CN115677269B - Organic-inorganic composite diaphragm, slurry for preparing same and alkaline water electrolysis device - Google Patents
Organic-inorganic composite diaphragm, slurry for preparing same and alkaline water electrolysis device Download PDFInfo
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- CN115677269B CN115677269B CN202211313567.5A CN202211313567A CN115677269B CN 115677269 B CN115677269 B CN 115677269B CN 202211313567 A CN202211313567 A CN 202211313567A CN 115677269 B CN115677269 B CN 115677269B
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- 239000002002 slurry Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 56
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 79
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 66
- 239000007790 solid phase Substances 0.000 claims abstract description 32
- 239000007791 liquid phase Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000012528 membrane Substances 0.000 claims description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 29
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 29
- 239000004408 titanium dioxide Substances 0.000 claims description 28
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- 229920002492 poly(sulfone) Polymers 0.000 claims description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 22
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyarylsulfone Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 18
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- 239000012466 permeate Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
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- 238000001075 voltammogram Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an organic-inorganic composite diaphragm, slurry for preparing the same and an alkaline water electrolysis device, wherein the slurry comprises a liquid phase component and a solid phase component, the solid phase component comprises inorganic oxide nano particles, a binder and a pore-forming agent, the mass ratio of the inorganic oxide nano particles in the solid phase component is 70-90%, and the mass of the liquid phase component is 1-1.5 times of the mass of the inorganic oxide nano particles. The organic-inorganic composite diaphragm prepared by the slurry has the advantages of small surface resistance, high gas barrier property, good insulativity and the like, and can be used for better reducing energy consumption and improving the purity of hydrogen production in the alkaline water electrolysis process.
Description
Technical Field
The invention relates to the technical field of alkaline electrolyzed water, in particular to an organic-inorganic composite diaphragm, slurry for preparing the same and an alkaline water electrolysis device.
Background
The clean energy hydrogen energy is one of the important energy carriers in the future, and has wide application prospect. Alkaline water electrolysis is used as a mature green hydrogen preparation technology, and the energy consumption is further reduced. In general, an alkaline water electrolysis apparatus includes an electrolysis cell, electrodes and a diaphragm, and generates hydrogen gas on a cathode side and oxygen gas on an anode side when energized.
The separator for alkaline water electrolysis is required to have properties such as ion permeability, mechanical strength, air tightness, and electrical insulation. Specifically, when the separator is required to have high ion permeability, the surface resistance of the separator can be reduced, and the electrolytic efficiency of the alkaline water electrolyzer can be improved. The separator is required to have good mechanical strength and can withstand the friction between the electrodes of the cell and the separator. The separator is required to have a gas barrier property, and the gas generated by electrolysis cannot permeate the separator, that is, the separator allows only ions to permeate. The diaphragm is required to be non-conductive and in an insulated state.
In the prior art, it is difficult to simultaneously achieve the above four performances of the separator for alkaline water electrolysis represented by PPS, and therefore, it is necessary to develop a new separator for alkaline water electrolysis.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides an organic-inorganic composite diaphragm, slurry for preparing the same and an alkaline water electrolysis device.
In a first aspect, the invention provides a slurry for an organic-inorganic composite membrane, the slurry comprises a liquid phase component and a solid phase component, the solid phase component comprises inorganic oxide nanoparticles, a binder and a pore-forming agent, the mass ratio of the inorganic oxide nanoparticles in the solid phase component is 70-90%, and the mass of the liquid phase component is 1-1.5 times of the mass of the inorganic oxide nanoparticles.
According to the slurry for the organic-inorganic composite membrane provided by the invention, the inorganic oxide nanoparticles comprise zirconium dioxide nanoparticles and/or titanium dioxide nanoparticles.
According to the slurry for the organic-inorganic composite membrane, the diameter of the inorganic oxide nano particles is 10-200nm.
