CN106532090A - Xuan-paper-enhanced non-fluorinated ionic membrane for flow battery, and preparation method for Xuan-paper-enhanced non-fluorinated ionic membrane - Google Patents
Xuan-paper-enhanced non-fluorinated ionic membrane for flow battery, and preparation method for Xuan-paper-enhanced non-fluorinated ionic membrane Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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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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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
The invention provides a Xuan-paper-enhanced non-fluorinated ionic membrane for a flow battery, and a preparation method for the Xuan-paper-enhanced non-fluorinated ionic membrane. The Xuan-paper-enhanced non-fluorinated ionic membrane for the flow battery comprises Xuan paper used as a framework-enhanced base material, and a sulfonic acid type non-fluorinated polymer filled in the Xuan paper base material; the preparation method for the Xuan-paper-enhanced non-fluorinated ionic membrane for the flow battery comprises the steps of dissolving the sulfonic acid type non-fluorinated polymer into an organic solvent based on mass volume ratio of 0.05-0.5g/mL, and stirring to prepare a sulfonic acid type non-fluorinated polymer solution; and then coating the Xuan paper with the solution, standing for 0.1-5h, drying and de-moulding to prepare the Xuan-paper-enhanced non-fluorinated ionic membrane for the flow battery. The Xuan-paper-enhanced non-fluorinated ionic membrane for the flow battery by adopting the technical scheme is low in cost, high in mechanical property and chemical stability, and capable of bearing long-term electrolyte washing and improving proton selectivity of the membrane, thereby enabling the flow battery to be higher in efficiency and longer in service life.
Description
Technical field
The present invention relates to flow battery, more particularly to a kind of flow battery rice paper enhancing non-fluorine ionic membrane and its preparation side
Method.
Background technology
Flow battery, particularly all-vanadium flow battery, with easy large-scale, overlength cycle life, addressing freely and
The outstanding advantages such as operation safety, become extensive energy storage technology at present with fastest developing speed, it is contemplated that will be in peak load regulation network and promote can
The aspects such as utilization of regenerative energy are obtained extensively to be applied.
Ionic membrane（Barrier film）It is the core component of flow battery, which is selected while positive and negative electrode electrolyte and electronics is isolated
Selecting property conducts ion.Ionic membrane directly determines the cost and efficiency of flow battery, so which should have following characteristic：Low cost
It is honest and clean, have good stability and ion selectivity is high.Ionic membrane needs are with low cost to be because that flow battery is mainly used in extensive storage
Can, so reducing the cost of film, the competitiveness of flow battery can be lifted.Ionic membrane needs good stability and is because liquid
Electrolyte in galvanic battery is constantly washed away to film, and electrolyte is often highly acid strongly corrosion liquid, in order to obtain
Permanent service life, it is necessary to strengthen the both macro and micro stability of film.Ionic membrane need higher ion selectivity be because
For flow battery is in charge and discharge process due to the effect of electric field, the vanadium ion in other cations such as all-vanadium flow battery
Ionic membrane just can be permeated, cause battery efficiency to reduce and battery capacity decay, so ionic membrane should selectively conduct matter
Transmission that is sub and intercepting other ions as far as possible.Flow battery is mainly using the perfluorosulfonic acid type with superior chemical stability at present
The Nafion membrane of film ionic membrane, such as E.I.Du Pont Company.But the expensive price of Nafion membrane and serious vanadium ion infiltration are limited
Its scale application in flow battery.
Various non-fluorine ionic membranes with sulfonated polyether-ether-ketone SPEEK as representative, it is not only with low cost, it is easy to scale metaplasia
Produce, and have the conduction of good proton selective, thus be accordingly used in when flow battery is particularly all-vanadium flow battery and be obtained in that
Very high coulombic efficiency and energy efficiency.But flow battery is different from fuel cell, especially under highly acid electrolyte environment
All-vanadium flow battery in, the strong oxidizing property of positive pole pentavalent vanadium ion is very big choosing to the structural stability of non-fluorine ionic membrane
War.Therefore, the poor shortcoming of its chemical stability and mechanical property also governs reality of the non-fluorine ionic membrane in flow battery
Using particularly all-vanadium flow battery.If the chemical stability and mechanical property of non-fluorine ionic membrane can be effectively improved, can be big
Sizable application is in flow battery particularly all-vanadium flow battery.At present, have and non-fluorine ionic membrane is changed using certain methods
Property, which mainly improves proton conduction efficiency, but its mechanical performance, chemical stability improve limited, therefore is only adapted to
The application of fuel cell, and the requirement of the more stringent flow battery of service condition cannot be met.
