CN106558662B - Ion-conductive membranes, flow battery and preparation method using the ion-conductive membranes - Google Patents
Ion-conductive membranes, flow battery and preparation method using the ion-conductive membranes Download PDFInfo
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- CN106558662B CN106558662B CN201510628988.0A CN201510628988A CN106558662B CN 106558662 B CN106558662 B CN 106558662B CN 201510628988 A CN201510628988 A CN 201510628988A CN 106558662 B CN106558662 B CN 106558662B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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 ion-conductive membranes, including ion-conductive membranes base layer, the ion-conductive membranes base layer is equipped with coating, and the swelling ratio of the covering layer material is not higher than 0.5 times of the swelling ratio of the ion-conductive membranes matrix layer material.The material of the coating is selected from least one of ceramic powder, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene (PTFE), polyvinyl chloride, polypropylene or epoxy resin.The present invention is not in Swelling after so that ion-conductive membranes is met water again by setting coating in ion-conductive membranes base layer, so that easy-to-use dry dress packaging technology is achieved.Compared with the assembling of the wet film of the prior art, battery coulombic efficiency and energy efficiency 2%~3% are improved, in addition, also substantially increasing the service life of flow battery.
Description
Technical field
Of the invention is related to flow battery technology field, in particular to a kind of flow battery ion-conductive membranes and its preparation
Method.
Background technique
Flow cell pile includes the structures such as electrode frame, positive and negative electrode and ion-conductive membranes.Electrode frame is hollow structure, just
Negative electrode is located therein empty region, and ion-conductive membranes are between positive and negative electrode, the surrounding of the both side surface of ion-conductive membranes
Portion and electrode frame are in close contact.
In the prior art, when assembling flow battery, it often cannot achieve the ionic conduction directlyed adopt under drying regime
Film (dry film) assembles pile, this is because after untreated ion-conductive membranes are assembled on pile, ion-conductive membranes and electrolysis
Water absorption and swelling phenomenon can occur for liquid contact, so that the area of ion-conductive membranes and size change, and the four of ion-conductive membranes
Peripheral portion is in close contact and compresses with electrode frame, causes the part membrane material that can not continue to extend to the outside of pile after swelling,
To accumulate a certain number of folds in the region, the appearance of fold will substantially reduce the close of ion-conductive membranes and two sides electrode frame
Feng Xing reduces pile operation stability to increase the risk of pile internal electrical losses and leakage, shortens the pile service life.Therefore, it is
Problem above is avoided, the mode for assembling pile in the prior art is to assemble electricity using the ion-conductive membranes (wet film) of moisture state
Dry film is first placed in water, forms the assembling that wet film carries out pile again in electrolyte after complete wetting by heap.
But using wet film assembling pile, there are following technical problem and defects:
1. dry film infiltration is after wet film, the tensile strength of membrane material at least declines 20%, causes the longevity of ion-conductive membranes
Life reduces, and after battery undergoes longtime running, ion-conductive membranes will appear situations such as crackle is even crushed.
2. due to having infiltrated a certain amount of liquid, inevitably there is the problem of thickness is thinning, aperture becomes larger, leads in wet film
The ion in fluid cell electrolyte is caused to accelerate by the speed that film two sides are permeated, so that the coulombic efficiency of flow battery reduces
2%-3%, energy efficiency also decrease.
3. wet film is since the public runner through-hole wall of its electrolyte directly contacts the electrolyte with corrosivity and electric conductivity,
When flow battery operation, the electrolyte realization infiltrated in the electrolyte of the public runner through hole of electrolyte and membrane material inside is led
Logical, to generate by-pass current, so that interior leaky occurs again and again, and the electric energy generated that leaks electricity often is disappeared in a manner of heat
Consumption, so as to cause the public runner through hole overheat (local temperature can exceed that 50 DEG C) of wet film electrolyte, so that electrolyte is active
Substance is precipitated at high operating temperatures and is formed the crystalline material of strong oxidizing property, these solid matters are deposited in the electricity of ion-conductive membranes
It solves on the public runner of liquid, has further speeded up the corrosion rate of the public runner inner wall of ion-conductive membranes especially electrolyte, so that
There is hole, crackle since the public runner through hole of electrolyte first in ion-conductive membranes, and ion-conductive membranes is caused integrally to rupture
Damage, pile are integrally scrapped, and battery system can not continue to run.
