CN111224123B - Preparation method of composite ion-conducting membrane, composite membrane and application thereof - Google Patents

Preparation method of composite ion-conducting membrane, composite membrane and application thereof Download PDF

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CN111224123B
CN111224123B CN201811417439.9A CN201811417439A CN111224123B CN 111224123 B CN111224123 B CN 111224123B CN 201811417439 A CN201811417439 A CN 201811417439A CN 111224123 B CN111224123 B CN 111224123B
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conducting membrane
water
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membrane
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CN111224123A (en
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李先锋
鲁文静
张华民
史丁秦
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Zhongke Chemical Dalian Technology Industry Co ltd
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
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Abstract

The invention relates to a preparation method of a composite ion-conducting membrane, a composite membrane and application thereof, wherein the composite ion-conducting membrane with a three-layer structure is prepared by a three-time solvent evaporation phase separation method and is finally placed in water; the preparation process comprises preparing single-layer ion-conducting membrane by solvent evaporation phase separation method; then coating a layer of polymer solution on the surface of the ion-conducting membrane as an intermediate layer, and evaporating and separating the solvent to prepare a double-layer composite ion-conducting membrane; coating a layer of polymer solution on the surface of the middle layer of the double-layer composite ion-conducting membrane, and evaporating and separating the solvent to obtain the composite ion-conducting membrane with a three-layer structure; finally, the composite ion-conducting membrane is soaked in water to obtain the required composite ion-conducting membrane. Compared with the traditional ion conduction membrane, the water-soluble organic polymer resin in the ion conduction membrane on the surface layer of the composite ion conduction membrane is dissolved in water to form pores, so that the composite ion conduction membrane has the characteristics of a porous ion conduction membrane and an ion conduction membrane, and the assembled battery has high battery efficiency and long cycle life. The preparation method of the high-stability composite ion conduction membrane has the advantages of simple operation process, environment-friendly process, economy and effectiveness, and is easy to realize batch production.

Description

Preparation method of composite ion-conducting membrane, composite membrane and application thereof
Technical Field
The invention relates to a preparation method of a high-stability composite ion conduction membrane for a flow battery, in particular to application of water-soluble organic polymer resin in an all-vanadium flow battery.
Background
The flow battery is a new electrochemical energy storage technology, and compared with other energy storage technologies, the flow battery has the advantages of flexible system design, large storage capacity, free site selection, high energy conversion efficiency, deep discharge, safety, environmental protection, independent design of power and capacity, low maintenance cost and the like, and can be widely applied to the aspects of power generation and energy storage of renewable energy sources such as wind energy, solar energy and the like, an emergency power supply system, a standby power station, an electric power system, peak clipping and valley filling and the like. The full Vanadium Flow Battery (VFB) has good application prospect due to its advantages of high safety, good stability, high efficiency, long service life (the service life is more than 15 years), low cost, etc.
The battery diaphragm is an important component in the flow battery and plays a role in blocking electrolyte of the positive electrode and the negative electrode and providing a proton transmission channel. The proton conductivity, chemical stability, ion selectivity, etc. of the membrane will directly affect the electrochemical performance and service life of the cell. The membrane should therefore have a high ion selectivity and a high proton conductivity, while also having a good chemical stability and a low cost. The membrane material used at home and abroad at present is mainly a Nafion membrane of perfluorosulfonic acid developed by DuPont company in America, which has high proton conductivity and excellent chemical stability, but is expensive, and has the defects of poor ion selectivity and the like when being applied to an all-vanadium flow battery, so that the industrial application of the membrane is limited. And the chemical stability of the non-fluoride ion conducting membrane in the all-vanadium flow battery is insufficient to meet the long-term use requirement of the battery due to the existence of ion exchange groups. Therefore, it is important to develop a battery separator having high selectivity, high stability and low cost.
Disclosure of Invention
The invention aims to develop a method for preparing a composite ion-conducting membrane for a flow battery, which has high conductivity, high selectivity and high chemical stability, and the membrane prepared by the method is particularly suitable for application in all-vanadium flow batteries.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
preparing a composite ion-conducting membrane with a three-layer structure by a three-time solvent evaporation phase separation method, and finally placing the composite ion-conducting membrane in water to obtain the composite ion-conducting membrane; the preparation process comprises preparing single-layer ion-conducting membrane by solvent evaporation phase separation method; then coating a layer of polymer solution on the surface of the ion-conducting membrane as an intermediate layer, and evaporating and separating the solvent to prepare a double-layer composite ion-conducting membrane; coating a layer of polymer solution on the surface of the middle layer of the double-layer composite ion-conducting membrane, and evaporating and separating the solvent to obtain the composite ion-conducting membrane with a three-layer structure; finally, the composite ion-conducting membrane is soaked in water to obtain the required composite ion-conducting membrane.
The composite ion-conducting membrane consists of two outer surface layer ion-conducting membranes and a middle layer ion-conducting membrane; the ion conducting membrane of the outer surface layer is prepared by taking water-insoluble organic polymer resin without ion exchange groups and water-soluble organic polymer resin as raw materials; the intermediate layer ion conduction membrane is prepared by taking water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange groups, or water-insoluble organic polymer resin and high-hydrophilicity water-insoluble organic polymer resin without ion exchange groups, or high-hydrophilicity water-insoluble organic polymer resin as raw materials; after the film is solidified into a film by a solvent evaporation phase separation method, the film is soaked in water to obtain the water-based anti-aging coating.
