CN106532081B - A kind of the flow battery perforated membrane with hierarchical porous structure and its preparation and application - Google Patents
A kind of the flow battery perforated membrane with hierarchical porous structure and its preparation and application Download PDFInfo
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- CN106532081B CN106532081B CN201510571868.1A CN201510571868A CN106532081B CN 106532081 B CN106532081 B CN 106532081B CN 201510571868 A CN201510571868 A CN 201510571868A CN 106532081 B CN106532081 B CN 106532081B
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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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
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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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- 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 present invention relates to a kind of flow battery perforated membrane with hierarchical porous structure and its preparations and application, the perforated membrane is so that by one of organic polymer resin or sulfonated polymer resin or two kinds, the above are raw materials, small molecule particle is that the perforated membrane that hard template is prepared is matrix, after submerging phase inversion film-forming, go template agent removing that the perforated membrane with hierarchical porous structure is prepared.The perforated membrane technical process of such hierarchical porous structure is simple, environmental friendly, aperture and controlled porosity, batch production easy to accomplish.Compared with original perforated membrane, the perforated membrane of the hierarchical porous structure can have good capacity retention ratio and preferable battery efficiency by controlling template agent content control hole structure with the battery that this is assembled.
Description
Technical field
The present invention relates to a kind of porous film material of flow battery with hierarchical porous structure, in particular to a kind of to be based on mould
The perforated membrane and its application in all-vanadium flow battery that the preparation of plate method has hierarchical porous structure.
Background technique
Flow battery is a kind of electrochemical energy storage new technology, compared with other energy storage technologies, has system flexible design, stores
Capacitance is big, addressing is free, energy conversion efficiency is high, can advantages, the Ke Yiguang such as deep discharge, safety and environmental protection, maintenance cost be low
It is general to be filled out applied to renewable energy power generations energy storage, emergency power system, stand-by station and electric system peak clippings such as wind energy, solar energy
Paddy etc..All-vanadium flow battery (Vanadium flow battery, VFB) due to highly-safe, stability is good, it is high-efficient,
Service life long (service life > 15 year), it is at low cost the advantages that, be considered to have good application prospect.
Battery diaphragm is the important component in flow battery, it plays barrier positive and negative electrode electrolyte, provides proton biography
The effect in defeated channel.Proton-conducting, chemical stability and ion selectivity of film etc. will directly affect the electrochemistry of battery
Energy and service life；Therefore it is required that film has lower active material permeability (having higher selectivity) and lower face electricity
It hinders (having higher ionic conductivity), while should also have preferable chemical stability and lower cost.Now both at home and abroad
The membrane material used is mainly the Nafion membrane of DuPont Corporation's exploitation, and Nafion membrane is in chemical property and service life etc.
Aspect has excellent performance, but due to expensive, and it is poor to be especially applied in all-vanadium flow battery that there are ion selectivities
The disadvantages of, to limit the industrial applications of the film.Therefore, exploitation has the electricity of highly selective, high stability and low cost
Pond diaphragm is most important.Rather than fluorine ion exchange membrane is due to the presence of ion-exchange group, it is chemical in all-vanadium flow battery
Stability is insufficient for long-term requirement.
In VFB, vanadium ion lotus proton exists in the form of hydrated ion.Since vanadium ion and hydrogen ion are hydrated radius
Difference, can be realized by porous diffusion barrier to vanadium ion and hydrionic Selective Separation.Using perforated membrane as VFB every
Film has the advantages such as chemical stability is good, material selection range is wide, technical maturity easily amplifies, and production cost is low.But perforated membrane pair
The selectivity and proton-conducting of hydrogen ion and vanadium ion are difficult to take into account, therefore improve perforated membrane selectivity, ionic conductivity, into
And it realizes its sizable application and has great importance.
Summary of the invention
Present invention aims at the perforated membranes with hierarchical porous structure for preparing a kind of aperture and controlled porosity, are keeping
Its selectivity to hydrogen ion and vanadium ion is improved on the basis of perforated membrane ionic conductivity, provides a kind of flow battery with having
Application of the perforated membrane of hierarchical porous structure in flow battery, especially application of such film in all-vanadium flow battery.
