CN110197911B - Porous diaphragm for all-vanadium redox flow battery and preparation method and application thereof - Google Patents
Porous diaphragm for all-vanadium redox flow battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a porous diaphragm for an all-vanadium redox flow battery and a preparation method and application thereof, wherein a polymer porous membrane is taken as a base membrane, a gel solution is introduced into pores of the polymer porous membrane, and gel substances in the gel solution are subjected to hydrolysis reaction in pore channels of the polymer porous membrane to form heteropoly acid coated nanoparticles; the porous diaphragm is applied to the all-vanadium redox flow battery, and the effective aperture is reduced by introducing the nano particles coated by heteropoly acid into the pore channel of the polymer porous membrane, so that the ion selectivity of the porous diaphragm for the all-vanadium redox flow battery is obviously improved. Meanwhile, the heteropoly acid with high ion conductivity can effectively reduce the influence of the reduction of the pore diameter on the ion conductivity of the porous diaphragm for the all-vanadium redox flow battery. The porous diaphragm has the advantages of low cost of preparation raw materials, excellent chemical stability, simple preparation process of the polymer porous membrane, controllable pore diameter and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of battery diaphragm preparation, and particularly relates to a porous diaphragm for an all-vanadium redox flow battery, and a preparation method and application thereof.
Background
The high-power and high-capacity energy storage technology is a key technology for pushing the energy structure to adjust and popularizing and applying renewable energy sources such as wind energy, solar energy and the like. The full Vanadium Flow Battery (VFB) uses Vanadium ions of different valence states as active substances of the battery, and overcomes the problem of cross contamination of the electrolyte of the flow battery. Due to the advantages of separate design of energy and power of the battery, high safety, long cycle life and the like, the battery is one of the most promising technologies in large-scale energy storage technology. The battery diaphragm is one of the important components forming the all-vanadium redox flow battery, and has the following functions: on one hand, the positive and negative electrolytes are separated so as to prevent the positive and negative active ions from cross contamination and generating self-discharge; and on the other hand, conductive ions such as protons are allowed to pass through to form an internal circuit of the battery. VFB battery separators should have the following characteristics: the high ionic conductivity enables the battery to have higher voltage efficiency so as to reduce the polarization phenomenon of the battery, has higher selectivity on vanadium ions, enables the battery to have higher coulombic efficiency, and reduces the self-discharge phenomenon of the battery; has better mechanical property, chemical corrosion resistance and electrochemical oxidation resistance, and ensures longer service life.
In flow batteries, the performance and cost of the separator largely determine the ultimate performance and cost of the battery. At present, the diaphragm material used by commercial vanadium batteries at home and abroad is mainly a Nafion membrane developed by DuPont, and the Nafion membrane has excellent performances in the aspects of ionic conductivity, mechanical property, chemical property, service life and the like, but the use of the membrane is limited due to high price and poor ionic selectivity. In view of the above problems, non-fluorine ion exchange membranes have become a hot point of research, common non-fluorine polymers are materials such as sulfonated polyaryletherketone, polyarylethersulfone, polyimide and the like, however, for most of non-fluorine ion exchange membranes, the structure of the materials is damaged when ion exchange groups are introduced, the oxidation stability of the membrane is greatly reduced, and the service life of the membrane in VFB is limited. Therefore, the development of battery separators with high ionic conductivity, high selectivity, high stability and low cost is crucial to driving the commercialization process of all-vanadium flow batteries.
Taking the all-vanadium redox flow battery as an example, because vanadium ions and protons exist in the electrolyte in the form of hydrated ions, and the stokes radius of the former is much larger than that of the latter, the protons can freely pass through and the vanadium ions are intercepted by adjusting the pore diameter or charge property of the porous diaphragm, so that the separation of the vanadium ions and the protons is realized.