The stability of the ion-conducting membrane of the two outer surface layers is higher than that of the ion-conducting membrane of the middle layer.
When the intermediate ion-conducting membrane is made of water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange groups, or water-insoluble organic polymer resin without ion exchange groups and high-hydrophilic water-insoluble organic polymer resin, the stability of the water-insoluble organic polymer resin of the two outer surface layers is higher than that of the water-insoluble organic polymer resin of the intermediate ion-conducting membrane, wherein the stability of the resin is characterized by the tensile strength of the resin per se, that is, the tensile strength of the water-insoluble organic polymer resin selected for the ion-conducting membrane of the two outer surface layers is higher than that of the water-insoluble organic polymer resin selected for the ion-conducting membrane of the intermediate layer: the tensile strength of the water-insoluble organic polymer resin is between 3 and 100 MPa; the non-water soluble organic polymer resin without ion exchange groups is one or more than two of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyether sulfone, polysulfone, polyether ketone, polystyrene and polytetrafluoroethylene; the water-soluble organic high molecular resin is one or more of polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and polylactic acid;
the high hydrophilic water-insoluble organic polymer resin is one or more of sulfonated polymers such as sulfonated polyether ether ketone, sulfonated polyether ketone, sulfonated poly (arylene sulfide ether ketone), sulfonated poly (fluorenyl ether ketone), sulfonated poly (tetramethyl diphenyl ether ketone), sulfonated polyoxadiazole and sulfonated polystyrene, and quaternized polymers such as quaternized poly (tetramethyl diphenyl ether sulfone), quaternized poly (phthalazinone ether ketone) and polybenzimidazole.
The sulfonation degree of the high hydrophilic water-insoluble organic polymer resin is between 30 and 120 percent; the quaternization degree of the high hydrophilic water-insoluble organic polymer resin is between 30 and 120 percent.
The preparation method of the high-stability composite ion conduction membrane comprises the following steps:
(1) dissolving water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange group in organic solvent, and stirring at 10-80 deg.C for 2-48h to obtain polymer solution; wherein the final concentration of the water-insoluble organic polymer resin containing no ion exchange group is 10-50 wt%; the final concentration of the water-soluble organic polymer resin is between 5 and 30 weight percent;
(2) directly pouring the polymer solution prepared in the step (1) onto a glass plate or a stainless steel plate, volatilizing the solvent for 0-60s, and heating at 40-150 ℃ to evaporate the solvent; preparing to obtain a single-layer ion-conducting membrane, wherein the thickness of the single-layer ion-conducting membrane is between 10 and 50 mu m;
(3) dissolving water-insoluble organic polymer resin without ion exchange group and water-soluble organic polymer resin in organic solvent, or dissolving water-insoluble organic polymer resin without ion exchange group and highly hydrophilic water-insoluble organic polymer resin in organic solvent, or dissolving highly hydrophilic water-insoluble organic polymer resin in organic solvent, and stirring at 10-80 deg.C for 2-48h to obtain polymer solution; wherein the final concentration of the water-insoluble organic polymer resin containing no ion exchange group is 10-50 wt%; the final concentration of the water-soluble organic polymer resin is between 5 and 30 weight percent; the final concentration of the high hydrophilic water-insoluble organic polymer resin is between 5 and 30 percent;
(4) pouring the polymer solution prepared in the step (3) onto the single-layer ion-conducting membrane prepared in the step (2), volatilizing the solvent for 0-60s, and heating at 40-150 ℃ to evaporate the solvent; preparing to obtain a double-layer composite ion-conducting membrane, wherein the thickness of the double-layer composite ion-conducting membrane is between 20 and 100 mu m;
(5) dissolving water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange group in organic solvent, and stirring at 10-80 deg.C for 2-48h to obtain polymer solution. Wherein the final concentration of the water-insoluble organic polymer resin containing no ion exchange group is 10-50 wt%; the final concentration of the water-soluble organic polymer resin is between 5 and 30 weight percent;
(6) pouring the polymer solution prepared in the step (5) on the double-layer composite ion-conducting membrane prepared in the step (4), volatilizing the solvent for 0-60s, and heating at the temperature of 40-150 ℃ to evaporate the solvent to dryness; preparing the composite ion-conducting membrane with the three-layer structure, wherein the thickness of the composite ion-conducting membrane with the three-layer structure is 30-150 mu m;
(7) and (3) soaking the three-layer composite ion-conducting membrane obtained in the step (6) in water at 25-60 ℃ for at least 12h to dissolve water-soluble polymer resin in the ion-conducting membranes on the two outer surface layers of the three-layer composite ion-conducting membrane to form pores, so as to obtain the required composite ion-conducting membrane, wherein the two outer surface layers are of a porous structure, the pore diameter is 0.001-10nm, preferably 0.001-1nm, and the middle layer is of a compact structure.
The organic solvent is one or more than two of DMAC, NMP and DMF.
The surface layer of the composite ion conduction membrane is of a porous structure, and the aperture is 0.001-10 nm; the intermediate layer is a compact structure, and the thickness of the composite ion-conducting membrane is 30-150 mu m.