The content of the invention
For above technical problem, the invention discloses a kind of flow battery strengthens non-fluorine ionic membrane and its preparation with rice paper
Method, not only its ionic conduction efficiency be improved, also with more preferable mechanical performance, good stability is with low cost, Neng Gouchang
Washing away for time tolerance electrolyte, while also reducing the infiltration of other ions, improves the proton selective of film, so that liquid stream is electric
Pond has high efficiency and long-life.
In this regard, the technical scheme is that：
A kind of flow battery with rice paper strengthen non-fluorine ionic membrane, it include as skeleton enhancing base materials rice paper and be filled in institute
State the sulfonic acid type non-fluorinated polymer in rice paper base material.
This technical scheme, using the rice paper with three-dimensional netted loose structure as enhancing base materials（Skeleton）, wherein fiber
Diameter can preferably improve the mechanical property of film in micron order, enable enhancing film to tolerate washing away for electrolyte for a long time, together
When also reduce the infiltration of other ions, improve the proton selective of film, so that flow battery has high efficiency and long-life.A surname
The hydroxyl of the cellulose surface in paper forms hydrogen bond with the sulfonic group of sulfonic acid type non-fluorinated polymer, improves ionic conductance；Simultaneously
The stability of film is increased substantially, make use of the skeletal support of fiber in rice paper to cause flow battery rice paper to strengthen non-fluorine ion
Film has good mechanical strength；In addition, and sulfonic acid type non-fluorinated polymer can be reduced because itself occupying a part of volume
Consumption reducing the cost of film, it is only necessary to using less sulfonic acid type non-fluorinated polymer be obtained the more preferable non-fluorine of performance from
Sub- film.That is, using technical scheme, it is provided simultaneously with that with low cost, have good stability the advantage high with ion selectivity.
As a further improvement on the present invention, the flow battery of volume per cubic centimeter is strengthened in non-fluorine ionic membrane with rice paper
Quality containing sulfonic acid type non-fluorinated polymer is 0.1 ~ 0.5 g.
As a further improvement on the present invention, the flow battery of volume per cubic centimeter is strengthened in non-fluorine ionic membrane with rice paper
Quality containing sulfonic acid type non-fluorinated polymer is 0.25 ~ 0.35 g.
As a further improvement on the present invention, the porosity of the rice paper is 10% ~ 50%；The thickness of the rice paper be 10 ~
500 μm。
As a further improvement on the present invention, the sulfonic acid type non-fluorinated polymer includes sulfonated polyether-ether-ketone, sulfonation polyamides
One or more mixing in imines, sulfonate polybenzimidazole, SPSF, sulfonated polyether sulfone, sulfonated polystyrene
Thing.
As a further improvement on the present invention, the ion exchange capacity of the sulfonic acid type non-fluorinated polymer is 0.1 ~ 10
mmol/g 。
As a further improvement on the present invention, flow battery rice paper strengthens non-fluorine ionic membrane using following steps system
It is standby to obtain：
Step S1：The sulfonic acid type non-fluorinated polymer is dissolved in organic solvent by 0.05 ~ 0.5 g/mL of mass volume ratio, 20
At ~ 90 DEG C, 0.5 ~ 48 h of magnetic agitation makes sulfonic acid type non-fluorinated polymer solution；
Step S2：It is laid on rice paper smooth on substrate, sulfonic acid type non-fluorinated polymer solution prepared by step S1 is poured on into a surname
On paper, by sulfonic acid type non-fluorinated polymer solution in rice paper surface even spread, 0.1-5 h are stood, successively in 70 ~ 100 DEG C of dryings 1
~ 48 h, 100 ~ 150 DEG C of 1 ~ 48 h of vacuum drying, then demoulding, is obtained flow battery rice paper enhancing non-fluorine ionic membrane.
