CN103840178A - Application of fluorine-containing sulfonate ion exchange membrane in flow energy storage battery - Google Patents
Application of fluorine-containing sulfonate ion exchange membrane in flow energy storage battery 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0293—Matrices for immobilising electrolyte solutions
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- 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 relates to application of a fluorine-containing sulfonate ion exchange membrane in a flow energy storage battery. The fluorine-containing sulfonate ion exchange membrane is a perfluoro-sulfonate ion-exchanged membrane, or a meta-fluorine-containing sulfonate ion exchange membrane, or a fluorine partial-containing sulfonate ion exchange membrane of a short-chain branch; the ion exchange membrane is of a structure with a relatively short chain branch which reduces the radius of a model cluster in the membrane, and thus the ion transmission channel can be reduced, the selectivity of the membrane to vanadium ions can be improved, the permeation of vanadium ions and the water migration of an all-vanadium flow energy storage battery are reduced, the cross flowing of anode and cathode electrolyte can be effectively reduced, and the reduction of the capacity of the battery during long-term discharging is also suppressed; in addition, the service life of the electrolyte can be prolonged.
Description
Technical field
The present invention relates to preparation and application thereof for the short-chain branch sulfonate film of the amberplex of all-vanadium liquid flow energy storage battery, belong to the ion exchange membrane material technical field of all-vanadium liquid flow energy storage battery.
Background technology:
Society, along with the fast development of human economy, the present situation of energy shortage and environmental pollution is increasingly severe.For realizing sustainable development, must greatly develop the regenerative resource such as solar energy and wind energy.And these renewable energy power generations are subject to the impact of the condition such as region, meteorology to have significantly discontinuous, unsteadiness.For the time difference contradiction of level and smooth and stable renewable energy power generation output and solution generating and electricity consumption, improve power quality and electric network reliability, must develop high-efficiency energy-storage technology.All-vanadium liquid flow energy storage battery (VFB) is owing to having separate adjustable, the response of power system capacity and power rapidly; safe and reliable; have extended cycle life; Operation and Maintenance is simple; outstanding advantages such as environmental friendliness and become renewable energy power generation; electrical network peak load shifting, one of the most promising technology in the scale energy storage such as emergent and stand-by station.
At present, the technological break-through that all-vanadium liquid flow energy storage battery exists mainly contains three aspects:: electrolyte poor stability; Vanadium ion migration and the water diffusion of different valence state cause logistics unbalance; Running current density is low.As the amberplex of one of all-vanadium liquid flow energy storage battery critical material, play dual parts to separate both positive and negative polarity active material (different valence state ion) and conducting proton.Desirable amberplex must possess following characteristics: resistance vanadium is high; Good proton conductivity, good chemical stability and mechanical stability, with low cost etc.
The perfluoro sulfonic acid membrane of E.I.Du Pont Company---Nafion film series is owing to having good ionic conductivity, chemistry and mechanical stability excellence and be able to extensive use in all-vanadium liquid flow energy storage battery.But due to one side, the selectivity of Nafion film is not high, vanadium ion mutually string is serious, causes self-discharge phenomenon, thereby causes the capacity of battery obviously to be decayed in long-term cyclic process, and energy content of battery conversion efficiency is corresponding reduction also; In addition on the one hand, because its cost is higher, film production process complexity, procedure parameter control production cost strict, film are too high, have restricted to a great extent its industrialization at perfluoro sulfonic acid membrane and commercialization.
For the high deficiency of Nafion series perfluorinated sulfonic acid base amberplex vanadium permeability, numerous researchers have made study on the modification to it, and expectation can improve the vanadium ion infiltration of film, thereby improve the operating characteristics of battery.Study on the modification direction mainly contains the aperture that utilizes some organic molecules or inorganic particulate to improve amberplex, and grafting amberplex, develops non-fluorine ion exchange membrane and anion-exchange membrane etc.But except minority perfluoro sulfonic acid membrane, most of business-like amberplex is all easily degraded at the anode electrolyte of VFB strong oxidizing property.Therefore in utilizing perfluoro sulfonic acid membrane high stability, from improving in essence the important development direction that the vanadium permeance property of perfluorinated sulfonic acid ion exchange membrane is also VFB membrane material.