Summary of the invention
In order to solve technical problem caused by prior art wet film assembled battery pile, the present invention provides a kind of liquid stream electricity
Pond ion-conductive membranes and preparation method thereof, avoidable ion-conductive membranes tensile strength is low, the interior electric leakage of battery, battery coulombic efficiency
The low, technological deficiencies such as energy efficiency is low, improve the performance and service life of flow cell pile.
It is an object of that present invention to provide a kind of ion-conductive membranes, including ion-conductive membranes base layer, the ion-conductive membranes
Base layer is equipped with coating, and the swelling ratio of the covering layer material is not higher than the swelling ratio of the ion-conductive membranes matrix layer material
0.5 times.
Ion-conductive membranes base layer material of the present invention is flow battery versatile material, specifically preferably containing acidic group or
Fluorine-containing, the non-fluorinated polymer of acyloxy derivatives.
The material of the coating is selected from ceramic powder, ethylene-tetrafluoroethylene copolymer, gathers as a preferred technical solution,
At least one of tetrafluoroethene, polyvinyl chloride, polypropylene or epoxy resin.
As a preferred technical solution, the coating with a thickness of 0.01mm-0.5mm.
At least one surface on two surfaces of the ion-conductive membranes base layer is equipped with as a preferred technical solution,
Rectangular-ambulatory-plane coating；The outer edge size of the rectangular-ambulatory-plane coating is not less than the peripheral dimension of ion-conductive membranes base layer, institute
The inward flange size for stating rectangular-ambulatory-plane coating I is greater than the peripheral dimension of electrode.
As a preferred technical solution, at least one side of four cross sectional sides of the ion-conductive membranes base layer
Equipped with the coating.
The ion-conductive membranes base layer is equipped with the public runner through-hole of electrolyte, the electricity as a preferred technical solution,
The inner wall surface for solving the public runner through-hole of liquid is equipped with the coating.
The ion-conductive membranes base layer is equipped with location hole, the inner wall table of the location hole as a preferred technical solution,
Face is equipped with the coating.
The present invention another object is that ion-conductive membranes processing technology, by covering layer material described above by brush, spray
It applies, bond, impregnating or the mode of hot pressing is engaged in the ion-conductive membranes base layer.
Still a further object of the present invention is to provide flow battery electricity and pushes away, and includes above-described ion-conductive membranes.
Beneficial effects of the present invention:
1, water-swellable characteristic is met since flow battery ion-conductive membranes exist, is swollen out after causing dry dress to meet water in the process
Existing problem of leakage, therefore ion-conductive membranes can not be using dry dress in the prior art.And the present invention passes through in ion-conductive membranes matrix
Layer sets coating, is not in Swelling after so that ion-conductive membranes is met water again, so that easy-to-use dry dress packaging technology obtains
To realize.Compared with the assembling of the wet film of the prior art, battery coulombic efficiency and energy efficiency 2%~3% are improved, in addition, also
Substantially increase the service life of flow battery.
2, untreated ion-conducting membrane material intensity difference restricts the flow battery service life, and ion provided by the invention passes
Guided membrane sets rectangular-ambulatory-plane coating in the one or both sides in the region that it is contacted with electrode frame, and two sides can be same material can also be with
It is that different materials are constituted, while not influencing flow battery voltage efficiency, the mechanical strength of ion-conductive membranes is improved
50% or more, to greatly improve flow cell pile performance.
3, ion-conductive membranes provided by the invention, at least one side of four cross sectional sides of ion-conductive membranes base layer
Face is equipped with the coating；The capillarity for preventing ion-conductive membranes secures the ruler of ion-conductive membranes from thickness direction
It is very little.
4, ion-conductive membranes provided by the invention also set covering in the inner wall of the public runner of the electrolyte of ion-conductive membranes
Layer avoids the electrolyte and the public runner through hole of electrolyte received inside ion-conductive membranes by the isolation of coating
Electrolyte directly contacts, fundamentally prevented interior electric leakage caused by the leak channel formed inside ion-conductive membranes and caused by
Ion-conductive membranes permanent damage；Meanwhile also overcoming the problem of ion-conductive membranes are corroded.