As a further improvement on the present invention, the organic solvent be DMF, N, N- dimethylacetamides
The mixture of one or two or more kinds in amine, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetrahydrofuran；The substrate is glass
Glass plate, plastic plate, ceramic wafer.
As a further improvement on the present invention, the flow battery is all-vanadium flow battery, full iron liquid galvanic battery, full copper liquid
Galvanic battery, full stress-strain flow battery, zinc/bromine flow battery, iron/chrome liquor galvanic battery, sodium polysulfide/bromine redox flow cell, vanadium/bromine liquid
Galvanic battery, zinc/cerium flow battery, iron/vanadium flow battery, vanadium/air or vanadium/hydrogen flow battery.
The invention discloses a kind of flow battery as above strengthens the preparation method of non-fluorine ionic membrane with rice paper, including
Following steps：
Step S1：The sulfonic acid type non-fluorinated polymer is dissolved in organic solvent by 0.05 ~ 0.5 g/mL of mass volume ratio, 20
At ~ 90 DEG C, 0.5 ~ 48 h of magnetic agitation makes sulfonic acid type non-fluorinated polymer solution；
Step S2：It is laid on rice paper smooth on substrate, sulfonic acid type non-fluorinated polymer solution prepared by step S1 is poured on into a surname
On paper, by sulfonic acid type non-fluorinated polymer solution in rice paper surface even spread, 0.1-5 h are stood, successively in 70 ~ 100 DEG C of dryings 1
~ 48 h, 100 ~ 150 DEG C of 1 ~ 48 h of vacuum drying, then demoulding, is obtained flow battery rice paper enhancing non-fluorine ionic membrane；
Wherein, the porosity of the rice paper is 10% ~ 50%；The thickness of the rice paper is 10 ~ 500 μm.
Preferably, the flow battery of volume per cubic centimeter rice paper strengthens poly- containing sulfonic acid type non-fluorine in non-fluorine ionic membrane
The quality of compound is 0.25 ~ 0.35 g.
Preferably, the organic solvent is DMF, DMA, N- crassitudes
The mixture of one or two or more kinds in ketone, dimethyl sulfoxide (DMSO), tetrahydrofuran.
Preferably, the substrate is glass plate, plastic plate, ceramic wafer.
Preferably, the sulfonic acid type non-fluorinated polymer includes sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonated polyphenyl miaow
One or more mixture in azoles, SPSF, sulfonated polyether sulfone, sulfonated polystyrene.
Preferably, the ion exchange capacity of the sulfonic acid type non-fluorinated polymer is 0.1 ~ 10 mmol/g.
Preferably, the flow battery is all-vanadium flow battery, full iron liquid galvanic battery, full copper flow battery, full stress-strain liquid
Galvanic battery, zinc/bromine flow battery, iron/chrome liquor galvanic battery, sodium polysulfide/bromine redox flow cell, vanadium/bromine flow battery, zinc/cerium liquid
Galvanic battery, iron/vanadium flow battery, vanadium/air or vanadium/hydrogen flow battery.
Compared with prior art, beneficial effects of the present invention are：
First, technical scheme by rice paper fill sulfonic acid type non-fluorinated polymer, be obtained rice paper strengthen non-fluorine from
Sub- film, the sulfonic group of hydroxyl and sulfonic acid type non-fluorinated polymer that rice paper both can pass through its cellulose surface form hydrogen bond and improve ion
Conductivity, while the stability of film is increased substantially, in addition, and sulfonic acid type can be reduced because itself occupying a part of volume
The consumption of non-fluorinated polymer is reducing the cost of film, it is only necessary to just can obtain performance more using less sulfonic acid type non-fluorinated polymer
Good non-fluorine ionic membrane.Rice paper enhancing non-fluorine ionic membrane is applied to flow battery to be particularly in all-vanadium flow battery, can be obtained
Obtain lower manufacturing cost and more stable battery performance.
Second, the lower cost for material, preparation process is simple, easily realization large-scale production used by the present invention is conducive to
Promote the commercialized development of flow battery especially all-vanadium flow battery.
Description of the drawings
Fig. 1 is the Performance comparision figure of the all-vanadium flow battery that embodiment 1 and comparative example 1 ~ 2 are assembled.
Fig. 2 is the cycle life figure of the all-vanadium flow battery that embodiment 1 and comparative example 1 are assembled.