High this characteristic of vanadium permeability of Nafion film is mainly determined by its microstructure.Fig. 1 is the chemical structural formula (wherein x=6-10, y=z=1) of perfluorinated sulfonic acid ion exchange membrane.Can find out, perfluorinated sulfonic acid ion exchange membrane is made up of with the side chain of hydrophily ion-exchange group (sulfonic acid group) hydrophobic polytetrafluoroethylene skeleton and end.
The chemical structural formula of formula 1 perfluorinated sulfonic acid ion exchange membrane
In the microstructure of perfluoro sulfonic acid membrane has been carried out researching and analysing in a large number, comparatively generally acknowledged microstructure models is threephase region model.Perfluorinated sulfonic acid ion exchange membrane is divided into three regions by this model: A district is carbon-fluorine skeleton district (Hydrophobic Region) of hydrophobic; C district is ion cluster district (Ionic ClusterRegion), is the enrichment region of fixed ion group, counter ion and hydrone; B district is between the boundary zone in A district and C interval (Interfacial Zone), is mainly made up of dangle side chain and a small amount of hydrone, fixed ion and counter ion.Therefore, there is microphase-separated in perfluoro sulfonic acid membrane inside, sulfonic acid group is not uniformly distributed in film, but produce micron-scale phase separation with form and hydrophobicity carbon-fluorine skeleton of ion cluster, between ion cluster, be interconnected to form passage by hydrone, transmit along these passages for ion (proton).Test the existence of cluster in susceptible of proof film by small angle X ray scattering, and study and find that ion cluster radius increases along with a chain length increases, the increase of Prague spacing.(Robert B.Moore, Macromolecules, 24 (1991) 1376-1382.) therefore the high essential reason of vanadium permeability of Nafion film are that its side chain is longer, and the ion cluster radius of formation is larger, causes ion transfer passage larger.Otherwise, can improve film resistance vanadium compared with the perfluor of short-chain branch (short-side-chain) or inclined to one side fluosulfonic acid film by synthetic.From the practical application angle of VFB, developing targetedly and obtaining stability compared with fluorine-containing (perfluor, fluorine or part are fluorine-containing partially) sulfonic acid ion exchange membrane of short-chain branch is the direction that can further investigate with the amberplex that resistance vanadium has both.
Summary of the invention
The object of the invention is to provide one to be applicable to all-vanadium liquid flow energy storage battery, having better vanadium ion optionally contains compared with the fluorine-containing (perfluor of short-chain branch (short-side-chain), fluorine or part are fluorine-containing partially) sulfonic acid polymer amberplex, and be applied in liquid-flow energy storage battery with acidic electrolyte.
For achieving the above object, the technical solution used in the present invention is:
The perfluorinated sulfonic acid ion exchange membrane that described sulfonic fluoropolymer amberplex is short-chain branch or partially fluosulfonic acid amberplex or part sulfonic fluoropolymer amberplex;
The perfluorinated sulfonic acid ion exchange membrane material of short-chain branch is unordered copolymer or the alternate copolymer that segments A and segment B form;
Segments A structure is:
segment B structure is:
in perfluorinated sulfonic acid ion exchange membrane, the quantity of construction unit segments A and B is than being 3-10, the positive integer that n is 1-2;
The inclined to one side fluosulfonic acid ion exchange membrane material of short-chain branch is segment C and the unordered copolymer of segment D or alternate copolymer;
Segment C-structure is:
segment D structure is:
in perfluorinated sulfonic acid ion exchange membrane, the quantity of construction unit segment C and D is than being 3-10, the positive integer that n is 1-2;
The part sulfonic fluoropolymer amberplex of short-chain branch is segments A, segment B, segment C, the unordered copolymer of segment D;
In part sulfonic fluoropolymer amberplex, construction unit segments A+C is 3-10 with the quantity ratio of segment B+D, the positive integer that n is 1-2;
Segments A, segment C, segment B, the structure of segment D is respectively:
The synthetic method of synthetic film perfluorovinyl sulfide ether monomer used or vinylidene fluoride ether monomer can be reported with reference to pertinent literature (L.Merlo, Journal of Power Sources, 171 (2007) 140-147.).Synthetic route is as follows:
Synthetic sulphonyl perfluorovinyl sulfide ether monomer (SFVE) or sulphonyl vinylidene fluoride ether monomer (DFVE):
The preparation method of the described sulfonic fluoropolymer film containing short-chain branch (SSC) is as follows:
(1) tetrafluoroethene (TFE) is passed in the reactor that sulfur trioxide is housed, controlling tetrafluoroethene is 1:1 or 2:1 with the ratio of the amount of substance of sulfur trioxide, keep certain pressure 5-10bar and lower temperature 10-50 DEG C, reaction 5-10h obtains perfluor β-second sultone through distillation.