To achieve the above object, The technical solution adopted by the invention is as follows:
The perforated membrane with hierarchical porous structure is by organic polymer resin or sulfonated polymer resin
One or two or more kinds are raw material, and small molecule particle is that the perforated membrane that hard template is prepared is matrix, by submerging inversion of phases
After method film-forming, go template agent removing that the perforated membrane with hierarchical porous structure is prepared.
The organic polymer resin is polyether sulfone, polyacrylonitrile, polyimides, polyethers ketone, polytetrafluoroethylene (PTFE), gathers
Vinylidene, polybenzimidazoles or polyvinyl pyridine；Sulfonated polymer resin is that sulfonated polysulfone, sulfonated polyimide, sulfonation are poly-
Ether ketone or sulfonate polybenzimidazole；Small molecule particle is phenolphthalein, nano silica, nanometer calcium carbonate or nanometer ZIF-8 points
Son sieve.
The porosity of the perforated membrane is 5~90%, with a thickness of 40~500 μm；The perforated membrane include macropore, mesoporous and
Aperture, aperture are located on the hole wall of mesoporous and/or macropore, and macropore is having a size of 0.5 μm~140 μm；Intermediate pore size be 0.1 μm~
0.5μm；Orifice size is 0.1nm~100nm；Preferred scope: macropore is having a size of 20 μm~120 μm；Intermediate pore size be 0.1 μm~
0.2μm；Orifice size is 0.1~100nm.
The perforated membrane with hierarchical porous structure is prepared using following steps:
(1) organic polymer resin or sulfonated polymer resin, small molecule template are dissolved or dispersed in organic solvent
In, 20~60h is sufficiently stirred at being 20~100 DEG C in temperature, blend solution is made；Wherein organic polymer resin or sulfonation are high
Molecule resin concentration is between 10~60wt%；Small molecule template agent concentration is 1~50wt% of macromolecule resin content；
(2) blend solution prepared by step (1) is poured over nonwoven fabric base bottom or be poured directly on glass plate, volatilized molten
Agent 0~60 second, its mass-impregnation is then entered into 10~120s in the poor solvent of resin, is prepared at a temperature of 0~50 DEG C more
Pore membrane；The thickness of film is between 40~500 μm；
(3) according to template used, perforated membrane prepared by step (2) is placed in corresponding solvent and is impregnated at least
48h is to remove template；
(4) taking out in step (3) sufficiently goes the film after template agent removing to be dipped in deionized water, stands 12h；Finally prepare
Perforated membrane with hierarchical porous structure.
If template does not completely remove in the perforated membrane after step (3) immersion, perforated membrane is taken out from solvent, is further continued for
Perforated membrane is dipped in again sufficiently to remove the template in striping in fresh solvent, i.e., repeatedly the process of step (3) 2 times with
On.
The organic solvent is one of DMSO, DMAC, NMP, DMF or two kinds or more；The poor solvent of resin is first
One of alcohol, ethyl alcohol, propyl alcohol or isopropanol or two kinds or more.
The solvent for removing phenolphthalein template is one of methanol, ethyl alcohol, isopropanol or sodium hydroxide or two kinds or more；It goes
Except the solvent of Colloidal Nanosize Silica Template agent is sodium hydroxide and/or potassium hydroxide；Remove nanometer calcium carbonate or ZIF-8 molecular sieve
The solvent of template is sulfuric acid, hydrochloric acid or acetic acid.
For in flow battery, the flow battery to include all-vanadium flow battery, zinc/cerium flow battery, vanadium/bromine liquid stream
Battery or iron/chrome liquor galvanic battery.