Specific embodiment
Below in conjunction with the accompanying drawings, the preferably embodiment of the present invention is described in further detail.
Embodiment 1
A kind of flow battery strengthens non-fluorine ionic membrane with rice paper, is prepared using following steps：
（1）The sulfonated polyether-ether-ketone that 1.0 g ion exchange capacities are 2.0 mmol/g is added to into the N of 10 mL, N- dimethyl
In formamide solvent, at 25 DEG C, 24 h of magnetic agitation makes the homogeneous solution of sulfonated polyether-ether-ketone.
（2）It is laid on length is 30 cm, width is 10 cm, thickness is 100 μm rice paper smooth in horizontal glass plate.
（3）By step（1）The sulfonated polyether-ether-ketone solution of preparation is poured over step（2）Rice paper on, using scraper by sulphur
Change polyether-ether-ketone solution uniformly to strike off on rice paper surface, stand 0.5 h, successively in 70 DEG C of 12 h of drying, 120 DEG C of vacuum drying
12 h, then demoulding in deionized water, rice paper can be obtained strengthens sulfonated polyether-ether-ketone film.In the present embodiment, a surname for being obtained
It is 300 cm that paper strengthens the area of sulfonated polyether-ether-ketone film2, thickness be 110 μm.
Strengthen sulfonated polyether-ether-ketone film assembling all-vanadium flow battery using the rice paper, electrode is Activated Graphite felt, end plate is
Graphite cake, the effective area of film is 25 cm2, both positive and negative polarity electrolyte volume is 50 mL, wherein 2 mol of vanadium ion concentration/L,
2 mol/L of sulfuric acid concentration.The all-vanadium flow battery being assembled into is carried out into performance test, charging and discharging currents density is 80 mA/
cm2, the coulombic efficiency of battery is 98.5%, and energy efficiency is 84.3%, as shown in Figure 1.In life experiment, charging and discharging currents are close
Degree is 120 mA/cm2, in the continuous charge and discharge cycles of 5000 circles, coulombic efficiency is basically stable at 99.0%, as shown in Fig. 2
Illustrate that the rice paper strengthens sulfonated polyether-ether-ketone film and has excellent circulating battery stability.
Comparative example 1
Comparative example 1 is sulfonated polyether-ether-ketone film, and preparation method is with embodiment 1, but does not contain rice paper enhancing base materials.The sulfonated polyether ether
The area of ketone film is 150 cm2, thickness be 100 μm.All-vanadium flow battery is assembled with this sulfonated polyether-ether-ketone film, other assemblings
Condition and test condition are with embodiment 1.In performance test, the coulombic efficiency of battery is 97.6%, and energy efficiency is 84.6%, such as
Shown in Fig. 1.In life experiment, the Initial Coulombic Efficiencies of battery are 98.3%, when the circulation number of turns reaches 160 circle, coulombic efficiency
Drastically reduce, as shown in Fig. 2 the less stable of explanation sulfonated polyether-ether-ketone film.
From embodiment 1 and comparative example 1, rice paper strengthens sulfonated polyether-ether-ketone film and not only maintains sulfonated polyether-ether-ketone film
High battery efficiency, and greatly extend the cycle life of sulfonated polyether-ether-ketone film, improve stability test；In addition,
Because strengthening the rice paper enhancing base materials in sulfonated polyether-ether-ketone film in rice paper has occupied certain volume in itself, put into identical
Sulfonated polyether-ether-ketone raw material, for 2 times of sulfonated polyether-ether-ketone film, i.e., obtained rice paper strengthen the area of sulfonated polyether-ether-ketone film
The amount of the sulfonated polyether-ether-ketone contained in the film of volume per cubic centimeter in embodiment 1 is only the half of comparative example 1, but still
High battery efficiency is so realized, and cycle life is extended, in the continuous charge and discharge cycles of 5000 circles, coulombic efficiency is remained to surely
99.0% is scheduled on, with good stability.
It is extremely cheap in view of the cost of rice paper, this also significantly reduce rice paper strengthen sulfonated polyether-ether-ketone film into
This.