PVDF has a porous diaphragm with good oxidation resistance, and has been widely used in water treatment, lithium battery and other industries. However, the membrane has strong hydrophobicity, and when the pore diameter is small, the hydrated hydrogen ions are difficult to transmit in the pore diameter, so that a large resistance is generated. Therefore, if PVDF is applied to an all-vanadium flow battery, it is necessary to ensure that the PVDF porous membrane has a pore size of an appropriate size to satisfy the balance between the ion conductivity and the selectivity of the membrane.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to solve the contradiction between the ion conductivity and the selectivity of the porous diaphragm for the all-vanadium redox flow battery, form heteropoly acid coated nano particles in the pore channel of the porous diaphragm by an in-situ gel hydrolysis method, and adjust the pore size of the porous diaphragm by controlling the amount of the filled nano particles; the nanometer particles can reduce the aperture of the porous diaphragm, and the heteropoly acid can effectively reduce the influence of the nanometer particles on the ion conductivity of the porous diaphragm. In order to facilitate the gel solution to enter the porous diaphragm, the porous diaphragm is subjected to expansion treatment, the gel solution is hydrolyzed inside a pore channel to form nano particles, the ion selectivity of the porous diaphragm is improved, and hydroxyl on the surface of the nano particles can interact with heteropoly acid, so that the heteropoly acid is coated on the surface of the nano particles to form fixed ion exchange groups, the ion conduction capability of the porous diaphragm is increased, and the ion conduction performance of the prepared porous diaphragm and the porous diaphragm with controllable vanadium ion selectivity are improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a porous diaphragm for an all-vanadium flow battery comprises the following steps:
taking a polymer porous membrane as a base membrane, introducing a gel solution into pores of the polymer porous membrane, wherein gel substances in the gel solution generate hydrolysis reaction in the pore channels of the polymer porous membrane to form heteropoly acid-coated nano particles, and preparing a porous diaphragm filled with the heteropoly acid-coated nano particles, namely the porous diaphragm for the all-vanadium redox flow battery; wherein the gel solution comprises a nanoparticle precursor, water and a heteropoly acid.
According to an embodiment of the present invention, the polymer porous membrane is selected from at least one of a polyvinylidene fluoride-based porous membrane, a polysulfone-based porous membrane, a polyethersulfone-based porous membrane, a polyacrylonitrile-based porous membrane, a polyimide-based porous membrane, a polyetherketone-based porous membrane, a polytetrafluoroethylene-based porous membrane, a polybenzimidazole-based porous membrane, or a polyvinylpyridine-based porous membrane. Also preferably, the polymeric porous membrane is selected from polyvinylidene fluoride-based porous membranes.
According to an embodiment of the present invention, the nanoparticles are silica, titania, zirconia, or the like nanoparticles.
According to an embodiment of the present invention, the nanoparticle precursor is selected from one or more of ethyl orthosilicate, butyl titanate or zirconium oxychloride, and the heteropoly acid is selected from one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid or silicomolybdic acid.
According to an embodiment of the present invention, the nanoparticles in the porous separator accounts for 0.2-15wt% of the total mass of the porous separator.
According to the embodiment of the invention, the heteropoly acid in the porous membrane accounts for 0.16-14.8wt% of the total mass of the porous membrane.
According to an embodiment of the invention, the method comprises the steps of:
(3) immersing the polymer porous membrane into an expanding agent, and standing;
(4) mixing the nanoparticle precursor, water and heteropoly acid to prepare a gel solution;
(5) and (3) soaking the polymer porous membrane obtained in the step (3) into the gel solution obtained in the step (4) by adopting an in-situ gel hydrolysis method, standing and taking out to obtain the porous membrane filled with the heteropoly acid-coated nano particles, namely the porous membrane for the all-vanadium redox flow battery.
According to an embodiment of the present invention, the polymer porous membrane may be prepared by:
(1) dissolving a polymer and a high-molecular pore-foaming agent in an organic solvent to prepare a mixed solution;
(2) and (3) coating the mixed solution obtained in the step (1) on the surface of a base material, standing, and then immersing into a coagulating bath for solidification to prepare the polymer porous membrane.
According to the embodiment of the invention, in the step (1), the mass concentration of the polymer in the mixed solution is 10-40wt%, and the mass concentration of the polymeric porogen is 1-15%.
According to an embodiment of the present invention, in the step (1), the organic polymer resin is at least one selected from polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyether ketone, polytetrafluoroethylene, polybenzimidazole, and polyvinylpyridine.
According to an embodiment of the present invention, in step (1), the polymeric porogen is selected from one or more of polyvinylpyrrolidone (PVP), polyethylene glycol or polyvinyl alcohol.
According to an embodiment of the present invention, in the step (1), the organic solvent is one or more selected from Dimethylformamide (DMF), Dimethylacetamide (DMAC) or Dimethylsulfoxide (DMSO).
According to an embodiment of the present invention, in the step (2), the substrate is a glass plate, a stainless steel plate or a nonwoven fabric.
According to an embodiment of the present invention, in the step (2), the standing time is 1 to 30 min.
According to an embodiment of the present invention, in the step (2), the coagulation bath is selected from one or two or more of water, ethanol, propanol, butanol, isopropanol, or methanol.
According to an embodiment of the present invention, in the step (2), the curing time is 1 to 60 min.