Beneficial achievement of the invention:
1. the perforated membrane prepared by the present invention with hierarchical porous structure is applied in flow battery, using hard template method, benefit
The evenly dispersed or dissolution in good solvent with hard template, and the principle being precipitated in poor solvent (water), then with appropriate molten
Agent remove template, by template agent content can Effective Regulation pore size, the selectivity of film is effectively improved, to obtain more
Good battery performance；By change templating species can also Effective Regulation membrane aperture and porosity size.Template is due to insoluble
It is precipitated in poor solvent, the template of precipitation can be used suitable solvent to dissolve or etch and remove.
2. the perforated membrane prepared by the present invention with hierarchical porous structure can be contained by changing Template Types and template
Amount, to regulate and control the selectivity and conductibility of such film.
3. the perforated membrane prepared by the present invention with hierarchical porous structure, aperture is adjustable, mass production easy to accomplish.
3. the hard template method preparation that the present invention uses has the perforated membrane of hierarchical structure, ion exchange resin need to be only used
Aqueous solution and cleaning solvent, preparation process clean and environmental protection.
4. type and use scope that the present invention has widened flow battery membrane material.
5. the present invention can be achieved to the battery efficiency of flow battery especially all-vanadium flow battery and the controllability of capacity.
Detailed description of the invention
Fig. 1 has the preparation process schematic diagram of the perforated membrane of hierarchical porous structure；
Fig. 2 is not added with template and removes the SEM figure of film before and after template agent removing；
A- is not added with the perforated membrane section SEM figure of template, perforated membrane section SEM figure of the b- containing template, and c- removes mould
The section SEM figure of perforated membrane after plate agent, porous film surface SEM figure of the d- containing template；The perforated membrane that a '-is not added with template is cut
Face SEM enlarged drawing, perforated membrane section SEM enlarged drawing of the b '-containing template, c '-remove the section SEM of perforated membrane after template agent removing
Figure, d '-remove the surface SEM enlarged drawing of perforated membrane after template agent removing；
Fig. 3 removes the high power SEM figure of film before and after template agent removing；A- removes the section high power SEM figure enlarged drawing of template agent removing cephacoria,
B- removes the section high power SEM figure enlarged drawing of template agent removing caudacoria, scale: 200nm.
Perforated membrane prepared by 2 different templates agent content of Fig. 4 embodiment 1 and embodiment with hierarchical porous structure is assembled
The volume test figure of battery.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Comparative example
9.975g polyether sulfone and 0.525g sulfonated polyether-ether-ketone are dissolved in 19.5g DMAC, stir 48 hours, formation
Polymer solution is laid in glass plate, then immerses in 4L water rapidly, solidification, forms porous septum, and film thickness is 175 μm of (films
Cross section structure it is as shown in Figure 2 a, shown in section cortex construction such as Fig. 2 a ').
All-vanadium flow battery is assembled using the perforated membrane with hierarchical porous structure of preparation, wherein Catalytic Layer is active carbon
Felt, bipolar plates are graphite plate, and film effective area is 9cm2, current density 80mA.cm-2, vanadium ion concentration is in electrolyte
1.50mol L-1, H2SO4Concentration is 3mol L-1.Since the section cortex of film is fine and close (Fig. 2 a '), the surface resistance of film is larger, institute's group
The flow battery of dress can not normal charge and discharge.
Embodiment 1
The phenolphthalein of 9.975g polyether sulfone, 0.525g sulfonated polyether-ether-ketone and 1.0506g are dissolved in 19.5g DMAC, stirring 48
A hour, the polymer solution of formation are laid in glass plate, then immerse in 4L water rapidly, and solidification forms porous septum, film
With a thickness of 175 μm.Porous septum obtained is impregnated 48 hours in ethanol, to prepare except the phenolphthalein template in striping
At the perforated membrane with hierarchical porous structure.Then washing continues to be soaked in ethyl alcohol to completely remove the template in film.It is porous
Film intermediate pore size is 0.1 μm~0.2 μm, and orifice size is 0.1~100nm.Utilize the porous with hierarchical porous structure of preparation
Film assembles all-vanadium flow battery, and wherein Catalytic Layer is activated carbon felt, and bipolar plates are graphite plate, and film effective area is 9cm2, electric current
Density is 80mA.cm-2, vanadium ion concentration is 1.50mol L in electrolyte-1, H2SO4Concentration is 3molL-1.The liquid stream assembled
Battery coulombic efficiency is 94.39%, voltage efficiency 85.47%, energy efficiency 80.40%, and battery recycles it at 70
Interior, capacity is without significantly decaying (Fig. 4 embodiment 1).