(2) reaction system will strictly dewater, and needs that all reactants are carried out to high temperature (100-120 DEG C) vacuumize and thoroughly dewater before reaction.Under the catalytic action of alkali metal fluoride CsF or KF, in system, pass into excessive F
2, make perfluor β-second sultone and F
2there is ring-opening polymerization.
(3) in the product of previous step, add 1 in 1:1 ratio, 2-bis-chloro-1, after the fluoro-ethene generation of the chloro-1-of 2-difluoroethylene or 1-addition reaction, then remove chlorine or chlorine monofluoride (ClF) and generate sulphonyl perfluorovinyl sulfide ether monomer (SFVE) or sulphonyl vinylidene fluoride ether monomer (DFVE).
(4) in autoclave, pass through half batch methods charging, keep sulphonyl perfluorovinyl sulfide ether monomer (SFVE) or (and) sulphonyl vinylidene fluoride ether monomer (DFVE) and tetrafluoroethene (TFE) or (and) ratio of vinylidene (VDF) feed rate is between 1:3-1:10, the pressure of controlling TFE or VDF is 4-10bar, with emulsion or microemulsion method synthetic polymer presoma, the reaction time is controlled between 10-30h.
(5) from emulsion, obtain polymerizate by freeze-thaw method, with after deionized water washing, the dry polymer precursor that obtains at 100 DEG C-120 DEG C.
(6) ethylene glycol (EG), N will be dissolved in after polymer granulation, in the solvent of one or more highers such as dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP), solution temperature is at 20～80 DEG C, make polymer solution, the concentration of solution is controlled at 5wt%-15wt%.
(7) polymer solution obtaining is watered and cast from glass plate or corrosion resistant plate, at 60～100 DEG C more than dry 5h, the then above film forming of vacuumize 1h at 80～150 DEG C, the thickness of film is between 30～200 μ m.
(8) (containing-SO compared with the ion exchange polymer film of short-chain branch preparation
2f) processing that is hydrolyzed: first immerse concentration in the hot strong base solution of 1-25mol/L, soak time is 0.5-100h, and temperature is 60-100 DEG C, and described highly basic is potassium hydroxide or NaOH; Immersing concentration is in 0.1-25mol/L strong acid solution again, soak time 0.5-100h, and solution temperature is 5-100 DEG C, described strong acid is sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid.
The invention still further relates to prepared by said method compared with short-chain branch perfluor, the fluorine-containing amberplex of fluorine or part removes and can be applicable to liquid-flow energy storage battery with acidic electrolyte partially, comprising: all-vanadium liquid flow energy storage battery, siderochrome liquid flow energy storage battery, zinc bromine liquid flow energy storage battery, vanadium bromine liquid flow energy storage battery or vanadium cerium liquid flow energy storage battery.
Useful result of the present invention
(1) the prepared amberplex of the present invention contains compared with short-chain branch structure, reduce the ion cluster radius in film, thereby dwindle ion transfer passage, and then the selectivity of raising film to vanadium ion, vanadium ion infiltration and the water migration of all-vanadium liquid flow energy storage battery are reduced, effectively reduce both positive and negative polarity electrolyte and go here and there mutually, suppressed the capacity attenuation of battery in long-term charge and discharge process, and extended the useful life of electrolyte.
(2) the prepared ion exchange membrane material of the present invention has good dissolubility and processing characteristics.
(3) the prepared ion exchange membrane material of the present invention has good mechanical strength and good toughness, shows good thermal stability and mechanical stability.