Comparative example 2
Nafion 115 film of the comparative example 2 for E.I.Du Pont Company, thickness are 160 μm.All-vanadium flow battery is assembled with this film, other
Assembling condition and test condition are with embodiment 1.In performance test, the coulombic efficiency of battery is 91.8%, and energy efficiency is
79.6%, as shown in Figure 1.
Contrasted from embodiment 1 and comparative example 1,2, rice paper strengthens sulfonated polyether-ether-ketone film and simple sulfonated polyether ether
Ketone film all has higher battery efficiency than 115 films of commercial Nafion, but rice paper strengthens sulfonated polyether-ether-ketone film than simple
Sulfonated polyether-ether-ketone film maintain ionic conduction it is efficient while, with higher battery efficiency and stability, and low cost,
Life-span length.
Comparative example 3
Comparative example 3 is sulfonated polyether-ether-ketone/cellulose composite membrane, and its preparation method is as follows：
（1）0.2 g celluloses are added in the DMF solvent of 10 mL, 1 h of ultrasonic disperse, obtain uniform
Dispersion liquid, is subsequently adding the sulfonated polyether-ether-ketone that 1.0 g ion exchange capacities are 2.0 mmol/g, the magnetic agitation at 25 DEG C
24 h make the homogeneous mixture solotion of sulfonated polyether-ether-ketone/cellulose.
（2）By step（1）The homogeneous mixture solotion of the sulfonated polyether-ether-ketone/cellulose of preparation is poured over horizontal glass plate
On, solution is uniformly struck off on a glass using scraper, successively in 70 DEG C of 12 h of drying, 120 DEG C of 12 h of vacuum drying, then
Demoulding, can be obtained sulfonated polyether-ether-ketone/cellulose composite membrane in deionized water.Sulfonated polyether-ether-ketone/the cellulose composite membrane
Area be 150 cm2, thickness be 110 μm.
With this sulfonated polyether-ether-ketone/cellulose composite membrane assembling all-vanadium flow battery, other assembling conditions and test condition
With embodiment 1.In performance test, the coulombic efficiency of battery is 97.8%, and energy efficiency is 84.4%.In life experiment, electricity
The Initial Coulombic Efficiencies in pond are 98.0%, and when the circulation number of turns reaches 190 circle, coulombic efficiency declines suddenly, illustrates sulfonated polyether ether
The less stable of ketone/cellulose composite membrane.
From embodiment 1 and comparative example 1,3, the method by mixing cellulose in sulfonated polyether-ether-ketone, to improving
Stability action of the sulfonated polyether-ether-ketone film in flow battery is limited, and fills sulphur with the rice paper of three-dimensional reticular fiber composition
Change the ionic membrane that polyether-ether-ketone can then obtain super stable.
Comparative example 4
Comparative example 4 is the enhanced sulfonated polyether-ether-ketone film of filter paper, and preparation method simply changed rice paper into diameter with embodiment 1
The filter paper of 11 cm, 210 μm of thickness, the consumption of sulfonated polyether-ether-ketone is 0.7 g, using preparation method same as Example 1
Filter paper to prepare the present embodiment strengthens sulfonated polyether-ether-ketone film.It is 220 μ that the filter paper strengthens the thickness of sulfonated polyether-ether-ketone film
m.Sulfonated polyether-ether-ketone film assembling all-vanadium flow battery is strengthened with this filter paper, other assembling conditions and test condition are with embodiment 1.
In performance test, the coulombic efficiency of battery is 98.1%, and energy efficiency is 80.2%.It is in life experiment, continuous in 1000 circles
In charge and discharge cycles, coulombic efficiency is basically stable at 98.1%, is compared with the data of embodiment 1, finds the electricity of embodiment 1
Pond has higher battery efficiency and stability.
Embodiment 2
On the basis of embodiment 1, the ion exchange capacity of sulfonated polyether-ether-ketone in embodiment 1 is changed to into 2.2 mmol/g, is adopted
The rice paper that the present embodiment is prepared with preparation method same as Example 1 strengthens sulfonated polyether-ether-ketone film.The rice paper strengthens sulphur
The thickness for changing polyether-ether-ketone film is 105 μm.Sulfonated polyether-ether-ketone film assembling all-vanadium flow battery, other groups are strengthened with this rice paper
Dress condition and test condition are with embodiment 1.In performance test, the coulombic efficiency of battery is 98.2%, and energy efficiency is 86.0%.