According to the slurry for the organic-inorganic composite membrane, provided by the invention, the inorganic oxide nano particles consist of zirconium dioxide and titanium dioxide in a mass ratio of 1:150-200, wherein the diameter of the zirconium dioxide is d1, and the diameter of the titanium dioxide is d2, so that the following conditions are satisfied:
according to the slurry for the organic-inorganic composite membrane, provided by the invention, the inorganic oxide nano particles consist of zirconium dioxide and titanium dioxide in a mass ratio of 350-400:1, wherein the diameter of the zirconium dioxide is d1, and the diameter of the titanium dioxide is d2, so that the following conditions are satisfied:
according to the slurry for the organic-inorganic composite membrane, the binder is at least one of polysulfone, polyethersulfone, polyarylsulfone and chitosan, and the mass ratio of the binder in the solid phase component is 9-29%.
According to the slurry for the organic-inorganic composite membrane, the pore-forming agent is at least one of polyvinylpyrrolidone and polyvinyl alcohol, and the mass ratio of the pore-forming agent in the solid phase component is 1%.
According to the slurry for the organic-inorganic composite membrane, the liquid phase component is at least one of N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide and water.
In a second aspect, the present invention also provides a method for preparing the slurry for organic-inorganic composite separator, comprising: the binder and pore-forming agent are mixed with the liquid phase component and the resulting material is mixed with the inorganic oxide nanoparticles.
In a third aspect, the invention provides an organic-inorganic composite membrane prepared from any one of the above slurries for organic-inorganic composite membranes.
In a fourth aspect, the present invention provides an alkaline water electrolysis apparatus comprising the above organic-inorganic composite separator.
The invention provides an organic-inorganic composite diaphragm, slurry for preparing the same and an alkaline water electrolysis device, and the slurry controls the composition and the dosage of a solid phase component and a liquid phase component, so that the organic-inorganic composite diaphragm prepared by using the slurry has the advantages of small surface resistance, high gas barrier property, good insulativity and the like, and can be used for better reducing energy consumption and improving the purity of hydrogen production in the alkaline water electrolysis process.
Drawings
FIG. 1 is a flow chart showing the preparation of a slurry for organic-inorganic composite separator in example 4;
FIG. 2 shows the room temperature electrolysis water voltammograms of the ZIRFON diaphragms of example 1 and comparative example, with a membrane area of 1cm 2 。
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
In a first aspect, the invention provides a slurry for an organic-inorganic composite membrane, the slurry comprises a liquid phase component and a solid phase component, the solid phase component comprises inorganic oxide nanoparticles, a binder and a pore-forming agent, the mass ratio of the inorganic oxide nanoparticles in the solid phase component is 70-90%, and the mass of the liquid phase component is 1-1.5 times of the mass of the inorganic oxide nanoparticles.
According to the invention, the composition of the solid phase component is regulated and controlled, the proportion of the main component inorganic oxide nano particles is controlled to be 70-90%, and meanwhile, the dosage of the liquid phase component is regulated and controlled, so that uniform slurry can be obtained, the slurry is prepared into a diaphragm, and the performance of the diaphragm can meet the requirements of alkaline water electrolysis technology.
According to some embodiments of the invention, the inorganic oxide nanoparticles comprise zirconium dioxide nanoparticles and/or titanium dioxide nanoparticles.
That is, in some embodiments of the invention, the inorganic oxide nanoparticles are zirconium dioxide nanoparticles.
In some embodiments of the invention, the inorganic oxide nanoparticles are titanium dioxide nanoparticles.
In some embodiments of the invention, the inorganic oxide nanoparticles are a mixture of zirconium dioxide nanoparticles and titanium dioxide nanoparticles.
Further preferably, the diameter of the inorganic oxide nanoparticle is 10 to 200nm. The particle size of the inorganic oxide nano particles can influence the porosity, the pore diameter, the ion permeability, the mechanical strength and the like of the subsequent diaphragm, and the invention researches show that the particle size is better controlled within the range of 10-200nm.
According to some embodiments of the invention, the inorganic oxide nanoparticles consist of zirconium dioxide and titanium dioxide in a mass ratio of 1:150-200, the zirconium dioxide having a diameter d1 and the titanium dioxide having a diameter d2, satisfying:
according to some embodiments of the invention, the inorganic oxide nanoparticles consist of zirconium dioxide and titanium dioxide in a mass ratio of 350-400:1, the zirconium dioxide having a diameter d1 and the titanium dioxide having a diameter d2, satisfying:
under the above conditions, the inorganic nano particles of zirconium dioxide and titanium dioxide can be mutually embedded between gaps of spherical particles, so that the sufficiency of mutual mixing of the nano particles can be ensured, the slurry is more uniform, a more compact skin layer can be formed during phase inversion, and the performance of the diaphragm is improved.