According to the embodiment of the present invention, in the step (2), the thickness of the polymer porous membrane is 50 to 250 μm, preferably 100-200 μm, and more preferably 100-150 μm; preferably, the pore size of the polymer porous membrane is 0.05-50nm, and the porosity of the polymer porous membrane is 30-70%.
According to an embodiment of the present invention, in the step (3), the swelling agent is one or more selected from ethanol, methanol, isopropanol, or water.
According to the embodiment of the invention, in the step (3), the standing time is 1-6 h.
According to an embodiment of the present invention, in step (4), the heteropoly acid in the gel solution: nanoparticle precursor: the molar ratio of water is (0.05-3): (1): (2-4).
According to an embodiment of the present invention, in the step (5), the standing time is 0.5 to 6 hours.
The invention provides a high-selectivity porous diaphragm for an all-vanadium redox flow battery, which is prepared by the method.
The invention provides application of a porous diaphragm in an all-vanadium flow battery.
The invention provides an all-vanadium redox flow battery which comprises the porous diaphragm.
The beneficial results are that:
(1) the porous diaphragm for the all-vanadium redox flow battery is characterized in that a polymer porous membrane is used as a base membrane, a gel solution is introduced into pores of the polymer porous membrane, gel substances in the gel solution generate hydrolysis reaction in the pore channels of the polymer porous membrane to form heteropoly acid coated nano particles, and the porous diaphragm filled with the heteropoly acid coated nano particles is prepared, namely the porous diaphragm for the all-vanadium redox flow battery; wherein the gel solution comprises a nanoparticle precursor, water and a heteropoly acid.
(2) The porous diaphragm for the all-vanadium redox flow battery is applied to the all-vanadium redox flow battery, and the effective aperture is reduced by introducing the nano particles coated by the heteropoly acid into the pore channel of the polymer porous membrane, so that the ion selectivity of the porous diaphragm for the all-vanadium redox flow battery is obviously improved. Meanwhile, the heteropoly acid with high ion conductivity can effectively reduce the influence of the reduction of the pore diameter on the ion conductivity of the porous diaphragm for the all-vanadium redox flow battery.
(3) The porous diaphragm for the all-vanadium redox flow battery has the advantages of low cost of preparation raw materials, excellent chemical stability, simple preparation process of the polymer porous membrane, controllable pore diameter and easy large-scale production.
(4) The preparation method provided by the invention can be used for controllably adjusting the ion conductivity and selectivity of the porous diaphragm for the all-vanadium redox flow battery, optimizing the charge-discharge efficiency of the all-vanadium battery, and obtaining higher coulombic efficiency and energy efficiency.
Drawings
Fig. 1 is a graph showing charge and discharge efficiencies of the porous separators prepared in comparative example 1, comparative example 2, and example 1 in the all-vanadium flow battery.
Fig. 2 is an SEM image of the porous separators prepared in comparative example 1 and example 1.
Detailed Description
[ preparation method of porous separator for all-vanadium redox flow battery ]
As described above, the invention provides a preparation method of a porous diaphragm for an all-vanadium redox flow battery, which comprises the following steps:
taking a polymer porous membrane as a base membrane, introducing a gel solution into pores of the polymer porous membrane, wherein gel substances in the gel solution generate hydrolysis reaction in the pore channels of the polymer porous membrane to form heteropoly acid-coated nano particles, and preparing a porous diaphragm filled with the heteropoly acid-coated nano particles, namely the porous diaphragm for the all-vanadium redox flow battery; wherein the gel solution comprises a nanoparticle precursor, water and a heteropoly acid.
In a preferred embodiment of the present invention, the polymer porous membrane is not particularly limited, and may be any one known to those skilled in the art that can prepare a base membrane of a porous separator and achieve the purpose of using the porous separator for the all-vanadium redox flow battery. Preferably, the polymer porous membrane is selected from at least one of a polyvinylidene fluoride-based porous membrane, a polysulfone-based porous membrane, a polyether sulfone-based porous membrane, a polyacrylonitrile-based porous membrane, a polyimide-based porous membrane, a polyether ketone-based porous membrane, a polytetrafluoroethylene-based porous membrane, a polybenzimidazole-based porous membrane, or a polyethylene pyridine-based porous membrane. Also preferably, the polymeric porous membrane is selected from polyvinylidene fluoride-based porous membranes.
In a preferred embodiment of the present invention, the method comprises the steps of:
(3) immersing the polymer porous membrane into an expanding agent, and standing;
(4) mixing the nanoparticle precursor, water and heteropoly acid to prepare a gel solution;
(5) and (3) soaking the polymer porous membrane obtained in the step (3) into the gel solution obtained in the step (4) by adopting an in-situ gel hydrolysis method, standing and taking out to obtain the porous membrane filled with the heteropoly acid-coated nano particles, namely the porous membrane for the all-vanadium redox flow battery.