(4) the prepared ion exchange membrane material Stability Analysis of Structures of the present invention, can meet the performance of liquid-flow energy storage battery with acidic electrolyte and the demand of use steady in a long-term effectively.
Brief description of the drawings
Fig. 1 is short-chain branch perfluoro sulfonic acid membrane transmission electron microscope picture prepared by embodiment 1; (left side-SSC-M1; The right side-Nafion212);
Fig. 2 is the charging and discharging curve (a) of all-vanadium liquid flow energy storage battery and the efficiency chart (b) of battery that embodiment 2 assembles;
Fig. 3 is the charging and discharging curve of the all-vanadium liquid flow energy storage battery assembled of embodiment 3.
Embodiment
The following examples are to further illustrate of the present invention, instead of limit the scope of the invention.
Tetrafluoroethene (TFE) is passed in the autoclave that sulfur trioxide is housed, and controlling tetrafluoroethene is 1:1 with the ratio of the amount of sulfur trioxide, keeps pressure 5bar, and temperature is 20 DEG C, after reaction 10h, obtains perfluor β-second sultone through distillation.Under 100 DEG C of vacuumizes, to after all reactant dehydrations, under the catalytic action of alkali metal fluoride CsF or KF, in system, pass into excessive F
2, make perfluor β-second sultone and F
2there is ring-opening polymerization.Add 1,2-bis-chloro-1 in 1:1 ratio, after 2-difluoroethylene generation addition reaction, then remove chlorine (Cl
2) generation sulphonyl perfluorovinyl sulfide ether monomer (SFVE).SFVE and TFE are added in autoclave with the feed rate of 1:6, and the pressure of controlling TFE is 5bar, and the reaction time is 10h, reclaims polymer afterwards with deionized water washing, the dry polymer precursor that obtains at 100 DEG C.The short-chain branch perfluorinated sulfonic acid ion exchange membrane polymer architecture formula of preparation as shown in Figure 1, confirm from the transmission electron microscope picture of Fig. 1 the hydrophilic area that this film exists the hydrophobic region that formed by carbon-fluorine main chain of hydrophobic and sulfonate radical cation exchange groups to form, thereby form the phase separation structure similar to Nafion film, but due to the existence of short-chain branch in this exchange membrane containing fluorine of preparation, cause its Nafion212 film than long-chain branch degree that is separated less, the distribution continuity of hydrophilic area is lower, ion cluster radius is less, thereby causes ion transfer passage narrower.
Embodiment 2
To after polymer granulation prepared embodiment 1, be dissolved in the solution that forms 5wt% in NMP, solution temperature is 50 DEG C, and gained solution-cast, on glass plate or corrosion resistant plate, is dried to 10h under 60 DEG C of conditions, then 80 DEG C of vacuumize 12h film forming, the thickness of film is in 50 μ m left and right.The film of preparation is first soaked to 10h in the hot strong base solution of 5mol/L, then soak 15 hours in 3M sulfuric acid solution, obtain amberplex (being designated as SSC-M1).
By prepared amberplex assembling all-vanadium liquid flow energy storage battery, Catalytic Layer is activated carbon-fiber felt, and bipolar plates is graphite cake, and film effective area is 48cm
2, current density is 80mA cm
-2, in electrolyte solution, vanadium ion concentration is 1.50mol L
-1, H
2sO
4concentration is 3mol L
-1.Film thickness is the current efficiency 96.9% of 50 μ m amberplex assembled batteries, and voltage efficiency is 86.0%, and energy efficiency is 83.3%.Battery charging and discharging curve is as Fig. 2. (a), in figure, charging interval and discharge time are substantially suitable, with condition of equivalent thickness (condition of equivalent thickness m) of 50 μ, compared with compared with under the all-vanadium liquid flow energy storage battery comparable applications condition of long-chain branch Nafion212 assembling, discharge milder, show that the vanadium permeability of film is lower.
Fig. 2. the coulombic efficiency that (b) shows SSC-M1 battery is obviously high than Nafion212, and voltage efficiency is a little less than Nafion212, and total energy efficiency is better than 212 films.