Embodiment 2
The phenolphthalein of 9.975g polyether sulfone, 0.525g sulfonated polyether-ether-ketone and 2.1g are dissolved in 19.5g DMAC, stir 48
Hour, the polymer solution of formation is laid in glass plate, then immerses in 4L water rapidly, and solidification forms porous septum, film thickness
Degree is 175 μm.Porous septum obtained is impregnated 48 hours in ethanol, to be prepared except the phenolphthalein template in striping
Perforated membrane with hierarchical porous structure.Then washing continues to be soaked in ethyl alcohol to completely remove the template in film.Utilize system
The standby perforated membrane with hierarchical porous structure assembles all-vanadium flow battery, and wherein Catalytic Layer is activated carbon felt, and bipolar plates are graphite
Plate, film effective area are 9cm2, current density 80mA.cm-2, vanadium ion concentration is 1.50mol L in electrolyte-1, H2SO4It is dense
Degree is 3mol L-1.The flow battery coulombic efficiency assembled is 85.31%, voltage efficiency 89.82%, and energy efficiency is
76.62%, for battery within 40 circulations, capacity sharply declines (Fig. 4 embodiment 2).
Fig. 4 in casting solution by adding different templates agent content, using going prepared after template agent removing have classification
The monocell of the perforated membrane assembling of pore structure carries out battery testing, and it is moderate to prepare aperture by control template agent content for discovery
Hole can Effective Regulation battery capacity retention ratio.
Embodiment 3
The phenolphthalein of 9.975g polyether sulfone, 0.525g sulfonated polyether-ether-ketone and 3.15g are dissolved in 19.5g DMAC, stir 48
Hour, the polymer solution of formation is laid in glass plate, then immerses in 4L water rapidly, and solidification forms porous septum, film thickness
Degree is 175 μm.Porous septum obtained is impregnated 48 hours in ethanol, to be prepared except the phenolphthalein template in striping
Perforated membrane with hierarchical porous structure.Then washing continues to be soaked in ethyl alcohol to completely remove the template in film.Utilize system
The standby perforated membrane with hierarchical porous structure assembles all-vanadium flow battery, and wherein Catalytic Layer is activated carbon felt, and bipolar plates are graphite
Plate, film effective area are 9cm2, current density 80mA.cm-2, vanadium ion concentration is 1.50mol L in electrolyte-1, H2SO4It is dense
Degree is 3mol L-1.The flow battery coulombic efficiency assembled is 83.22%, voltage efficiency 89.10%, and energy efficiency is
74.15%.
Fig. 1 is the preparation process schematic diagram of the perforated membrane with hierarchical porous structure；By polyether sulfone, sulfonated polyether-ether-ketone and phenol
Phthalein, which is dissolved in certain proportion in DMAc, to be sufficiently stirred to form uniform solution, and above-mentioned casting solution is coated uniformly on nothing after standing
In woven fabric or glass plate, 0~60s of solvent flashing is transferred in water, and phenolphthalein template not soluble in water and resin are in water simultaneously
It is precipitated, forms the perforated membrane with hierarchical porous structure after being removed with ethyl alcohol.It is controllable porous according to the content of added template
The aperture of film and porosity size.
It is tied it can be seen that being not added with perforated membrane prepared by the casting solution of template in apparent finger print hole from Fig. 2 a
Structure, cortex (Fig. 2 a ') compact structure.Fig. 2 b is to add perforated membrane prepared by the casting solution of template, due to phenolphthalein template
Hydrophobic property, more mechanical and thermal properties of film forming are influenced in film forming procedure so that the Cross Section Morphology of film occur it is obvious
Variation, finger print hole disappear, and the section of film is fine and close (Fig. 2 b ').When removing striping inner template agent with ethyl alcohol, the whole pattern of film is not sent out
There is apparent pore structure (Fig. 2 c ') in the section of raw significant change (Fig. 2 c), film, show that ethyl alcohol can be used as removing the molten of template
Agent, and will not influence when removing template agent removing the overall structure of film.It is in from the surface that Fig. 2 d can be seen that template agent removing cephacoria
The structure of even compact, and go after template agent removing (Fig. 2 d '), the surface of film is in the structure in apparent hole.