In a preferred embodiment of the present invention, the polymer porous membrane can be prepared by:
(1) dissolving a polymer and a high-molecular pore-foaming agent in an organic solvent to prepare a mixed solution;
(2) and (3) coating the mixed solution obtained in the step (1) on the surface of a base material, standing, and then immersing into a coagulating bath for solidification to prepare the polymer porous membrane.
In a preferred embodiment of the present invention, in step (1), the mixing temperature of the mixed solution is not particularly limited, and those skilled in the art can understand that it is required to completely mix the polymer and the polymeric porogen, and ensure that the mixing time is not too long, so as to improve the preparation efficiency of the porous membrane; preferably, the temperature for mixing the mixed solution is 50-100 ℃, and at the temperature, after 6-10 hours, the polymer and the high-molecular pore-forming agent can be completely dissolved in the organic solvent, and a uniform and stable mixed solution can be formed; it will be understood by those skilled in the art that the manner of mixing is not particularly limited, and may be ultrasonic mixing, magnetic stirring mixing, mechanical stirring mixing, etc., as long as a mixed solution can be prepared.
In a preferred embodiment of the present invention, in step (1), the mixing ratio of the polymer and the polymeric porogen in the mixed solution is not specifically limited, and it is sufficient that after the prepared mixed solution is solidified by a coagulation bath, the base membrane applicable to the porous membrane for the high-selectivity all-vanadium flow battery of the present invention can be prepared. Preferably, the mass concentration of the polymer in the mixed solution is 10-40wt%, and the mass concentration of the polymeric porogen is 1-15%.
In a preferred embodiment of the present invention, in the step (1), the molecular weight and the polymerization degree of the polymer are not particularly limited, and may be any molecular weight and polymerization degree known in the art that can be dissolved in the organic solvent. The selection of the polymer is not particularly limited, and any polymer capable of producing the porous membrane can be used, and the purpose of using the high-selectivity porous membrane for the all-vanadium redox flow battery can be achieved. Preferably, the organic polymer resin is at least one selected from polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyetherketoneketone, polytetrafluoroethylene, polybenzimidazole, and polyvinylpyridine.
In a preferred embodiment of the present invention, in step (1), the selection of the polymeric porogen is not specifically limited, and it is sufficient if it can be used in combination with a polymer and achieve a porogen effect. Preferably, the polymeric porogen is one or more selected from polyvinylpyrrolidone (PVP), polyethylene glycol or polyvinyl alcohol.
In a preferred embodiment of the present invention, in step (1), the organic solvent is not specifically limited, and may be any organic solvent known to those skilled in the art that can dissolve the polymer and the polymeric porogen and can prepare a uniform and stable mixed solution, and preferably, the organic solvent is selected from one or more of Dimethylformamide (DMF), Dimethylacetamide (DMAC) or Dimethylsulfoxide (DMSO).
In a preferred embodiment of the present invention, in the step (2), the substrate may be any flat substrate known to those skilled in the art that can be used to prepare a porous separator, and the size and shape of the substrate are not particularly limited, and may be appropriately selected according to the size and shape of the separator to be prepared, and a substrate with a suitable size and shape may be selected as known to those skilled in the art. Preferably, the substrate is a glass plate, a stainless steel plate or a nonwoven fabric.
In a preferred embodiment of the present invention, in the step (2), the coating manner is not particularly limited, and any coating manner known to those skilled in the art may be used to prepare the porous film, and preferably, the coating manner may be at least one of roll coating, knife coating, spray coating, dipping, and the like. As an example, the mixed solution is applied to a substrate having a flat surface by using an application blade having a thickness of 50 to 500 μm (e.g., 200 μm).
In a preferred embodiment of the present invention, in the step (2), the substrate coated with the mixed solution is left standing under an atmosphere of air at a suitable temperature (i.e., a temperature lower than the boiling point of each component in the mixed solution, preferably lower than the boiling point of the organic solvent in the mixed solution, for example, the temperature may be 0 to 100 ℃) in order to completely volatilize the organic solvent in the mixed solution as much as possible so as to solidify it in the coagulation bath. It will be understood by those skilled in the art that the time for the standing is not particularly limited, and is related to the coating thickness of the mixed solution on the surface of the substrate, and is extended when the coating thickness of the mixed solution on the surface of the substrate is thick, and is shortened when the coating thickness of the mixed solution on the surface of the substrate is thin; preferably, the standing time is 1-30 min.