The preparation method is based on the traditional solvent evaporation phase separation method for preparing the ion conduction membrane, and the substrate sequentially comprises a glass plate or a stainless steel plate, a single-layer ion conduction membrane and a double-layer composite ion conduction membrane consisting of two layers of single-layer ion conduction membranes;
the high conductivity ion conducting membrane may be used in a flow battery including, but not limited to, an all vanadium flow battery, a zinc/cerium flow battery, a vanadium/bromine flow battery, an iron/chromium flow battery, a zinc/bromine flow battery, a zinc/iron flow battery, a zinc/nickel flow battery, or a zinc/iodine flow battery.
The invention has the following beneficial results:
1. the preparation method of the high-stability composite ion conduction membrane has the advantages of simple process, convenient operation, economy, environmental protection and easy realization of mass production.
2. The porous structures on the surface and near-surface region of the high-stability composite ion conduction membrane prepared by the invention and the excellent mechanical and chemical stability of the adopted water-insoluble organic polymer resin without ion exchange groups improve the selectivity and chemical stability of the membrane; the porous structures on the surface and the near-surface region of the composite ion conduction membrane and the high hydrophilicity of the water-soluble organic polymer resin or the high-hydrophilicity water-insoluble polymer resin in the internal ion conduction membrane jointly improve the conductivity of the membrane, so that the prepared composite ion conduction membrane has high selectivity, high conductivity and high stability.
3. The preparation method of the high-stability composite ion-conducting membrane can simply and flexibly regulate the pore diameter and pore diameter distribution of the surface and near-surface regions of the membrane and the selectivity and conductivity of the intermediate ion-conducting membrane by changing the types and contents of the water-soluble organic polymer resin or the high-hydrophilic non-water-soluble organic polymer resin in the two outer surface layer ion-conducting membranes and the intermediate ion-conducting membrane, thereby realizing the controllability of the performance of the composite ion-conducting membrane.
4. The invention widens the variety and application range of membrane materials for the flow battery.
5. The method can realize the controllability of the battery efficiency of the redox flow battery, particularly the all-vanadium redox flow battery.
Drawings
1. FIG. 1 is a schematic diagram of a process for preparing composite ion-conducting membranes of examples 1-5.
2. FIG. 2 is a comparison of vanadium ion permeability of composite ion-conducting membranes prepared in examples 1-5 with that of comparative example 5 and Nafion 115.
3. FIG. 3 is a plot of the sheet resistance of the composite ion-conducting membranes prepared in examples 1-5 and in comparison to comparative example 5 and Nafion 115.
4. FIG. 4 is a graph of the efficiency of assembled cells of composite ion-conducting membranes prepared in examples 1-5 and compared to comparative example 5 and Nafion 115.
5. FIG. 5 is a cycle performance test of cells assembled with composite ion conductive membranes prepared in examples 1-5.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example 1
Dissolving 63g of polyether sulfone (PES) and 42g of polyvinylpyrrolidone (PVP) in 195g of DMAC, stirring for 24 hours to form a uniform polymer solution, standing at 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, spreading the polymer solution on a glass plate, transferring the glass plate to a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature, placing the glass plate in water for more than 12 hours to obtain a PES/PVP ion conduction membrane, wherein the thickness of the prepared PES/PVP ion conduction membrane is 45 mu m. The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2The voltage efficiency under the current density condition of (1) is about 75%, which is much lower than that of the commercial perfluorosulfonic acid membrane Nafion 115 membrane assembled all-vanadium flow battery (88.30%). And the battery is at 80mAcm-2The cycle life under the current density condition of (2) is 50 charge-discharge cycles.
Comparative example 2
36g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and 9g of polyvinylpyrrolidone (PVP) were dissolved in 255g of DMAC, stirred for 24 hours to form a uniform polymer solution, and then left to stand at 25-50 ℃ for 2 hours or more to removeAnd (3) flatly paving the polymer solution on a glass plate, transferring the glass plate to a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature, and placing the glass plate in water for more than 12 hours to prepare the PVDF-HFP/PVP ion conduction membrane, wherein the thickness of the prepared PVDF-HFP/PVP ion conduction membrane is 34 mu m. The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2The voltage efficiency under current density conditions of about 76% is much lower than that of commercial Nafion 115 membrane-assembled all-vanadium flow batteries (88.30%). And the battery is at 80mA cm-2The cycle life under the current density condition of (2) was 30 charge-discharge cycles.
Comparative example 3
Dissolving 45g of sulfonated polyether ether ketone (SPEEK, the sulfonation degree is 80%) in 255g of DMAC, stirring for 24 hours to form a uniform polymer solution, standing at the temperature of 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, flatly paving the polymer solution on a glass plate, transferring the glass plate to a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature to obtain the SPEEK ion conduction membrane, wherein the thickness of the prepared SPEEK ion conduction membrane is 30 mu m; the prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mA cm-2The coulombic efficiency under the current density condition of (1) is about 80%, which is far lower than that of the commercial Nafion 115 membrane assembled all-vanadium flow battery (93.38%). And the battery is at 80mA cm-2The cycle life under the current density condition of (2) is 10 charge-discharge cycles.