5, ion-conductive membranes provided by the invention also set coating in the inner wall of the location hole of ion-conductive membranes, by fixed
The isolation and solidification that the coating of upper and lower surface and inner wall is played around the hole of position ensure that location hole in contact electrolyte
Size, the location and shape of front and back are unchanged, thus solve in the prior art pile since a certain section monocell goes wrong
When disassembly being needed to re-assembly, because of the variation of ion-conductive membranes position of positioning hole and size, cause pile that can not fast implement two
The problem of secondary assembling.
6, ion-conductive membranes provided by the invention, coating can bear the acid solution that hydrogen ion concentration is less than 10M, described
The internal pressure that can be born between coating and ion-conductive membranes base layer is not less than 2kg/cm2。
Detailed description of the invention
5 width of attached drawing of the present invention,
Each part position relations schematic diagram of ion-conductive membranes of the Fig. 1 with coating；
Fig. 2 ion-conductive membranes coat finished product schematic after coating processing；
Sectional view A-A after the public runner processing of ion-conductive membranes of the Fig. 3 with coating；
Cross-sectional views B-B after ion-conductive membranes location hole processing of the Fig. 4 with coating；
Sectional view C-C after ion-conductive membranes outer edge processing of the Fig. 5 with coating；
In figure, 1 diaphragm, 2 coats, the public runner through-hole of 3 electrolyte, 4 location holes.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Membrane edge portion stretching strength determination method, with reference to GB/T 1040.3-2006.
Embodiment 1
Ion-conductive membranes base layer, material is Nafion115 ion-conductive membranes, having a size of 400mm × 300mm.
The material of coating is polypropylene hot melt adhesive film, with a thickness of 0.2mm.
Two surfaces of ion-conductive membranes base layer are equipped with rectangular-ambulatory-plane coating, outer edge having a size of 400mm ×
300mm, inward flange is having a size of 350mm × 250mm.
Processing technology is that polypropylene hot melt adhesive film is cut into the rectangular-ambulatory-plane of two above-mentioned sizes using resin cutting die
Structure, as rectangular-ambulatory-plane coating.Ion-conductive membranes two sides are respectively placed in, are guaranteed outside its outer edge and ion-conductive membranes
Edge is neatly aligned.The ion-conductive membranes that two sides are equipped with rectangular-ambulatory-plane coating are placed into hot press and carry out hot-pressing processing, hot pressing work
Skill is as follows: temperature is 100 DEG C, pressure 3MPa, hot pressing time 40S, obtains the ion-conductive membranes with coating.Using this from
Sub- conductive membranes assembling 2kW pile (electrode size is 350mm × 250mm) simultaneously carries out charge and discharge cycles, and test data is shown in Table 1.
Comparative example 1
Nafion115 ion-conductive membranes, having a size of 400mm × 300mm.It is assembling 2kW using the directly dry dress of the membrane material
Pile simultaneously carries out charge and discharge cycles, and test data is shown in Table 1.
Comparative example 2
Nafion115 ion-conductive membranes place it in deionized water after impregnating 2.5h having a size of 360mm × 270mm,
Size swelling is 400mm × 300mm.2kW pile is assembled into using the membrane material and carries out charge and discharge cycles, and test data is shown in Table
1。
Table 1
Embodiment 2
Ion-conductive membranes base layer, material are Nafion117 ion-conductive membranes, and membrane edge portion is set there are four the public stream of electrolyte
Road through-hole, having a size of 580mm × 750mm.
The material of coating is ceramic powder (addition binder is mixed into pottery slurry), thickness 0.1mm.
The inner wall surface of the public runner through-hole of four electrolyte is equipped with coating.
Two surfaces of ion-conductive membranes base layer are equipped with rectangular-ambulatory-plane coating, outer edge having a size of 590mm ×
760mm, inward flange 530mm × 680mm.