In a preferred embodiment of the present invention, in the step (2), the thickness of the mixed solution on the surface of the substrate is not specifically limited, and it can be understood by those skilled in the art that the thickness of the mixed solution is related to the thickness of the porous film to be prepared, and if the thickness of the porous film to be prepared is thick, the thickness of the mixed solution on the surface of the substrate is also thick, and similarly, if the thickness of the porous film to be prepared is thin, the thickness of the mixed solution on the surface of the substrate is also thin; as will be understood by those skilled in the art, the thickness of the mixed solution changes after the substrate surface is allowed to stand and solidify. Preferably, the thickness of the mixed solution on the surface of the substrate is such that the thickness of the prepared porous membrane is 50-250 μm, more preferably 100-200 μm, and even more preferably 100-150 μm.
In a preferred embodiment of the present invention, in the step (2), the selection of the coagulation bath is not particularly limited, and any liquid known to those skilled in the art may be used in which the solidification of the mixed solution occurs. Preferably, the coagulation bath is selected from one or more of water, ethanol, propanol, butanol, isopropanol, or methanol.
In a preferred embodiment of the present invention, in step (2), the curing temperature and time in the coagulation bath are not particularly limited, and those skilled in the art can know the temperature and time for curing the mixed solution, and the prepared porous polymer membrane can be ensured to achieve the purpose of being used as a porous membrane for a high-selectivity all-vanadium flow battery. Preferably, the curing time is 1-60 min.
In a preferred embodiment of the present invention, in the step (2), the thickness, pore size and porosity of the polymer porous membrane are not particularly limited, and may be selected for use therewith and for the purpose of use thereof as a porous separator for a high-selectivity all-vanadium flow battery. Preferably, the thickness of the polymer porous membrane is 50-250 μm, more preferably 100-200 μm, and further preferably 100-150 μm; preferably, the pore size of the polymer porous membrane is 0.05-50nm, and the porosity of the polymer porous membrane is 30-70%.
In a preferred embodiment of the present invention, in the step (3), the swelling agent is not particularly limited, and may be any compound known to those skilled in the art that can achieve swelling of the polymer porous membrane. The swelling agent can be used for enlarging the pore diameter of the polymer porous membrane so as to facilitate the gel substance in the gel solution to enter and fill in the pore channel. Preferably, the swelling agent is selected from one or more of ethanol, methanol, isopropanol or water.
In a preferred embodiment of the present invention, in the step (3), the standing time is not particularly limited, and it can be understood by those skilled in the art that, according to the difference of the thickness and the pore size of the polymer porous membrane, the standing time is selected to be suitable so that the pore size of the polymer porous membrane is increased to facilitate the entry of the gel solution and complete the swelling. Preferably, the standing time is 1-6 h.
In a preferred embodiment of the present invention, in step (4), the nanoparticle precursor is selected from one or more of ethyl orthosilicate, butyl titanate or zirconium oxychloride, and the heteropolyacid is selected from one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid or silicomolybdic acid. The heteropoly acid and the nanoparticle precursor are matched for use, the prepared gel solution can fully enter the pore channel of the polymer porous membrane which is completely expanded, hydrolysis is carried out in the pore channel of the polymer porous membrane to form the nanoparticle coated with the heteropoly acid and the hydrolyzed nanoparticle of the nanoparticle precursor, and the porous diaphragm filled with the heteropoly acid-coated nanoparticle is prepared.
In a preferred embodiment of the present invention, in step (4), the mixing ratio of the nanoparticle precursor, water and heteropoly acid in the gel solution is not specifically limited, which enables the prepared gel solution to enter into the pore channels of the polymer porous membrane and to be hydrolyzed in the pore channels to form heteropoly acid-coated nanoparticles; preferably, the heteropolyacid: nanoparticle precursor: the molar ratio of water is (0.05-3): (1): (2-4).
In a preferred embodiment of the present invention, in the step (5), during the standing process, a gel in the gel solution may enter the pore channels of the expanded polymer porous membrane, and hydrolyze in the pore channels of the polymer porous membrane to form heteropoly acid coated nanoparticles, that is, a hydrolysis process of the nanoparticle precursor, and the standing time is not specifically limited, so that the gel in the gel solution may fully enter the pore channels of the expanded polymer porous membrane and completely react. Preferably, the standing time is 0.5-6 h.
In a preferred embodiment of the present invention, in step (5), the nanoparticles are nanoparticles of silica, titania, zirconia, or the like, and the nanoparticles are obtained by hydrolyzing a nanoparticle precursor.