Embodiment 3
To after polymer granulation prepared embodiment 1, be dissolved in the solution that forms 10wt% in NMP, solution temperature is 50 DEG C, and gained solution-cast, on glass plate or corrosion resistant plate, is dried to 10h under 60 DEG C of conditions, then 80 DEG C of vacuumize 12h film forming, the thickness of film is in 130 μ m left and right.The film of preparation is soaked to 10h in the hot strong base solution of 5mol/L, then soak 15 hours in 3M sulfuric acid solution, obtain amberplex (being designated as SSC-M2).By prepared amberplex assembling all-vanadium liquid flow energy storage battery, Catalytic Layer is activated carbon-fiber felt, and bipolar plates is graphite cake, and film effective area is 48cm
2, current density is 60mA cm
-2, in electrolyte, vanadium ion concentration is 1.50mol L
-1, H
2sO
4concentration is 3mol L
-1.Film thickness is the current efficiency 96.14% of 130 μ m amberplex assembled batteries, and voltage efficiency is 88.87%, and energy efficiency is 85.44%.Battery charging and discharging curve is as Fig. 3.In figure charging interval and discharge time substantially suitable, discharge milder, show that the vanadium permeability of film is lower.
Embodiment 4
Tetrafluoroethene (TFE) is passed in the autoclave that sulfur trioxide is housed, and controlling TFE is 1:1 with the ratio of the amount of sulfur trioxide, keeps pressure 5bar, and temperature is 20 DEG C, after reaction 10h, obtains perfluor β-second sultone through distillation.Under 100 DEG C of vacuumizes, to after all reactant dehydrations, under the catalytic action of alkali metal fluoride CsF or KF, in system, pass into excessive F
2, make perfluor β-second sultone and F
2there is ring-opening polymerization.Add after the fluoro-ethene generation of the chloro-1-of 1-addition reaction in 1:1 ratio, then remove chlorine monofluoride (ClF) and generate sulphonyl vinylidene fluoride ether monomer (DFVE).DFVE and VDF are added in autoclave with the feed rate of 1:6, and the pressure of TFE is 5bar, and the reaction time is 10h, reclaims polymer afterwards with deionized water washing, the dry polymer precursor that obtains at 100 DEG C.The inclined to one side fluosulfonic acid amberplex of the short-chain branch polymer architecture formula of preparation is as follows.
Embodiment 5
To after polymer granulation prepared embodiment 4, be dissolved in the solution that forms 8wt% in NMP, solution temperature is 50 DEG C, and gained solution-cast, on glass plate or corrosion resistant plate, is dried to 10h under 60 DEG C of conditions, then 80 DEG C of vacuumize 12h film forming, the thickness of film is in 100 μ m left and right.The film of preparation is first soaked to 10h in the hot strong base solution of 5mol/L, then soak 15 hours in 3M sulfuric acid solution, obtain amberplex.
Embodiment 6
Tetrafluoroethene (TFE) is passed in the autoclave that sulfur trioxide is housed, and controlling tetrafluoroethene is 2:1 with the ratio of the amount of substance of sulfur trioxide, keeps pressure 10bar, and temperature is 20 ° of C, after reaction 10h, obtains perfluor β-second sultone through distillation.Under 100 DEG C of vacuumizes, to after all reactant dehydrations, under the catalytic action of alkali metal fluoride CsF or KF, in system, pass into excessive F
2, make perfluor β-second sultone and F
2there is ring-opening polymerization.Add 1,2-bis-chloro-1 in 1:1 ratio, after 2-difluoroethylene generation addition reaction, then remove chlorine (Cl
2) generation sulphonyl perfluorovinyl sulfide ether monomer (SFVE).SFVE and TFE are added in autoclave with the feed rate of 1:6, and the pressure of TFE is 5bar, and the reaction time is 10h, reclaims polymer afterwards with deionized water washing, the dry polymer precursor that obtains at 100 DEG C.The short-chain branch perfluorinated sulfonic acid ion exchange membrane polymer architecture formula of preparation is as follows.
Embodiment 7
To after polymer granulation prepared embodiment 6, be dissolved in the solution that forms 8wt% in NMP, solution temperature is 50 DEG C, and gained solution-cast, on glass plate or corrosion resistant plate, is dried to 10h under 60 DEG C of conditions, then 80 DEG C of vacuumize 12h film forming, the thickness of film is in 100 μ m left and right.The film of preparation is first soaked to 10h in the hot strong base solution of 5mol/L, then soak 15 hours in 3M sulfuric acid solution, obtain amberplex.