According to some embodiments of the invention, the binder is at least one of polysulfone, polyethersulfone, polyarylsulfone and chitosan, and the mass ratio of the binder in the solid phase component is 9-29%.
Among them, polysulfone refers to a common bisphenol A type polysulfone (PSF for short), and polysulfone with an average molecular weight of about 8 ten thousand is preferable in the present invention. Polyether sulfone (PES for short), polyarylsulfone (PASF for short). When the binder is a mixture of polysulfone, polyethersulfone and polyarylsulfone, the three can be mixed in any ratio.
The viscosity of chitosan may be low (< 200 mPa-s), medium viscosity (200-400 mPa-s), or high viscosity (> 400 mPa-s).
According to some embodiments of the invention, the pore-forming agent is at least one of polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA), and the mass ratio of the pore-forming agent in the solid phase component is 1%. The pore-forming agent has low mass ratio but cannot be omitted, otherwise, the slurry is easy to disperse unevenly, and powder can be dropped after phase inversion. And the pore-forming agent is also beneficial to forming finger macropores of the loose porous layer, so that the surface resistance is reduced.
The alcoholysis degree of the polyvinyl alcohol is 87-89 mol% and the viscosity is 3.2-3.6 mPa.s.
The average molecular weight of the polyvinylpyrrolidone was 40000.
According to some embodiments of the invention, the liquid phase component is at least one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), water.
In a preferred embodiment of the invention, the inorganic oxide nanoparticles in the slurry are zirconium dioxide nanoparticles and titanium dioxide nanoparticles in a mass ratio of 370:1, the binder is polysulfone, the pore-forming agent is PVP, and the liquid phase component is NMP.
In the scheme, polysulfone has good mechanical strength, acid and alkali resistance and excellent heat resistance, and has the defect of strong hydrophobicity, and the membrane has good hydrophilicity due to the doping of hydrophilic inorganic nano particles.
In a second aspect, the present invention also provides a method for preparing the slurry for organic-inorganic composite separator, comprising: the binder and pore-forming agent are mixed with the liquid phase component and the resulting material is mixed with the inorganic oxide nanoparticles.
Further, it is preferable to mix the binder with the liquid phase component before adding the pore-forming agent.
When the inorganic oxide nanoparticles are plural, it is preferable that the plural inorganic oxide nanoparticles are mixed first and then added to the liquid phase component in which the binder and the pore-forming agent have been dispersed. Further preferably, the liquid phase component is added in multiple portions and mixed uniformly.
In a third aspect, the invention provides an organic-inorganic composite membrane prepared from any one of the above slurries for organic-inorganic composite membranes.
Specifically, the method for preparing the organic-inorganic composite membrane from the slurry comprises the following steps: (1) The slurry components are fully stirred for 3 hours, then the support body is fully immersed in the casting film liquid, then a film scraping device is adopted, a double-sided scraper is adopted, the distance between the support body and the scraper is controlled to be about 200 mu m, and the composite diaphragm in a wet state is prepared. (2) The composite membrane in the wet state is placed into phase inversion liquid for phase inversion, the phase inversion temperature is 20 ℃, the phase inversion liquid is a mixed solution composed of water and NMP, the phase inversion time is 1h, and the phase inversion is ensured to be thorough. In the process, the organic polymer resin in the casting solution is solidified, the solvent is dissolved in water, and the polymer resin and the solvent are subjected to phase separation and become solid resin to form a porous structure. (3) After the phase inversion process is completed, the membrane is boiled in boiling water for 10min, the solvent remained in the membrane is removed, and then the membrane is put into deionized water for preservation.
The organic-inorganic composite diaphragm prepared by the slurry has low surface resistance under the preferable condition, and the surface resistance is 0.12 Ω cm in 30wt% KOH at normal temperature 2 The method comprises the steps of carrying out a first treatment on the surface of the And has high gas barrier performance, 11.94bar, breaking strength up to 26MPa, complete non-conduction and capability of meeting the requirement of further reducing energy consumption of alkaline water electrolysis.
