or preferably bilateral unilateral at sulfonated ion exchange membrane
Microporous membrane is protected, and can meet high stability and the macroion selectivity of ion exchange membrane simultaneously, tool
Have broad application prospects.By sulphonated polymers-politef interlayer protection ion exchange membrane application
In flow battery particularly all-vanadium flow battery, more stable battery performance can be obtained, and longer
Battery cycle life.
Above content is that to combine concrete preferred implementation made for the present invention the most specifically
Bright, it is impossible to assert the present invention be embodied as be confined to these explanations.For technology belonging to the present invention
For the those of ordinary skill in field, without departing from the inventive concept of the premise, it is also possible to if making
Dry simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (7)
1. a politef interlayer protection ion exchange membrane, exchanges including sulphonated polymers ion
Film basement membrane, it is characterised in that also include interlayer protection film, described sulphonated polymers ion exchange membrane
Basement membrane is well prepared in advance, and described interlayer protection film is by the politef micropore of forming in advance
Film is directly against the one side or double being combined in the described sulphonated polymers ion exchange membrane basement membrane prepared
Side, the thickness of described microporous teflon membran is 5 μm～1000 μm, and porosity is 1%～99%,
Pore-size distribution is 5nm～50 μm, and the thickness of described sulphonated polymers ion exchange membrane is 5 μm
～500 μm.
2. politef interlayer protection ion exchange membrane as claimed in claim 1, its feature exists
In, described sulphonated polymers is perfluorinated sulfonic resin, sulfonated polyether ketone, sulfonated polyether-ether-ketone, sulphur
Change polyether ether ketone ketone, SPSF, sulfonated polyether sulfone, sulfonated polyether ether sulfone, sulfonated polyethylene sulfone,
Sulfonate polybenzimidazole, sulfonated polyimide, sulfonated polystyrene, sulfonated polytrifluorostyrene, sulphur
Change poly-(4-phenoxy benzonitrile acyl group-1,4-Asia benzene), sulfonation poly, sulfonated poly (phenylene oxide), sulfonated polyphenyl
One or two or more kinds in thioether.
3. politef interlayer protection ion exchange membrane as claimed in claim 1, its feature exists
In, the ion exchange capacity of described sulphonated polymers is 0.1～5mmol g-1。
4. the politef interlayer protection ion that a kind is prepared as described in any one of claims 1 to 3
The preparation method of exchange membrane, it is characterised in that comprise the following steps:
(1) sulphonated polymers is pressed mass volume ratio 0.1～0.5g mL-1Join in organic solvent,
Abundant ultrasonic disperse, magnetic agitation 0.5～make mixed solution in 48 hours at 20～100 DEG C；
(2) mixed solution step (1) prepared removes bubble and impurity, utilizes the tape casting, painting
Mixed solution is uniformly spread out film forming on substrate by slurry processes, successively 40～120 DEG C be dried 2～48 hours,
40～140 DEG C are vacuum dried 2～48 hours, and demoulding the most in deionized water prepares sulfonated
Ion exchange polymer film basement membrane；
(3) microporous teflon membran of forming in advance is directly placed in step (2) prepared
The one side of sulphonated polymers ion exchange membrane basement membrane or bilateral compress and fit.
5. the preparation method of politef interlayer protection ion exchange membrane as claimed in claim 4,
It is characterized in that, described organic solvent is DMF (DMF), N, N-dimethyl
Acetamide (DMAC), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), four
One or two or more kinds in hydrogen furan (THF).
6. a flow battery, it is characterised in that have as described in any one of claims 1 to 3
Politef interlayer protection ion exchange membrane.
7. flow battery as claimed in claim 6, it is characterised in that described flow battery is full vanadium
Flow battery, zinc/bromine flow battery, ferrum/chrome liquor galvanic battery, sodium polysulfide/bromine redox flow cell, vanadium/bromine
Flow battery, zinc/cerium flow battery, ferrum/vanadium flow battery or vanadium/air redox flow battery.
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| CN103985890B (en) * | 2014-05-21 | 2017-02-01 | 清华大学深圳研究生院 | Polyolefin double-layer protective ion exchange membrane, preparation method thereof and redox flow battery |
| IT201800004325A1 (en) * | 2018-04-09 | 2019-10-09 | Flow battery | |
| CN108905645A (en) * | 2018-08-29 | 2018-11-30 | 深圳合核环境科技有限公司 | A kind of amberplex and preparation method thereof with polymer protective film |
| CN109585872A (en) * | 2018-10-24 | 2019-04-05 | 长沙理工大学 | A kind of preparation method applied to zinc-iron flow battery SPEEK diaphragm |
| CN109687007A (en) * | 2018-11-26 | 2019-04-26 | 电子科技大学 | A kind of organic quinones flow battery and its construction method |
| CN110783591B (en) * | 2019-10-25 | 2022-08-19 | 中国科学院山西煤炭化学研究所 | Preparation method and application of ion exchange membrane |
| CN112825359B (en) * | 2019-11-21 | 2022-07-26 | 重庆神华薄膜太阳能科技有限公司 | Composite ion exchange membrane and preparation method and application thereof |
| CN112159988A (en) * | 2020-08-21 | 2021-01-01 | 广东臻鼎环境科技有限公司 | Polytetrafluoroethylene interlayer protective ion exchange membrane, preparation method thereof and application thereof in electrolysis field |
| CN117069988A (en) * | 2023-08-10 | 2023-11-17 | 山西国润储能科技有限公司 | Preparation method of sulfonated polyether-ether-ketone-based composite ionic membrane, product and application thereof |
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