Embodiment 8
Tetrafluoroethene (TFE) is passed in the autoclave that sulfur trioxide is housed, and controlling TFE is 1:1 with the ratio of the amount of sulfur trioxide, keeps pressure 5bar, and temperature is 20 DEG C, after reaction 10h, obtains perfluor β-second sultone through distillation.Under 100 DEG C of vacuumizes, to after all reactant dehydrations, under the catalytic action of alkali metal fluoride CsF or KF, in system, pass into excessive F
2, make perfluor β-second sultone and F
2there is ring-opening polymerization.Add 1,2-bis-chloro-1 in 1:1 ratio, 2-difluoroethylene mixture generation addition reaction, removes chlorine (Cl after then
2) generation sulphonyl perfluorovinyl sulfide ether monomer (SFVE).SFVE and VDF are added in autoclave with the feed rate of 1:6, and the pressure of TFE is 5bar, and the reaction time is 10h, reclaims polymer afterwards with deionized water washing, the dry polymer precursor that obtains at 100 DEG C.The short-chain branch part exchange membrane containing fluorine polymer architecture formula of preparation is as follows.
Embodiment 9
To after polymer granulation prepared embodiment 8, be dissolved in the solution that forms 8wt% in NMP, solution temperature is 50 DEG C, and gained solution-cast, on glass plate or corrosion resistant plate, is dried to 10h under 60 DEG C of conditions, then 80 DEG C of vacuumize 12h film forming, the thickness of film is in 100 μ m left and right.The film of preparation is first soaked to 10h in the hot strong base solution of 5mol/L, then soak 15 hours in 3M sulfuric acid solution, obtain amberplex.
Claims (2)
1. the application of sulfonic fluoropolymer amberplex in liquid flow energy storage battery, is characterized in that: the perfluorinated sulfonic acid ion exchange membrane that described sulfonic fluoropolymer amberplex is short-chain branch or partially fluosulfonic acid amberplex or part sulfonic fluoropolymer amberplex;
The perfluorinated sulfonic acid ion exchange membrane material of short-chain branch is unordered copolymer or the alternate copolymer that segments A and segment B form;
Segments A structure is:
segment B structure is:
in perfluorinated sulfonic acid ion exchange membrane, the quantity of construction unit segments A and B is than being 3-10, the positive integer that n is 1-2;
The inclined to one side fluosulfonic acid ion exchange membrane material of short-chain branch is segment C and the unordered copolymer of segment D or alternate copolymer;
Segment C-structure is:
segment D structure is:
in perfluorinated sulfonic acid ion exchange membrane, the quantity of construction unit segment C and D is than being 3-10, the positive integer that n is 1-2;
The part sulfonic fluoropolymer amberplex of short-chain branch is segments A, segment B, segment C, the unordered copolymer of segment D;
In part sulfonic fluoropolymer amberplex, construction unit segments A+C is 3-10 with the quantity ratio of segment B+D, the positive integer that n is 1-2;
Segments A, segment C, segment B, the structure of segment D is respectively:
2. application according to claim 1, is characterized in that,
Liquid flow energy storage battery is liquid-flow energy storage battery with acidic electrolyte, and it comprises: all-vanadium liquid flow energy storage battery, siderochrome liquid flow energy storage battery, zinc bromine liquid flow energy storage battery, vanadium bromine liquid flow energy storage battery or vanadium cerium liquid flow energy storage battery.
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Cited By (4)
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| CN110350150A (en) * | 2019-07-16 | 2019-10-18 | 深圳市南科燃料电池有限公司 | A kind of transfer printing process and membrane electrode |
| CN110612627A (en) * | 2017-05-11 | 2019-12-24 | 旭化成株式会社 | Polymer electrolyte membrane, membrane electrode assembly, and solid polymer fuel cell |
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| JPWO2020080523A1 (en) * | 2018-10-18 | 2021-09-02 | ダイキン工業株式会社 | Fluorine-containing elastomers, crosslinkable compositions and molded articles |
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