Comparative example 4
36g of polyvinylidene fluoride (PVDF) and 9g of polyvinyl alcohol (PEG) were dissolved in 255g of DMAnd stirring for 24 hours in AC to form a uniform polymer solution, standing for more than 2 hours at the temperature of 25-50 ℃ to remove air bubbles in the solution, flatly paving the polymer solution on a glass plate, transferring the glass plate to a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature, and placing the glass plate in water for more than 12 hours to prepare the PVDF/PEG ion conduction membrane, wherein the thickness of the prepared PVDF/PEG ion conduction membrane is 40 mu m. The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mA cm-2The coulombic efficiency under the current density condition of (1) is about 85%, which is far lower than that of the commercial Nafion 115 membrane assembled all-vanadium flow battery (93.38%). And the battery is at 80mA cm-2The cycle life under the current density condition of (2) is 20 charge-discharge cycles.
Comparative example 5
36g of Polystyrene (PS) and 45g of polybenzimidazole (PBI, the quaternization degree of which is 100%) are dissolved in 219g of DMAC, the mixture is stirred for 24 hours to form a uniform polymer solution B, then the mixture is kept stand at 25-50 ℃ for more than 2 hours to remove bubbles in the solution, the polymer solution is flatly spread on a glass plate, the glass plate is transferred to a 50 ℃ hot bench to be heated for 3-12 hours after being cooled at room temperature, the glass plate is placed in water for more than 12 hours to prepare the PS/PBI ion conduction membrane, and the thickness of the prepared PS/PBI ion conduction membrane is 45 microns. The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mA cm-2The coulombic efficiency under the current density condition of (1) is about 90%, the voltage efficiency is about 82%, and both are lower than those of the commercial Nafion 115 membrane assembled all-vanadium flow battery (93.38%) and the voltage efficiency (88.30%). And the battery is at 80mA cm-2The cycle life under the current density condition of (2) is 40 charge-discharge cycles.
Example 1
(1)63g of polyether sulfone (PES, tensile strength 50MPa) and 42g of polyvinylpyrrolidone (PVP) are dissolved in 195g of DMAC, stirred for 24 hours to form a uniform polymer solution A, then kept stand at 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, the polymer solution A is laid on a glass plate, then the glass plate is transferred to a 50 ℃ hot table to be heated for 3-12 hours, and after cooling at room temperature, a single-layer PES/PVP ion conduction membrane is prepared, wherein the thickness of the prepared single-layer PES/PVP ion conduction membrane is 45 mu m. The preparation process is shown in figure 1;
(2)42g of PES (tensile strength 50MPa) and 63g of PVP are dissolved in 195g of DMAC, stirring is carried out for 24 hours, a uniform polymer solution B is formed, then the solution is kept still at the temperature of 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, the polymer solution B is flatly paved on the single-layer PES/PVP ion conduction membrane prepared in the step (1), then a glass plate is transferred to a hot table at the temperature of 50 ℃ to be heated for 3-12 hours, a double-layer PES/PVP composite ion conduction membrane consisting of two layers of single-layer PES/PVP ion conduction membranes is prepared after cooling at room temperature, and the thickness of the prepared double-layer PES/PVP ion conduction membrane is 85 mu m;
(3) and (3) flatly paving the polymer solution A on the double-layer PES/PVP composite ion conduction membrane prepared in the step (2), transferring a glass plate to a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature, and placing in water for more than 12 hours to prepare the PES/PVP composite ion conduction membrane consisting of three layers of single-layer PES/PVP ion conduction membranes, wherein the thickness of the prepared PES/PVP composite ion conduction membrane is 120 mu m, and the aperture is 0.002 nm.
The vanadium ion permeability of the prepared ion-conducting membrane is shown in fig. 2, and the vanadium ion permeability is smaller than that of Nafion 115 with excellent chemical stability; the surface resistance test result of the prepared ion-conducting membrane is shown in fig. 3, and the surface resistance of the prepared ion-conducting membrane is lower than that of Nafion 115 with excellent conductivity, which indicates that the prepared composite ion-conducting membrane has high selectivity and high conductivity.