Processing technology are as follows: the region for being not required to coating coating to ion-conductive membranes base layer carries out insulation blocking, then will mix
It closes in uniform pottery slurry coating to the rectangular-ambulatory-plane region on two surfaces of ion-conductive membranes, and in the public runner through-hole of electrolyte
Wall is carefully smeared, and the region that the ion-conductive membranes that coating finishes are placed in air circulation is dried, and is obtained with covering
The ion-conductive membranes of layer.Batch working can be completed using coating line direct operation, be can also be used to brush manually on a small quantity and be made
Industry is completed.Use this ion-conductive membranes assembling 20kW pile (electrode size is 530mm × 680mm) and carries out charge and discharge cycles,
Test data is shown in Table 2.
Comparative example 3
Nafion117 ion-conductive membranes, having a size of 580mm × 750mm.It is assembling 20kW using the directly dry dress of the membrane material
Pile simultaneously carries out charge and discharge cycles, and test data is shown in Table 2.
Comparative example 4
Nafion117 ion-conductive membranes place it in the electrolysis of 1.4mol/L sulfuric acid system vanadium having a size of 540mm × 690mm
After liquid impregnates 1.5h, size swelling is 580mm × 750mm.20kW pile, which is assembled into, using the membrane material and carries out charge and discharge follows
Ring, test data are shown in Table 2.
Table 2
Embodiment 3
Ion-conductive membranes base layer, material is porous ion conductive membranes, having a size of 500mm × 700mm.
The material of tectum structure is polytetrafluoroethylene (PTFE), thickness 0.15mm.
One surface of ion-conductive membranes base layer be equipped with rectangular-ambulatory-plane coating, outer edge size 500mm × 700mm,
Inward flange size 450mm × 620mm；Four cross sectional sides of ion-conductive membranes base layer are equipped with coating.
Processing technology are as follows: the region for being not required to coating coating to ion-conductive membranes base layer carries out insulation blocking, by poly- four
Vinyl fluoride, which is dissolved in acetone, forms polytetrafluoroethylsolution solution.It is using resin spray apparatus that uniformly mixed polytetrafluoroethylene (PTFE) is molten
Liquid be sprayed on the rectangular-ambulatory-plane region of ion-conductive membranes side and four cross sectional sides on, will the ion-conductive membranes that finish of spraying
The region for being placed in air circulation is dried, and obtains the ion-conductive membranes with coating.It is assembled using this ion-conductive membranes
10kW pile (electrode size is 450mm × 620mm) simultaneously carries out charge and discharge cycles, and test data is shown in Table 3.
Comparative example 5
Porous ion conductive membranes, having a size of 500mm × 700mm.It is assembling 10kW pile using the directly dry dress of the membrane material
And charge and discharge cycles are carried out, test data is shown in Table 3.
Comparative example 6
Porous ion conductive membranes place it in deionized water after impregnating 2h having a size of 460mm × 650mm, size swelling
For 500mm × 700mm.10kW pile is assembled into using the membrane material and carries out charge and discharge cycles, and test data is shown in Table 3.
Table 3
Embodiment 4
Ion-conductive membranes base layer, material are non-fluorine ion-conductive membranes, having a size of 600mm × 950mm, if membrane edge portion is equipped with
Dry location hole.
The material of coating is epoxy resin, thickness 0.2mm.
The inner wall surface of location hole is equipped with coating.
Two surfaces of ion-conductive membranes base layer are equipped with rectangular-ambulatory-plane coating, outer edge 600mm × 950mm, inner edge
Edge 550mm × 870mm.
Processing technology are as follows: the region for being not required to coating coating to ion-conductive membranes base layer carries out insulation blocking, by epoxy
Resin, which is dissolved in ethyl alcohol, forms epoxy resin solution.The surrounding of non-fluorine ion-conductive membranes is successively impregnated in epoxy resin solution
In, the depth of ion-conductive membranes short side dipping is 25mm, the depth of long side dipping is 40mm, guarantees that location hole is complete in dipping process
Portion enters the lower section of epoxy resin solution.The region that the non-fluorine ion-conductive membranes that dipping finishes are placed in air circulation is done
It is dry, obtain the ion-conductive membranes with coating.Use this ion-conductive membranes assembling 30kW pile (electrode size for 550mm ×
870mm) and charge and discharge cycles are carried out, test data is shown in Table 4.
Comparative example 7
Non-fluorine ion-conductive membranes, having a size of 600mm × 950mm.It is assembling 30kW pile using the directly dry dress of the membrane material
And charge and discharge cycles are carried out, test data is shown in Table 4.