In life experiment, in the continuous charge and discharge cycles of 1000 circles, coulombic efficiency is basically stable at 98.6%, illustrates that the rice paper strengthens
Sulfonated polyether-ether-ketone film has excellent stability.
Embodiment 3
On the basis of embodiment 1, by rice paper size in embodiment 1 be changed to length for 40 cm, width be 15 cm, thickness be 50
μm, the rice paper that the present embodiment is prepared using preparation method same as Example 1 strengthens sulfonated polyether-ether-ketone film.The rice paper increases
The area of strong sulfonated polyether-ether-ketone film is 600 cm2, thickness be 53 μm.The assembling of sulfonated polyether-ether-ketone film is strengthened with this rice paper complete
Vanadium flow battery, other assembling conditions and test condition are with embodiment 1.In performance test, the coulombic efficiency of battery is
98.3%, energy efficiency is 86.7%.In life experiment, in the continuous charge and discharge cycles of 1000 circles, coulombic efficiency is basicly stable
98.8%, illustrate that the rice paper strengthens sulfonated polyether-ether-ketone film and has excellent stability.
Embodiment 4
On the basis of embodiment 1, sulfonated polyether-ether-ketone in embodiment 1 is changed to into the sulphur that ion exchange capacity is 2.0 mmol/g
Change polyimides, the rice paper that the present embodiment is prepared using preparation method same as Example 1 strengthens sulfonated polyimide film.
It is 112 μm that the rice paper strengthens the thickness of sulfonated polyimide film.Sulfonated polyimide film assembling all-vanadium flow is strengthened with this rice paper
Battery, other assembling conditions and test condition are with embodiment 1.In performance test, the coulombic efficiency of battery is 98.5%, energy
Efficiency is 82.5%.In life experiment, in the continuous charge and discharge cycles of 2000 circles, coulombic efficiency is basically stable at 99.1%, says
The bright rice paper strengthens sulfonated polyether-ether-ketone film and has excellent stability.
In summary, rice paper strengthens non-fluorine ionic membrane simultaneously with high stability and high battery efficiency, answers with great
Use potentiality.Rice paper enhancing non-fluorine ionic membrane is applied to flow battery to be particularly in all-vanadium flow battery, can be in reduces cost
Higher battery performance and longer battery life are obtained simultaneously.
Above content is with reference to specific preferred embodiment further description made for the present invention, it is impossible to assert
The present invention be embodied as be confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of without departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. a kind of flow battery strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：Which includes a surname as skeleton enhancing base materials
Paper and the sulfonic acid type non-fluorinated polymer being filled in the rice paper base material.
2. flow battery according to claim 1 strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：Body per cubic centimeter
During long-pending flow battery rice paper strengthens non-fluorine ionic membrane, the quality containing sulfonic acid type non-fluorinated polymer is 0.1 ~ 0.5 g.
3. flow battery according to claim 2 strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：Body per cubic centimeter
During long-pending flow battery rice paper strengthens non-fluorine ionic membrane, the quality containing sulfonic acid type non-fluorinated polymer is 0.25 ~ 0.35 g.
4. flow battery according to claim 2 strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：The hole of the rice paper
Gap rate is 10% ~ 50%；The thickness of the rice paper is 10 ~ 500 μm.
5. flow battery according to claim 4 strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：The sulfonic acid type is non-
Fluoropolymer includes sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonate polybenzimidazole, SPSF, sulfonated polyether sulfone, sulfonation
One or more mixture in polystyrene.
6. flow battery according to claim 5 strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：The sulfonic acid type is non-
The ion exchange capacity of fluoropolymer is 0.1 ~ 10 mmol/g.