Assembling an all-vanadium flow battery using the prepared composite ion-conducting membrane, whereinThe layered layer is activated carbon felt, the bipolar plate is graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2The coulombic efficiency under the current density condition of (1) is over 98%, the voltage efficiency is over 90%, both are higher than the coulombic efficiency and the voltage efficiency of the commercial Nafion 115 assembled all-vanadium flow battery (fig. 4). And the battery is at 80mA cm-2Can continuously and stably run for more than 100 cycles under the current density condition, and the performance is not obviously attenuated. (FIG. 5)
Example 2
(1) Dissolving 36g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP, the tensile strength is 20MPa) and 36g of polyvinylpyrrolidone (PVP) in 228g of DMAC, stirring for 24 hours to form a uniform polymer solution A, standing for more than 2 hours at the temperature of 25-50 ℃ to remove air bubbles in the solution, flatly paving the polymer solution A on a glass plate, transferring the glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature to prepare a single-layer PVDF-HFP/PVP ion conduction membrane, wherein the thickness of the prepared PVDF-HFP/PVP ion conduction membrane is 35 mu m;
(2)36g of PVDF-HFP (tensile strength of 20MPa) and 45g of PVP are dissolved in 219g of DMAC, stirring is carried out for 24 hours to form a uniform polymer solution B, then the solution B is kept still for more than 2 hours at the temperature of 25-50 ℃ to remove air bubbles in the solution, the polymer solution B is flatly paved on the single-layer PVDF-HFP/PVP ion conduction membrane prepared in the step (1), then a glass plate is transferred to a 50 ℃ hot bench to be heated for 3-12 hours, and after cooling at room temperature, a double-layer PVDF-HFP/PVP composite ion conduction membrane consisting of two layers of PVDF-HFP/PVP ion conduction membranes is prepared, wherein the thickness of the prepared double-layer PVDF-HFP/PVP ion conduction membrane is 65 mu m. The preparation process is shown in figure 1;
(3) and (3) flatly paving the polymer solution A on the double-layer PVDF-HFP/PVP composite ion conduction membrane prepared in the step (2), transferring the glass plate to a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature, and placing in water for more than 12 hours to prepare the PVDF-HFP/PVP composite ion conduction membrane consisting of three layers of PVDF-HFP/PVP ion conduction membranes, wherein the thickness of the prepared three layers of PVDF-HFP/PVP composite ion conduction membranes is 94 mu m, and the aperture of a surface layer is 0.008 nm.
The vanadium ion permeability of the prepared ion-conducting membrane is shown in fig. 2, and the vanadium ion permeability is smaller than that of Nafion 115 with excellent chemical stability; the surface resistance test result of the prepared ion-conducting membrane is shown in fig. 3, and the surface resistance of the prepared ion-conducting membrane is lower than that of Nafion 115 with excellent conductivity, which indicates that the prepared composite ion-conducting membrane has high selectivity and high conductivity.
The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2The coulombic efficiency under the current density condition of (1) is over 98%, the voltage efficiency is over 90%, both are higher than the coulombic efficiency and the voltage efficiency of the commercial Nafion 115 assembled all-vanadium flow battery (fig. 4). And the battery is at 80mA cm-2Can continuously and stably run for more than 100 cycles under the current density condition, and the performance is not obviously attenuated. (FIG. 5)
Example 3
(1) Dissolving 36g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP, the tensile strength is 20MPa) and 9g of polyvinylpyrrolidone (PVP) in 255g of DMAC, stirring for 24 hours to form a uniform polymer solution A, standing for more than 2 hours at the temperature of 25-50 ℃ to remove air bubbles in the solution, flatly paving the polymer solution A on a glass plate, transferring the glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature to obtain a single-layer PVDF-HFP/PVP ion conduction membrane, wherein the thickness of the prepared single-layer PVDF-HFP/PVP ion conduction membrane is 35 mu m;
(2) dissolving 45g of sulfonated polyether ether ketone (SPEEK with a sulfonation degree of 80%) in 255g of DMAC, stirring for 24 hours to form a uniform polymer solution B, standing at 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, flatly paving the polymer solution B on the single-layer PVDF-HFP/PVP ion conduction membrane prepared in the step (1), transferring a glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature to prepare a double-layer (PVDF-HFP/PVP)/SPEEK composite ion conduction membrane consisting of the single-layer PVDF-HFP/PVP ion conduction membrane and the single-layer SPEEK ion conduction membrane, wherein the thickness of the prepared double-layer (PVDF-HFP/PVP)/SPEEK composite ion conduction membrane is 60 mu m;
(3) dissolving 36g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP, tensile strength 20MPa) and 15g of polyvinylpyrrolidone (PVP) in 249g of DMAC, stirring for 24 hours to form a uniform polymer solution C, standing at 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, flatly paving the polymer solution C on a double-layer (PVDF-HFP/PVP)/SPEEK composite ion conduction membrane, transferring a glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature, placing in water for more than 12 hours to prepare the (PVDF-HFP/PVP)/SPEEK/(PVDF-HFP/PVP) composite ion conduction membrane consisting of a single-layer PVDF-HFP/PVP ion conduction membrane, a single-layer SPEEK ion conduction membrane and a single-layer PVDF-HFP/PVP ion conduction membrane, the thickness of the prepared three-layer (PVDF-HFP/PVP)/SPEEK/(PVDF-HFP/PVP) composite ion-conducting membrane is 85 μm, and the pore diameter of the surface layer (PVDF-HFP/PVP) is 0.004nm (36g of PVDF-HFP and 9g of PVP) and 0.006nm (36g of PVDF-HFP and 15g of PVP) respectively. The preparation process is shown in figure 1;
the vanadium ion permeability of the prepared ion-conducting membrane is shown in fig. 2, and the vanadium ion permeability is smaller than that of Nafion 115 with excellent chemical stability; the surface resistance test result of the prepared ion-conducting membrane is shown in fig. 3, and the surface resistance of the prepared ion-conducting membrane is lower than that of Nafion 115 with excellent conductivity, which indicates that the prepared composite ion-conducting membrane has high selectivity and high conductivity.