From high power SEM Fig. 3 can be seen that template agent removing before (Fig. 3 a), the section of film is in the structure of uniform compact, and goes
After template agent removing (Fig. 3 b), the section of film is in obvious hierarchical porous structure.By being characterized above it can be seen that being template using phenolphthalein
Agent, ethyl alcohol are that the solvent of template agent removing can prepare the perforated membrane with hierarchical porous structure.
Claims (7)
1. a kind of perforated membrane of flow battery with hierarchical porous structure, it is characterised in that: described with hierarchical porous structure
Perforated membrane is so that by one of organic polymer resin or sulfonated polymer resin or two kinds, the above are raw material, small molecule particles
It is matrix for the perforated membrane that hard template is prepared, after submerging phase inversion film-forming, template agent removing is gone to be prepared
Perforated membrane with hierarchical porous structure；
Small molecule particle is phenolphthalein, nano silica, nanometer calcium carbonate or nanometer ZIF-8 molecular sieve；
The perforated membrane with hierarchical porous structure is prepared using following steps:
(1) organic polymer resin or sulfonated polymer resin, small molecule template are dissolved or dispersed in organic solvent,
Temperature is 20~60 h to be sufficiently stirred at 20~100 DEG C blend solution is made；Wherein organic polymer resin or sulfonated polymer
Resin concentration is between 10~60 wt%；Small molecule template agent concentration is 1~50 wt% of macromolecule resin content；
(2) blend solution prepared by step (1) is poured over nonwoven fabric base bottom or be poured directly on glass plate, solvent flashing 0
~60 seconds, its mass-impregnation is then entered into 10~120 s in the poor solvent of resin, is prepared at a temperature of 0~50 DEG C porous
Film；The thickness of film is between 40~500 μm；
(3) according to template used, perforated membrane prepared by step (2) is placed in corresponding solvent impregnate at least 48 h with
Remove template；
(4) taking out in step (3) sufficiently goes the film after template agent removing to be dipped in deionized water, stands 12 h；Final preparation is provided
There is the perforated membrane of hierarchical porous structure；
The poor solvent of resin is water；
The solvent for removing phenolphthalein template is one of methanol, ethyl alcohol, isopropanol or sodium hydroxide or two kinds or more；Removal is received
The solvent of rice silica template agent is sodium hydroxide and/or potassium hydroxide；Remove nanometer calcium carbonate or ZIF-8 Molecular Sieves as Template
The solvent of agent is sulfuric acid, hydrochloric acid or acetic acid.
2. the perforated membrane according to claim 1 with hierarchical porous structure, it is characterised in that: the organic polymer tree
Rouge is polyether sulfone, polyacrylonitrile, polyimides, polyethers ketone, polytetrafluoroethylene (PTFE), Kynoar, polybenzimidazoles or poly- second
Annulated pyridine；Sulfonated polymer resin is sulfonated polysulfone, sulfonated polyimide, sulfonated polyether ketone or sulfonate polybenzimidazole.
3. the perforated membrane according to claim 1 with hierarchical porous structure, it is characterised in that: the hole of the perforated membrane
Rate is 5~90%, with a thickness of 40~500 μm；The perforated membrane includes macropore, mesoporous and aperture, and aperture is located at mesoporous and/or big
On the hole wall in hole, macropore is having a size of 0.5 μm~140 μm；Intermediate pore size is 0.1 μm~0.5 μm；Orifice size is 0.1 nm
~100 nm.