7. the flow battery according to claim 1 ~ 6 any one strengthens non-fluorine ionic membrane with rice paper, it is characterised in that its
Prepared using following steps：
Step S1：The sulfonic acid type non-fluorinated polymer is dissolved in organic solvent by 0.05 ~ 0.5 g/mL of mass volume ratio, 20
At ~ 90 DEG C, 0.5 ~ 48 h of magnetic agitation makes sulfonic acid type non-fluorinated polymer solution；
Step S2：It is laid on rice paper smooth on substrate, sulfonic acid type non-fluorinated polymer solution prepared by step S1 is poured on into a surname
On paper, by sulfonic acid type non-fluorinated polymer solution in rice paper surface even spread, 0.1-5 h are stood, successively in 70 ~ 100 DEG C of dryings 1
~ 48 h, 100 ~ 150 DEG C of 1 ~ 48 h of vacuum drying, then demoulding, is obtained flow battery rice paper enhancing non-fluorine ionic membrane.
8. flow battery according to claim 7 strengthens non-fluorine ionic membrane with rice paper, it is characterised in that：The organic solvent
For in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetrahydrofuran
Kind or more than two kinds of mixture；The substrate is glass plate, plastic plate, ceramic wafer.
9. a kind of flow battery as described in claim 1 ~ 8 any one strengthens the preparation method of non-fluorine ionic membrane with rice paper,
Characterized in that, comprising the following steps：
Step S1：The sulfonic acid type non-fluorinated polymer is dissolved in organic solvent by 0.05 ~ 0.5 g/mL of mass volume ratio, 20
At ~ 90 DEG C, 0.5 ~ 48 h of magnetic agitation makes sulfonic acid type non-fluorinated polymer solution；
Step S2：It is laid on rice paper smooth on substrate, sulfonic acid type non-fluorinated polymer solution prepared by step S1 is poured on into a surname
On paper, by sulfonic acid type non-fluorinated polymer solution in rice paper surface even spread, 0.1-5 h are stood, successively in 70 ~ 100 DEG C of dryings 1
~ 48 h, 100 ~ 150 DEG C of 1 ~ 48 h of vacuum drying, then demoulding, is obtained flow battery rice paper enhancing non-fluorine ionic membrane；
Wherein, the porosity of the rice paper is 10% ~ 50%；The thickness of the rice paper is 10 ~ 500 μm；
The flow battery of volume per cubic centimeter strengthens the quality containing sulfonic acid type non-fluorinated polymer in non-fluorine ionic membrane with rice paper
For 0.25 ~ 0.35 g；
The organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl Asia
The mixture of one or two or more kinds in sulfone, tetrahydrofuran；
The substrate is glass plate, plastic plate, ceramic wafer.
10. flow battery according to claim 9 strengthens the preparation method of non-fluorine ionic membrane with rice paper, it is characterised in that：
The flow battery is all-vanadium flow battery, full iron liquid galvanic battery, full copper flow battery, full stress-strain flow battery, zinc/bromine liquid stream
Battery, iron/chrome liquor galvanic battery, sodium polysulfide/bromine redox flow cell, vanadium/bromine flow battery, zinc/cerium flow battery, iron/vanadium liquid stream
Battery, vanadium/air or vanadium/hydrogen flow battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109873187A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
| CN112467179A (en) * | 2019-09-06 | 2021-03-09 | 中国科学院大连化学物理研究所 | Alkaline all-iron flow battery |
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| CN202150529U (en) * | 2010-12-13 | 2012-02-22 | 依诺特生物能量控股公司 | Battery with a battery cell |
| CN103950239A (en) * | 2014-04-24 | 2014-07-30 | 合肥国轩高科动力能源股份公司 | Multifunctional composite film for chemical power source |
| CN105958131A (en) * | 2016-06-20 | 2016-09-21 | 南开大学 | Rechargeable water system zinc ion battery with long cycle life and high energy density |
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| CN202150529U (en) * | 2010-12-13 | 2012-02-22 | 依诺特生物能量控股公司 | Battery with a battery cell |
| CN103950239A (en) * | 2014-04-24 | 2014-07-30 | 合肥国轩高科动力能源股份公司 | Multifunctional composite film for chemical power source |
| CN105958131A (en) * | 2016-06-20 | 2016-09-21 | 南开大学 | Rechargeable water system zinc ion battery with long cycle life and high energy density |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109873187A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
| CN112467179A (en) * | 2019-09-06 | 2021-03-09 | 中国科学院大连化学物理研究所 | Alkaline all-iron flow battery |
| CN112467179B (en) * | 2019-09-06 | 2022-03-08 | 中国科学院大连化学物理研究所 | Alkaline all-iron flow battery |
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