The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mAcm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2The coulombic efficiency under the current density condition of the catalyst exceeds 98 percent, the voltage efficiency exceeds 90 percent, and the coulombic efficiency and the voltage efficiency are all higher than that of the commercial NafioCoulombic and voltage efficiencies of n 115 assembled all vanadium flow batteries (fig. 4). And the battery is at 80mA cm-2Can continuously and stably run for more than 100 cycles under the current density condition, and the performance is not obviously attenuated. (FIG. 5)
Example 4
(1) Dissolving 39g of polysulfone (PSF, tensile strength 35MPa) and 12g of polyvinyl alcohol (PEG) in 249g of DMAC, stirring for 24 hours to form a uniform polymer solution A, standing at 25-50 ℃ for more than 2 hours to remove bubbles in the solution, flatly paving the polymer solution A on a glass plate, transferring the glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature to obtain a single-layer PSF/PEG ion conduction membrane, wherein the thickness of the prepared single-layer PSF/PEG ion conduction membrane is 35 mu m;
(2) dissolving 36g of polyvinylidene fluoride (PVDF, the tensile strength is 15MPa) and 9g of polylactic acid (PLA) in 255g of DMAC, stirring for 24 hours to form a uniform polymer solution B, standing for more than 2 hours at the temperature of 25-50 ℃ to remove air bubbles in the solution, flatly paving the polymer solution B on the single-layer PSF/PLA ion conduction membrane prepared in the step (1), transferring a glass plate onto a 50 ℃ hot table, heating for 3-12 hours, cooling at room temperature to prepare a double-layer (PSF/PEG)/(PVDF/PLA) composite ion conduction membrane consisting of the single-layer PSF/PEG ion conduction membrane and the single-layer PVDF/PLA ion conduction membrane, wherein the thickness of the prepared double-layer (PSF/PEG)/(PVDF/PLA) ion conduction membrane is 60 mu m;
(3) dissolving 36g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP, tensile strength 20MPa) and 12g of polyvinylpyrrolidone (PVP) in 252g of DMAC, stirring for 24 hours to form a uniform polymer solution C, standing at 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, paving the polymer solution C on a double-layer (PSF/PLA)/(PVDF/PEG) composite ion-conducting membrane, transferring a glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature, placing in water for more than 12 hours to obtain a (PSF/PEG/PLA)/(PVDF-HFP/PVP) composite ion-conducting membrane consisting of a single-layer PSF/PLA ion-conducting membrane, a single-layer PVDF/PEG ion-conducting membrane and a single-layer PVDF-HFP/PVP ion-conducting membrane, the thickness of the prepared three-layer (PSF/PEG)/(PVDF/PLA)/(PVDF-HFP/PVP)) ion-conducting membrane is 95 μm, the pore diameter of the PSF/PEG ion-exchange membrane of the surface layer is 0.009nm, and the pore diameter of the PVDF-HFP/PVP of the surface layer is 0.005 nm. The preparation process is shown in figure 1;
the vanadium ion permeability of the prepared ion-conducting membrane is shown in fig. 2, and the vanadium ion permeability is smaller than that of Nafion 115 with excellent chemical stability; the surface resistance test result of the prepared ion-conducting membrane is shown in fig. 3, and the surface resistance of the prepared ion-conducting membrane is lower than that of Nafion 115 with excellent conductivity, which indicates that the prepared composite ion-conducting membrane has high selectivity and high conductivity.
The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2The coulombic efficiency under the current density condition of (1) is over 98%, the voltage efficiency is over 90%, both are higher than the coulombic efficiency and the voltage efficiency of the commercial Nafion 115 assembled all-vanadium flow battery (fig. 4). And the battery is at 80mA cm-2Can continuously and stably run for more than 100 cycles under the current density condition, and the performance is not obviously attenuated. (FIG. 5)
Example 5
(1) Dissolving 36g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP, the tensile strength is 20MPa) and 36g of polyvinylpyrrolidone (PVP) in 228g of DMAC, stirring for 24 hours to form a uniform polymer solution A, standing for more than 2 hours at 25-50 ℃ to remove air bubbles in the solution, flatly paving the polymer solution A on a glass plate, transferring the glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature to obtain a single-layer PVDF-HFP/PVP ion conduction membrane, wherein the thickness of the prepared single-layer PVDF-HFP/PVP ion conduction membrane is 35 mu m;
(2)36g of polystyrene (PS, tensile strength 18MPa) and 45g of polybenzimidazole (PBI, degree of quaternization 100%) are dissolved in 219g of DMAC and stirred for 24 hours to form a homogeneous polymer solution B, then standing for more than 2 hours at the temperature of 25-50 ℃ to remove air bubbles in the solution, paving the polymer solution B on the single-layer PVDF-HFP/PVP ion conduction membrane prepared in the step (1), and then transferring the glass plate to a hot table at 50 ℃ to heat for 3-12 hours, cooling at room temperature to obtain the double-layer (PVDF-HFP/PVP)/(PS/PBI) composite ion-conducting membrane consisting of the single-layer PVDF-HFP/PVP ion-conducting membrane and the single-layer PS/PBI ion-conducting membrane, wherein the thickness of the prepared double-layer (PVDF-HFP/PVP)/(PS/PBI) composite ion-conducting membrane is 78 mu m. The preparation process is shown in figure 1;
(3) dissolving 52g of polyethersulfone (PES, tensile strength of 50MPa) and 53g of polyvinylpyrrolidone (PVP) in 195g of DMAC, stirring for 24 hours to form a uniform polymer solution C, then standing at 25-50 ℃ for more than 2 hours to remove air bubbles in the solution, spreading the polymer solution C on the double-layer (PVDF-HFP/PVP)/(PS/PBI) composite ion-conducting membrane prepared in the step (2), transferring the glass plate to a 50 ℃ hot bench, heating for 3-12 hours, cooling at room temperature to obtain a three-layer (PVDF-HFP/PVP)/(PS/PBI)/(PES/PVP) composite ion-conducting membrane consisting of a single-layer PVDF-HFP/PVP ion-conducting membrane, a single-layer PS/PBI ion-conducting membrane and a single-layer PES/PVP ion-conducting membrane, the thickness of the prepared three-layer (PVDF-HFP/PVP)/(PS/PBI)/(PES/PVP) composite ion conduction membrane is 100 mu m, the pore diameter of PVDF-HFP/PVP)/(an ion exchange membrane on the surface layer is 0.008nm, and the pore diameter of a PES/PVP ion exchange membrane on the surface layer is 0.005 nm. The preparation process is shown in figure 1;
the vanadium ion permeability of the prepared ion-conducting membrane is shown in fig. 2, and the vanadium ion permeability is smaller than that of Nafion 115 with excellent chemical stability; the surface resistance test result of the prepared ion-conducting membrane is shown in fig. 3, and the surface resistance of the prepared ion-conducting membrane is lower than that of Nafion 115 with excellent conductivity, which indicates that the prepared composite ion-conducting membrane has high selectivity and high conductivity.