In a preferable scheme of the invention, the percentage content of the nanoparticles in the porous membrane for the all-vanadium redox flow battery in the total mass of the porous membrane is not particularly limited, and the porous membrane for the all-vanadium redox flow battery can have ion selectivity. The nano particles in the porous diaphragm for the all-vanadium redox flow battery can effectively reduce the pore diameter, and the ion selectivity of the porous diaphragm for the all-vanadium redox flow battery is obviously improved. Preferably, the nano particles in the porous diaphragm for the all-vanadium redox flow battery account for 0.2-15wt% of the total mass of the porous diaphragm.
In a preferable embodiment of the invention, the percentage content of the heteropoly acid in the porous membrane for the all-vanadium flow battery in the total mass of the porous membrane is not particularly limited, and the porous membrane for the all-vanadium flow battery can have ion conduction performance. This is because the heteropoly acid has high ion conductivity, which can effectively reduce the influence of pore size reduction on the ion conductivity of the porous membrane for the all-vanadium flow battery. Preferably, the heteropoly acid in the porous diaphragm for the all-vanadium redox flow battery accounts for 0.16-14.8wt% of the total mass of the porous diaphragm.
[ porous separator for all-vanadium redox flow battery ]
As mentioned above, the invention provides a porous diaphragm for an all-vanadium redox flow battery, which is prepared by the method.
In a preferred scheme of the invention, the porous membrane is modified by an in-situ filling method, so that the selectivity of the porous membrane is effectively increased, and the influence of nanoparticle filling on the proton conductivity of the membrane is weakened by the load of heteropoly acid.
[ use of porous separator for all-vanadium flow battery ]
As previously mentioned, the present invention provides the use of a porous separator for an all vanadium flow battery.
[ all vanadium redox flow battery ]
As previously described, the present invention provides an all-vanadium flow battery comprising the above porous separator.
In a preferred embodiment of the invention, the charging voltage of the all-vanadium redox flow battery is lower than 1.45V, and the discharging voltage is higher than 1.35V.
In a preferable embodiment of the invention, the all-vanadium redox flow battery has a current efficiency of 94% or more, a voltage efficiency of 78% or more, and an energy efficiency of 73% or more.
The voltage efficiency refers to a ratio of an average voltage of a discharge voltage to an average voltage of a charge voltage.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Ultrasonically dispersing 0.5g of high-molecular pore-forming agent polyvinylpyrrolidone PVP in 15mL of dimethylacetamide to form a uniform solution, then adding 7.4g of polyvinylidene fluoride powder, heating and stirring at 80 ℃ to prepare a uniform polymer solution, adopting a mixed solution (volume ratio is 1: 1) of ethanol and water as a coagulating bath, adopting a manual scraper, controlling the thickness of a membrane formed by the mixed solution on a glass plate to be 200 mu m, evaporating the membrane formed by the mixed solution in air for 1min, then immersing the membrane in the coagulating bath for solidification for 30min, and storing the prepared PVDF porous membrane in water for later use. Before modification, the PVDF porous membrane is placed into an expanding agent ethanol for soaking for 2 hours, and the specific modification process is as follows: placing PVDF porous membraneThe obtained gel solution (n) is addedTetraethoxysilane：nWater (W):nPhosphotungstic acid1:2:1) for 1h, and replacing ethanol in the PVDF porous membrane.
The prepared porous diaphragm is assembled into an all-vanadium redox flow battery, wherein the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the porous diaphragm is 4cm2The current density is 60mA cm-2The concentration of vanadium ions in the electrolyte is 1.5 mol.L-1The concentration of sulfuric acid is 3 mol.L-1。
The coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 95.5%, the voltage efficiency is 80.2%, and the energy efficiency is 76.6%.
Example 2
The other conditions were the same as in example 1 except that ethyl orthosilicate was changed to butyl titanate.
The test conditions were the same as in example 1, and the results were: the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 94.8%, the voltage efficiency is 80.6%, and the energy efficiency is 76.4%.
Example 3
The other conditions were the same as in example 1 except that ethyl orthosilicate was changed to zirconium oxychloride.
The test conditions were the same as in example 1, and the results were: the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 95%, the voltage efficiency is 80.1%, and the energy efficiency is 76.1%.
Example 4
The other conditions were the same as in example 1 except that the PVDF porous membrane was immersed in ethanol for 1 hour.
The test conditions were the same as in example 1, and the results were: the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 94.2%, the voltage efficiency is 79.8%, and the energy efficiency is 75.2%.