In a fourth aspect, the present invention provides an alkaline water electrolysis apparatus comprising the above organic-inorganic composite separator.
Alkaline water electrolysis devices generally include an electrolysis cell, electrodes and a membrane that when energized produce hydrogen on the cathode side and oxygen on the anode side. The alkaline water electrolysis device adopts the composite diaphragm with ion permeability, mechanical strength, air tightness and electric insulation, so that the electrolysis efficiency of the alkaline water electrolysis device can be improved, the diaphragm can also withstand the friction between an electrode of an electrolysis tank and the diaphragm, the diaphragm has the property of blocking gas, the gas generated by electrolysis cannot permeate the diaphragm, and the diaphragm cannot conduct electricity and is in an insulation state. In sum, the method is safe and efficient.
The following examples are given as examples, and all materials used are commercially available from normal sources unless otherwise specified.
In the following examples, the polysulphone used has an average molecular weight of 8 ten thousand;
the average molecular weight of the polyvinylpyrrolidone was 40000.
The diameter of the zirconium dioxide particles is denoted by d1 and the diameter of the titanium dioxide particles is denoted by d 2.
Example 1
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (1:190 mass ratio of zirconium dioxide and titanium dioxide, d1=10 nm, d2=70 nm) 70%, binder (polysulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following steps:
dissolving polysulfone in N-methyl pyrrolidone, heating and stirring for 1.5 hours until polysulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, adding inorganic oxide nano particles, stirring for 3 hours until the inorganic oxide nano particles are uniformly mixed, and optionally carrying out degassing treatment to obtain the slurry for the organic-inorganic composite membrane.
Example 2
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (mass ratio of 370:1 zirconium dioxide and titanium dioxide, d1=70 nm, d2=10 nm) 70%, binder (polysulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following steps:
dissolving polysulfone in N-methyl pyrrolidone, heating and stirring for 1.5 hours until polysulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, adding inorganic oxide nano particles, stirring for 3 hours until the inorganic oxide nano particles are uniformly mixed, and optionally carrying out degassing treatment to obtain the slurry for the organic-inorganic composite membrane.
Example 3
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (1:200 mass ratio of zirconium dioxide and titanium dioxide, d1=10 nm, d2=200 nm) 70%, binder (polysulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following steps:
dissolving polysulfone in N-methyl pyrrolidone, heating and stirring for 1.5 hours until polysulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, adding inorganic oxide nano particles, stirring for 3 hours until the inorganic oxide nano particles are uniformly mixed, and optionally carrying out degassing treatment to obtain the slurry for the organic-inorganic composite membrane.
Example 4
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (mass ratio of 370:1 zirconium dioxide and titanium dioxide, d1=200 nm, d2=10 nm) 70%, binder (polyethersulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, a flow chart is shown in fig. 1, and the method specifically comprises the following steps:
dissolving polyethersulfone in N-methyl pyrrolidone, heating and stirring for 1.5 hours until the polyethersulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, adding inorganic oxide nano particles (zirconium dioxide and titanium dioxide particles are mixed in advance), stirring for 3 hours until the mixture is uniform, and optionally carrying out degassing treatment to obtain the slurry for the organic-inorganic composite membrane.
Example 5
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (1:200 mass ratio of zirconium dioxide and titanium dioxide, d1=10 nm, d2=70 nm) 70%, binder (polyarylsulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following steps:
dissolving polyarylsulfone in N-methyl pyrrolidone, heating and stirring for 1.5 hours until the polyarylsulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, adding inorganic oxide nano particles, stirring for 3 hours until the mixture is uniformly mixed, and optionally carrying out degassing treatment to obtain the slurry for the organic-inorganic composite membrane.
Example 6
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370:1, d1=70 nm, d2=10 nm) 70%, binder (chitosan) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following steps:
dissolving chitosan in N-methyl pyrrolidone, heating and stirring for 1.5 hours until the chitosan is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, adding inorganic oxide nano particles, stirring for 3 hours until the inorganic oxide nano particles are uniformly mixed, and optionally carrying out degassing treatment to obtain the slurry for the organic-inorganic composite membrane.