The prepared ion-conducting membrane is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Assembled flow battery at 80mAcm-2Current density condition ofThe lower coulombic efficiency exceeded 98%, the voltage efficiency exceeded 90%, both higher than those of commercial Nafion 115 assembled all-vanadium flow batteries (figure 4). And the battery is at 80mA cm-2Can continuously and stably run for more than 100 cycles under the current density condition, and the performance is not obviously attenuated (figure 5).

Claims (7)

1. A method of making a composite ion-conducting membrane, comprising: preparing a composite ion-conducting membrane with a three-layer structure by a three-time solvent evaporation phase separation method, and finally placing the composite ion-conducting membrane in water to obtain the composite ion-conducting membrane; the preparation process comprises preparing single-layer ion-conducting membrane by solvent evaporation phase separation method; then coating a layer of polymer solution on the surface of the ion-conducting membrane as an intermediate layer, and evaporating and separating the solvent to prepare a double-layer composite ion-conducting membrane; coating a layer of polymer solution on the surface of the middle layer of the double-layer composite ion-conducting membrane, and evaporating and separating the solvent to obtain the composite ion-conducting membrane with a three-layer structure; finally, the composite ion-conducting membrane is soaked in water to obtain the required composite ion-conducting membrane;
the preparation method of the composite ion-conducting membrane comprises the following steps:
(1) dissolving water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange group in organic solvent, and stirring at 10-80 deg.C for 2-48h to obtain polymer solution; wherein the final concentration of the water-insoluble organic polymer resin containing no ion exchange group is 10-50 wt%; the final concentration of the water-soluble organic polymer resin is between 5 and 30 weight percent;
(2) directly pouring the polymer solution prepared in the step (1) onto a glass plate or a stainless steel plate, volatilizing the solvent for 0-60s, and heating at 40-150 ℃ to evaporate the solvent; preparing to obtain a single-layer ion-conducting membrane, wherein the thickness of the single-layer ion-conducting membrane is between 10 and 50 mu m;
(3) dissolving water-insoluble organic polymer resin without ion exchange group and water-soluble organic polymer resin in organic solvent, or dissolving water-insoluble organic polymer resin without ion exchange group and highly hydrophilic water-insoluble organic polymer resin in organic solvent, or dissolving highly hydrophilic water-insoluble organic polymer resin in organic solvent, and stirring at 10-80 deg.C for 2-48h to obtain polymer solution; wherein the final concentration of the water-insoluble organic polymer resin containing no ion exchange group is 10-50 wt%; the final concentration of the water-soluble organic polymer resin is between 5 and 30 weight percent; the final concentration of the high hydrophilic water-insoluble organic polymer resin is between 5 and 30 percent;
(4) pouring the polymer solution prepared in the step (3) onto the single-layer ion-conducting membrane prepared in the step (2), volatilizing the solvent for 0-60s, and heating at 40-150 ℃ to evaporate the solvent; preparing to obtain a double-layer composite ion-conducting membrane, wherein the thickness of the double-layer composite ion-conducting membrane is between 20 and 100 mu m;
(5) dissolving water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange group in organic solvent, and stirring at 10-80 deg.C for 2-48h to obtain polymer solution; wherein the final concentration of the water-insoluble organic polymer resin containing no ion exchange group is 10-50 wt%; the final concentration of the water-soluble organic polymer resin is between 5 and 30 weight percent;
(6) pouring the polymer solution prepared in the step (5) on the double-layer composite ion-conducting membrane prepared in the step (4), volatilizing the solvent for 0-60s, and heating at the temperature of 40-150 ℃ to evaporate the solvent to dryness; preparing the composite ion-conducting membrane with the three-layer structure, wherein the thickness of the composite ion-conducting membrane with the three-layer structure is 30-150 mu m;
(7) and (3) soaking the three-layer composite ion-conducting membrane obtained in the step (6) in water at 25-60 ℃ for at least 12h to dissolve water-soluble polymer resin in the ion-conducting membranes on the two outer surface layers of the three-layer composite ion-conducting membrane to form pores, so as to obtain the required composite ion-conducting membrane, wherein the two outer surface layers are of a porous structure, the pore diameter is 0.001-10nm, and the middle layer is of a compact structure.