Example 5
Otherwise, the conditions were the same as in example 1 except that the composition of the gel solution was nTetraethoxysilane：nWater (W):nPhosphotungstic acid＝1:2:2。
The test conditions were the same as in example 1, and the results were: the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 94.6%, the voltage efficiency is 80.7%, and the energy efficiency is 76.3%.
Example 6
The other conditions were the same as in example 1 except that the swelling agent was methanol.
The test conditions were the same as in example 1, and the results were: the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 96%, the voltage efficiency is 78.1%, and the energy efficiency is 74.9%.
Example 7
The other conditions are the same as example 1, except that the polymeric porogen is ethylene glycol.
The test conditions were the same as in example 1, and the results were: the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 94.6%, the voltage efficiency is 81%, and the energy efficiency is 76.6%.
Comparative example 1
Ultrasonically dispersing 0.5g of high-molecular pore-forming agent polyvinylpyrrolidone PVP in 15mL of dimethylacetamide to form a uniform solution, then adding 7.4g of polyvinylidene fluoride powder, heating and stirring at 80 ℃ to prepare a uniform polymer solution, adopting a mixed solution (volume ratio is 1: 1) of ethanol and water as a coagulating bath, adopting a manual scraper, controlling the thickness of a membrane formed by the mixed solution on a glass plate to be 200 mu m, evaporating the membrane formed by the mixed solution in air for 1min, then immersing the membrane in the coagulating bath for solidification for 30min, and storing the prepared PVDF porous membrane in water for later use.
The prepared porous diaphragm is assembled into an all-vanadium redox flow battery, wherein the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the diaphragm is 4cm2The current density is 60mA cm-2The concentration of vanadium ions in the electrolyte is 1.5 mol.L-1The concentration of sulfuric acid is 3 mol.L-1。
The coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 84%, the voltage efficiency is 86.4%, and the energy efficiency is 72.6%.
Comparative example 2
0.5g of high-molecular pore-forming agent polyvinylpyrrolidone PVP is ultrasonically dispersed in 15mL of dimethylacetamide to form uniform solutionAdding 7.4g of polyvinylidene fluoride powder, heating and stirring at 80 ℃ to prepare a uniform polymer solution, adopting a mixed solution (volume ratio is 1: 1) of ethanol and water as a coagulating bath, adopting a manual scraper, controlling the thickness of a film formed by the mixed solution on a glass plate to be 200 mu m, evaporating the film formed by the mixed solution in the air for 1min, then immersing the film in the coagulating bath for solidification for 30min, and placing the prepared PVDF porous membrane in water for storage for later use. Before modification, the PVDF porous membrane is placed into an expanding agent ethanol for soaking for 2 hours, and the specific modification process is as follows: placing the PVDF porous membrane into the prepared gel solution (n)Tetraethoxysilane：nWater (W)1:2) for 2h, the PVDF porous membrane was replaced with ethanol, and the membrane was taken out and dried at 30 ℃.
The prepared porous diaphragm is assembled into an all-vanadium redox flow battery, wherein the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the porous diaphragm is 4cm2The current density is 60mA cm-2The concentration of vanadium ions in the electrolyte is 1.5 mol.L-1The concentration of sulfuric acid is 3 mol.L-1。
The coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm is 96%, the voltage efficiency is 71%, and the energy efficiency is 68.16%.
Fig. 1 is a graph showing charge and discharge efficiencies of the porous separators prepared in comparative example 1, comparative example 2, and example 1 in the all-vanadium flow battery. As can be seen from fig. 1, the coulombic efficiency of the porous separator is significantly increased by the filling of the nanoparticles, while the loading of the heteropoly acid optimizes the negative impact of the filling of the nanoparticles on the membrane.
Fig. 2 is SEM images of the porous separators prepared in example 1(b) and comparative example 1 (a). As can be seen from FIG. 2, after the porous diaphragm is modified, a layer of phosphotungstic acid-coated silica particle is formed on the surface of the diaphragm, and the aperture and the porosity of the diaphragm are obviously reduced.
The battery performance shows that the ion transmission channel is formed between the nano particles by the heteropoly acid of the modified film of the heteropoly acid coated nano particles, so the ion transmission capability of the nano particles is increased, meanwhile, the pore size of the nano particles is reduced, the selection performance of the film is greatly improved, and the charge and discharge performance of the battery assembled by the film is obviously superior to that of the film and the basal film which are only modified by the nano particles.