Example 7
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (mass ratio of 370:1 zirconium dioxide and titanium dioxide, d1=100 nm, d2=150 nm) 70%, binder (polysulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The preparation method is the same as in example 1.
Example 8
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (mass ratio of 370:1 zirconium dioxide and titanium dioxide, d1=70 nm, d2=10 nm) 90%, binder (polysulfone) 9%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 2 times of the mass of the inorganic oxide nano particles.
The preparation method is the same as in example 1.
Example 9
The embodiment provides a slurry for an organic-inorganic composite membrane, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide, d1=100 nm) 70%, binder (polysulfone) 29%, pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase component: n-methyl pyrrolidone is 1.2 times of the inorganic oxide nano particles.
The preparation method is the same as in example 1.
Performance testing
The slurries obtained in the examples were prepared into diaphragms and compared with commercial ZIRFON diaphragms (control) for performance testing, and the results are shown in table 1.
The method for preparing the slurry into the diaphragm comprises the following steps: (1) The slurry components are fully stirred for 3 hours, then the support body is fully immersed in the casting film liquid, then a film scraping device is adopted, a double-sided scraper is adopted, the distance between the support body and the scraper is controlled to be about 200 mu m, and the composite diaphragm in a wet state is prepared. (2) The composite membrane in the wet state is placed into phase inversion liquid for phase inversion, the phase inversion temperature is 20 ℃, the phase inversion liquid is a mixed solution composed of water and NMP, the phase inversion time is 1h, and the phase inversion is ensured to be thorough. In the process, the organic polymer resin in the casting solution is solidified, the solvent is dissolved in water, and the polymer resin and the solvent are subjected to phase separation and become solid resin to form a porous structure. (3) After the phase inversion process is completed, the membrane is boiled in boiling water for 10min, the solvent remained in the membrane is removed, and then the membrane is put into deionized water for preservation.
The performance test comprises test items such as surface resistance, bubble point and the like, and the specific method comprises the following steps:
the surface resistance test method is as follows:
the separator was cut into small pieces and after soaking in 30wt% KOH solution for 1 day, the resistance was tested using an electrochemical workstation.
The bubble point test method is as follows:
cutting the membrane into small pieces, soaking with high-purity water, placing into a bubble pressure method membrane aperture analyzer (BSD-PB) for testing, applying gas pressure on one side of the membrane, and taking the pressure as the bubble point of the membrane when the other side of the membrane detects 1mL/min gas flow. The bubble point is calculated as follows:
wherein D = pore diameter, units μm; γ=surface tension of liquid, unit: dny/cm; θ=contact angle, unit: a degree; Δp=differential pressure, unit KPa.
The tensile strength test method is as follows:
and cutting the rectangular small diaphragm, and placing the diaphragm on a tensile testing machine for testing.
The insulation performance test method is as follows:
a square diaphragm 5cm wide was taken, clamped by two stainless steel plates, and the resistance was tested by an electrochemical workstation.
TABLE 1
FIG. 2 is a graph of the room temperature electrolyzed water voltammograms of the ZIRFON membranes of example 1 and comparative example, with a membrane area of 1cm 2 The electrolyte performance of the separator prepared in this example was better than that of the comparative example.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The slurry for the organic-inorganic composite membrane is characterized by comprising a liquid phase component and a solid phase component, wherein the solid phase component comprises inorganic oxide nano particles, a binder and a pore-forming agent, the mass ratio of the inorganic oxide nano particles in the solid phase component is 70-90%, and the mass of the liquid phase component is 1-1.5 times of the mass of the inorganic oxide nano particles;
the diameter of the inorganic oxide nano-particles is 10-200nm;
the inorganic oxide nano particles consist of zirconium dioxide and titanium dioxide in a mass ratio of 1:150-200, wherein the diameter of the zirconium dioxide is d1, and the diameter of the titanium dioxide is d2, so that the following conditions are satisfied:
2. the slurry for the organic-inorganic composite membrane is characterized by comprising a liquid phase component and a solid phase component, wherein the solid phase component comprises inorganic oxide nano particles, a binder and a pore-forming agent, the mass ratio of the inorganic oxide nano particles in the solid phase component is 70-90%, and the mass of the liquid phase component is 1-1.5 times of the mass of the inorganic oxide nano particles;
the diameter of the inorganic oxide nano-particles is 10-200nm;
the inorganic oxide nano particles consist of zirconium dioxide and titanium dioxide in a mass ratio of 350-400:1, wherein the diameter of the zirconium dioxide is d1, and the diameter of the titanium dioxide is d2, so that the following conditions are satisfied:
3. the slurry for an organic-inorganic composite separator according to claim 1 or 2, wherein the binder is at least one of polysulfone, polyethersulfone, polyarylsulfone, and chitosan, and the mass ratio of the binder in the solid phase component is 9 to 29%;
and/or the pore-forming agent is at least one of polyvinylpyrrolidone and polyvinyl alcohol, and the mass ratio of the pore-forming agent in the solid phase component is 1%.