2. The method of claim 1, wherein: when the intermediate ion-conducting membrane is made of water-insoluble organic polymer resin and water-soluble organic polymer resin without ion exchange groups, or water-insoluble organic polymer resin without ion exchange groups and high-hydrophilic water-insoluble organic polymer resin, the stability of the water-insoluble organic polymer resin of the two outer surface layers is higher than that of the water-insoluble organic polymer resin of the intermediate ion-conducting membrane, wherein the stability of the resin is characterized by the tensile strength of the resin per se, that is, the tensile strength of the water-insoluble organic polymer resin selected for the ion-conducting membrane of the two outer surface layers is higher than that of the water-insoluble organic polymer resin selected for the ion-conducting membrane of the intermediate layer: the tensile strength of the water-insoluble organic polymer resin is between 3 and 100 MPa.
3. The method of claim 1, wherein: the water-insoluble organic polymer resin without ion exchange groups is one or more than two of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyether sulfone, polysulfone, polyether ketone, polystyrene and polytetrafluoroethylene;
the water-soluble organic high molecular resin is one or more of polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and polylactic acid;
the high hydrophilic water-insoluble organic polymer resin is one or more of sulfonated polymers such as sulfonated polyether ether ketone, sulfonated polyether ketone, sulfonated poly (arylene sulfide ketone), sulfonated poly (fluorenyl ether ketone), sulfonated poly (tetramethyl diphenyl ether ketone), sulfonated polyoxadiazole and sulfonated polystyrene, and quaternized polymers such as quaternized poly (tetramethyl diphenyl ether sulfone), quaternized poly (phthalazinone ether ketone) and polybenzimidazole.
4. The production method according to claim 3, characterized in that: the sulfonation degree of the high hydrophilic water-insoluble organic polymer resin is between 30 and 120 percent; the quaternization degree of the high hydrophilic water-insoluble organic polymer resin is between 30 and 120 percent.
5. The method of claim 1, wherein: the organic solvent is one or more than two of DMAC, NMP and DMF.
6. A composite ion-conducting membrane prepared by the preparation method of any one of claims 1 to 5, wherein the surface layer of the composite ion-conducting membrane is of a porous structure, and the pore diameter is between 0.001 and 10 nm; the middle layer is a compact structure, and the thickness of the composite ion-conducting membrane is between 30 and 150 mu m.
7. Use of a composite ion-conducting membrane according to claim 6, wherein: the composite ion conducting membrane is applied to flow batteries, including all-vanadium flow batteries, zinc/cerium flow batteries, vanadium/bromine flow batteries, iron/chromium flow batteries, zinc/bromine flow batteries, zinc/iron flow batteries, zinc/nickel flow batteries or zinc/iodine flow batteries.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101383404A (en) * 2007-09-05 2009-03-11 中国科学院大连化学物理研究所 Fluorine/hydrocarbon composite ion exchange film and preparation thereof
CN102237534A (en) * 2010-04-28 2011-11-09 中国科学院金属研究所 Perfluorinated sulfonic acid ion exchange membrane preparation process for vanadium redox battery
CN102544541A (en) * 2010-12-31 2012-07-04 中国科学院金属研究所 Preparation method of asymmetric PSFA (polysilicate ferric aluminum)/PP (polypropylene)/SPEEK (sulfonated polyetheretherketone) composite membrane
CN107528079A (en) * 2016-06-20 2017-12-29 中国科学院大连化学物理研究所 A kind of solvent processing method of flow battery polyalcohol stephanoporate ion-conductive membranes
CN107546398A (en) * 2016-06-29 2018-01-05 中国科学院大连化学物理研究所 A kind of ion-conductive membranes and its preparation and application with micro phase separation structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101383404A (en) * 2007-09-05 2009-03-11 中国科学院大连化学物理研究所 Fluorine/hydrocarbon composite ion exchange film and preparation thereof
CN102237534A (en) * 2010-04-28 2011-11-09 中国科学院金属研究所 Perfluorinated sulfonic acid ion exchange membrane preparation process for vanadium redox battery
CN102544541A (en) * 2010-12-31 2012-07-04 中国科学院金属研究所 Preparation method of asymmetric PSFA (polysilicate ferric aluminum)/PP (polypropylene)/SPEEK (sulfonated polyetheretherketone) composite membrane
CN107528079A (en) * 2016-06-20 2017-12-29 中国科学院大连化学物理研究所 A kind of solvent processing method of flow battery polyalcohol stephanoporate ion-conductive membranes
CN107546398A (en) * 2016-06-29 2018-01-05 中国科学院大连化学物理研究所 A kind of ion-conductive membranes and its preparation and application with micro phase separation structure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Advance dporous membranes with slit-like Selective layerforflow battery;Lin Qiao;《NANO ENERGY》;20181010;第73-81页 *

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