4. the perforated membrane according to claim 3 with hierarchical porous structure, it is characterised in that: the macropore is having a size of 20
μm~120 μm；Intermediate pore size is 0.1 μm~0.2 μm；Orifice size is 0.1~100 nm.
5. the perforated membrane described in accordance with the claim 1 with hierarchical porous structure, it is characterised in that:
If template does not completely remove in the perforated membrane after step (3) immersion, perforated membrane is taken out from solvent, being further continued for will be more
Pore membrane be dipped in again in fresh solvent with sufficiently remove striping in template, i.e., repeatedly the process of step (3) 2 times or more.
6. the perforated membrane described in accordance with the claim 1 with hierarchical porous structure, it is characterised in that:
The organic solvent is one of DMSO, DMAC, NMP, DMF or two kinds or more.
7. a kind of application of any perforated membrane with hierarchical porous structure of claim 1-3, it is characterised in that: be used for liquid
In galvanic battery, the flow battery includes all-vanadium flow battery, zinc/cerium flow battery, vanadium/bromine flow battery or iron/chrome liquor
Galvanic battery.
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| EP4104228A4 (en) * | 2020-02-14 | 2023-12-20 | Massachusetts Institute of Technology | Methods of formulating porous electrodes using phase inversion, and resulting devices from the same |
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| KR102028535B1 (en) * | 2017-03-31 | 2019-10-04 | 코오롱인더스트리 주식회사 | Ion exchanging membrane, method for manufacturing the same and energy storage system comprising the same |
| CN109873188A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | Application of the cluster ion exchange membrane in alkaline system zinc-iron flow battery |
| CN108878936B (en) * | 2018-07-03 | 2021-02-19 | 大连理工大学 | Hydrophobic side chain modified alkyl sulfonated polybenzimidazole amphoteric membrane and preparation method thereof |
| CN109233274B (en) * | 2018-09-13 | 2020-12-15 | 吉林大学 | Polybenzimidazole membrane with nano porous structure and preparation method thereof |
| CN110943237B (en) * | 2018-09-21 | 2021-09-28 | 中国科学院大连化学物理研究所 | Application of ion-conducting membrane in flow battery |
| CN111082117B (en) * | 2018-10-18 | 2021-06-01 | 中国科学院大连化学物理研究所 | Molecular sieve composite membrane and preparation method and application thereof |
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| CN110299551A (en) * | 2019-06-03 | 2019-10-01 | 贵州梅岭电源有限公司 | A kind of preparation method of proton exchange membrane used for all-vanadium redox flow battery |
| CN112151843A (en) * | 2019-06-28 | 2020-12-29 | 长沙理工大学 | Preparation method of neutral redox flow battery system |
| CN112652797B (en) * | 2019-10-11 | 2022-03-08 | 中国科学院大连化学物理研究所 | Porous ion-conducting membrane with pore size in gradient distribution, preparation and application |
| CN111082090A (en) * | 2019-12-04 | 2020-04-28 | 大连融科储能技术发展有限公司 | Bipolar plate with nano micro-pit surface and preparation method and application thereof |
| CN113036174B (en) * | 2019-12-09 | 2022-05-31 | 中国科学院大连化学物理研究所 | Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof |
| CN112940306B (en) * | 2019-12-10 | 2022-04-15 | 中国科学院大连化学物理研究所 | Porous ion conduction membrane for flow battery and preparation and application thereof |
| CN114649553B (en) * | 2022-02-11 | 2023-04-14 | 南京工业大学 | Porous membrane loaded by zeolite molecular sieve nanosheets, preparation method and application of porous membrane in zinc-based flow battery |
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| KR101852925B1 (en) * | 2011-11-29 | 2018-04-30 | 삼성전자주식회사 | Hybrid porous structured material, method of preparing hybrid porous structure material, membrane including hybrid porous structured material, and water treatment device including membrane including hybrid porous structured material |
| CN102755841B (en) * | 2012-08-02 | 2014-02-26 | 浙江工商大学 | Preparation method and product of hydrophobic PVDF (Polyvinylidene Fluoride) microporous membrane with beta crystalline phase structure |
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