From the coulombic efficiency, the voltage efficiency and the energy efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm prepared in the examples 1-7 and the comparative examples 1-2, the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous diaphragm prepared in the invention is more than 94%, the voltage efficiency is more than 78%, the energy efficiency is more than 73%, the coulombic efficiency is better than that of the comparative example 1, and the voltage efficiency and the energy efficiency are both better than that of the comparative example 2.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. A method of making a porous separator, comprising the steps of:
taking a polymer porous membrane as a base membrane, introducing a gel solution into pores of the polymer porous membrane, wherein gel substances in the gel solution generate hydrolysis reaction in the pore channels of the polymer porous membrane to form heteropoly acid-coated nano particles, and preparing a porous diaphragm filled with the heteropoly acid-coated nano particles, namely the porous diaphragm; wherein the gel solution comprises a nanoparticle precursor, water and a heteropoly acid;
the nano particles are silicon dioxide, titanium dioxide or zirconium oxide;
the nanoparticle precursor is selected from one or more of ethyl orthosilicate, butyl titanate or zirconium oxychloride, and the heteropolyacid is selected from one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid or silicomolybdic acid.
2. The production method according to claim 1, wherein the polymer porous membrane is at least one selected from a polyvinylidene fluoride-based porous membrane, a polysulfone-based porous membrane, a polyether sulfone-based porous membrane, a polyacrylonitrile-based porous membrane, a polyimide-based porous membrane, a polyether ketone-based porous membrane, a polytetrafluoroethylene-based porous membrane, a polybenzimidazole-based porous membrane, and a polyethylene pyridine-based porous membrane.
3. The preparation method according to claim 1, wherein the nanoparticles in the porous separator account for 0.2-15wt% of the total mass of the porous separator.
4. The production method according to claim 1, wherein the heteropoly acid in the porous separator accounts for 0.16 to 14.8wt% of the total mass of the porous separator.
5. The production method according to claim 1, wherein the polymer porous membrane is produced by:
(1) dissolving a polymer and a high-molecular pore-foaming agent in an organic solvent to prepare a mixed solution;
(2) and (3) coating the mixed solution obtained in the step (1) on the surface of a base material, standing, and then immersing into a coagulating bath for solidification to prepare the polymer porous membrane.
6. The method for preparing according to claim 1, characterized in that it comprises the steps of:
(1) immersing the polymer porous membrane into an expanding agent, and standing;
(2) mixing the nanoparticle precursor, water and heteropoly acid to prepare a gel solution;
(3) and (3) soaking the polymer porous membrane obtained in the step (1) into the gel solution obtained in the step (2) by adopting an in-situ gel hydrolysis method, standing and taking out to obtain the heteropoly acid coated nano particle filled porous membrane, namely the porous membrane.
7. The preparation method according to claim 5, wherein in the step (1), the mass concentration of the polymer in the mixed solution is 10-40wt%, and the mass concentration of the polymeric porogen is 1-15%.
8. The method according to claim 5, wherein in the step (1), the polymer is at least one selected from polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyetherketoneketone, polytetrafluoroethylene, polybenzimidazole, and polyvinylpyridine.
9. The preparation method according to claim 5, wherein in the step (1), the polymeric porogen is selected from one or more of polyvinylpyrrolidone (PVP), polyethylene glycol and polyvinyl alcohol.
10. The method according to claim 5, wherein in the step (1), the organic solvent is one or more selected from Dimethylformamide (DMF), Dimethylacetamide (DMAC) and Dimethylsulfoxide (DMSO).
11. The production method according to claim 5, wherein in the step (2), the substrate is a glass plate, a stainless steel plate or a nonwoven fabric.
12. The method according to claim 5, wherein the standing time in the step (2) is 1 to 30 min.
13. The production method according to claim 5, wherein in the step (2), the coagulation bath is one or more selected from water, ethanol, propanol, butanol, isopropanol, and methanol.
14. The method according to claim 5, wherein in the step (2), the curing time is 1 to 60 min.
15. The method according to claim 5, wherein in the step (2), the thickness of the polymer porous membrane is 50 to 250 μm, the pore size of the polymer porous membrane is 0.05 to 50nm, and the porosity of the polymer porous membrane is 30 to 70%.
16. The method according to claim 6, wherein in the step (1), the swelling agent is one or more selected from ethanol, methanol, isopropanol and water.
17. The preparation method according to claim 6, wherein in the step (1), the standing time is 1-6 h.
18. The production method according to claim 6, wherein in the step (2), the heteropoly acid: nanoparticle precursor: the molar ratio of water is (0.05-3): (1): (2-4).
19. The preparation method according to claim 6, wherein in the step (3), the standing time is 0.5-6 h.
20. A porous separator prepared by the method of any one of claims 1-19.
21. Use of the porous separator of claim 20 in an all vanadium flow battery.
22. An all vanadium flow battery comprising the porous separator of claim 20.
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