Comparative example 8
Non-fluorine ion-conductive membranes place it in 2.5mol/L sulfuric acid/hydrochloric acid system electrolyte having a size of 550mm × 870mm
After impregnating 1.5h, size swelling is 600mm × 950mm.30kW pile is assembled into using the membrane material and carries out charge and discharge cycles,
Test data is shown in Table 4.
Table 4
Claims (8)
1. a kind of ion-conductive membranes, including ion-conductive membranes base layer, which is characterized in that the ion-conductive membranes base layer is equipped with
Coating, the swelling ratio of the covering layer material are not higher than 0.5 times of the swelling ratio of the ion-conductive membranes matrix layer material；
At least one surface on two surfaces of the ion-conductive membranes base layer is equipped with rectangular-ambulatory-plane coating；
The outer edge size of the rectangular-ambulatory-plane coating is not less than the peripheral dimension of ion-conductive membranes base layer, and the rectangular-ambulatory-plane is covered
The inward flange size of cap rock is greater than the peripheral dimension of electrode.
2. ion-conductive membranes according to claim 1, it is characterised in that the material of the coating is selected from ceramic powder, second
At least one of alkene-TFE copolymer, polytetrafluoroethylene (PTFE), polyvinyl chloride, polypropylene or epoxy resin.
3. ion-conductive membranes according to claim 1, which is characterized in that the coating with a thickness of 0.01mm-
0.5mm。
4. ion-conductive membranes according to claim 1 or 2 or 3, which is characterized in that the four of the ion-conductive membranes base layer
At least one side of a cross sectional sides is equipped with the coating.
5. ion-conductive membranes according to claim 1 or 2 or 3, which is characterized in that the ion-conductive membranes base layer is equipped with
The inner wall surface of the public runner through-hole of electrolyte, the public runner through-hole of electrolyte is equipped with the coating.
6. ion-conductive membranes according to claim 1 or 2 or 3, which is characterized in that the ion-conductive membranes base layer is equipped with
The inner wall surface of location hole, the location hole is equipped with the coating.
7. the processing technology of ion-conductive membranes, which is characterized in that claims 1 or 2 or 3 covering layer materials are passed through painting
Brush, spraying, bonding, dipping or the mode of hot pressing are engaged in the ion-conductive membranes base layer.
It include ion-conductive membranes as claimed in any one of claims 1 to 6 8. flow battery electricity pushes away.
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| CN110416582B (en) * | 2018-04-26 | 2021-05-11 | 大连融科储能装备有限公司 | Ion exchange membrane with insulating high-strength non-reaction zone and preparation method thereof |
| CN108963158B (en) * | 2018-07-10 | 2021-10-22 | 福建师范大学 | Preparation method of polymer coating film containing P-O bond compound |
| CN111653803B (en) * | 2020-04-29 | 2022-07-01 | 上海电气集团股份有限公司 | Sealing method of flow frame of flow battery |
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| US7947405B2 (en) * | 2004-09-29 | 2011-05-24 | Giner Electrochemical Systems, Llc | Solid polymer electrolyte composite membrane comprising porous ceramic support |
| CN101432906B (en) * | 2006-04-28 | 2011-06-15 | 株式会社Lg化学 | Separator for battery with gel polymer layer |
| CN101488574A (en) * | 2008-01-16 | 2009-07-22 | 中国科学院金属研究所 | Proton exchange film fuel cell stainless steel bi-polar plate and production thereof |
| CN103993329B (en) * | 2014-06-06 | 2017-01-04 | 山东东岳高分子材料有限公司 | Ion-conductive membranes and preparation method thereof |
| CN204088480U (en) * | 2014-09-11 | 2015-01-07 | 四川中物电新能源科技有限公司 | Flow battery charge capacity monitoring device |
| CN104269511A (en) * | 2014-09-30 | 2015-01-07 | 成都赢创科技有限公司 | Flow battery diaphragm and preparing method thereof |
| CN105140543A (en) * | 2015-08-28 | 2015-12-09 | 中国东方电气集团有限公司 | Flow cell ion exchange membrane assembly, preparing method of flow cell ion exchange membrane assembly and flow cell comprising flow cell ion exchange membrane assembly |
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