4. The slurry for an organic-inorganic composite separator according to claim 1 or 2, wherein the liquid phase component is at least one of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, and water.
5. The method for producing a slurry for an organic-inorganic composite separator according to any one of claims 1 to 4, comprising:
the binder and pore-forming agent are mixed with the liquid phase component and the resulting material is mixed with the inorganic oxide nanoparticles.
6. An organic-inorganic composite separator prepared from the slurry for an organic-inorganic composite separator according to any one of claims 1 to 4.
7. An alkaline water electrolysis apparatus comprising the organic-inorganic composite separator according to claim 6.
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| CN202211313567.5A CN115677269B (en) | 2022-10-25 | 2022-10-25 | Organic-inorganic composite diaphragm, slurry for preparing same and alkaline water electrolysis device |
| PCT/CN2023/107896 WO2024087748A1 (en) | 2022-10-25 | 2023-07-18 | Organic-inorganic composite separator and slurry for preparing same, and alkaline water electrolysis device |
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| CN115677269B (en) * | 2022-10-25 | 2023-06-27 | 清华大学 | Organic-inorganic composite diaphragm, slurry for preparing same and alkaline water electrolysis device |
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| BE1006659A3 (en) * | 1992-01-29 | 1994-11-08 | Vito | Process for the manufacture of a membrane, membrane and thus manufactured with such membrane electrochemical cell. |
| JP2005285413A (en) * | 2004-03-29 | 2005-10-13 | Konica Minolta Holdings Inc | Proton conductive membrane, its manufacturing method, and solid polymer type fuel cell using proton conductive membrane |
| RU2322460C1 (en) * | 2006-12-07 | 2008-04-20 | Государственное образовательное учреждение высшего профессионального образования "Московский энергетический институт (технический университет)" (ГОУВПО "МЭИ(ТУ)") | Method for making membrane for electrolytic decomposition of water |
| WO2013143833A1 (en) * | 2012-03-28 | 2013-10-03 | Nv Bekaert Sa | Assembly of a porous metal diffusion substrate and a polymeric separator membrane |
| CN105304847B (en) * | 2014-07-30 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of application of heat resistant type porous septum in lithium ion battery |
| WO2018139610A1 (en) * | 2017-01-26 | 2018-08-02 | 旭化成株式会社 | Bipolar electrolytic vessel, bipolar electrolytic vessel for alkali water electrolysis, and method for manufacturing hydrogen |
| JP7136580B2 (en) * | 2018-04-17 | 2022-09-13 | 旭化成株式会社 | Diaphragm, method for manufacturing diaphragm, electrolytic cell, and method for producing hydrogen |
| JP7114726B2 (en) * | 2018-09-26 | 2022-08-08 | 株式会社日本触媒 | Diaphragm for alkaline water electrolysis |
| CN109524604A (en) * | 2018-12-07 | 2019-03-26 | 银隆新能源股份有限公司 | A kind of lithium ion battery separator and lithium ion battery |
| JP7284001B2 (en) * | 2019-06-27 | 2023-05-30 | 株式会社日本触媒 | Diaphragm for alkaline water electrolysis and method for producing the diaphragm |
| CN110752338B (en) * | 2019-10-17 | 2020-07-28 | 华南理工大学 | Lithium ion battery composite diaphragm |
| CN113871797A (en) * | 2020-06-11 | 2021-12-31 | 恒大新能源技术(深圳)有限公司 | Ceramic diaphragm and preparation method and application thereof |
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