CN115677269A - Organic-inorganic composite diaphragm and slurry for preparing same and alkaline water electrolysis device - Google Patents
Organic-inorganic composite diaphragm and slurry for preparing same and alkaline water electrolysis device Download PDFInfo
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- CN115677269A CN115677269A CN202211313567.5A CN202211313567A CN115677269A CN 115677269 A CN115677269 A CN 115677269A CN 202211313567 A CN202211313567 A CN 202211313567A CN 115677269 A CN115677269 A CN 115677269A
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- 239000002002 slurry Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 79
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 64
- 239000007790 solid phase Substances 0.000 claims abstract description 29
- 239000007791 liquid phase Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
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- 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 54
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 31
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 21
- 229920002492 poly(sulfone) Polymers 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 14
- 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
- 238000002156 mixing Methods 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
- 238000000034 method Methods 0.000 abstract description 13
- 239000007789 gas Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 20
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 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
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- 238000010998 test method Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 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
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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 nanoparticles, a binder and a pore-forming agent, the mass proportion 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 that of the inorganic oxide nanoparticles. 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 better reduce energy consumption and improve the hydrogen production purity when being used for 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. As a mature green hydrogen preparation technology, alkaline water electrolysis has a further reduced energy consumption space. Generally, an alkaline water electrolysis apparatus includes an electrolytic cell, electrodes and a diaphragm, and generates hydrogen on the cathode side and oxygen on the anode side when energized.
Separators for alkaline water electrolysis are required to have ion permeability, mechanical strength, airtightness, electrical insulation, and other properties. Specifically, if the separator is required to have high ion permeability, the surface resistance of the separator can be reduced, and the electrolysis efficiency of the alkaline water electrolysis cell can be improved. The separator is required to have a good mechanical strength so as to withstand the friction between the electrodes of the electrolytic cell and the separator. The separator is required to have gas barrier properties, and gases generated by electrolysis cannot permeate the separator, that is, the separator allows only ions to permeate. The separator is required to be in an insulating state without conducting electricity.
In the prior art, it is difficult to simultaneously achieve the above four properties of a diaphragm for alkaline water electrolysis represented by PPS, and therefore, it is necessary to develop a new diaphragm for alkaline water electrolysis.
Disclosure of Invention
Aiming at the problems 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 slurry for an organic-inorganic composite diaphragm, which comprises a liquid-phase component and a solid-phase component, wherein the solid-phase component comprises inorganic oxide nanoparticles, a binder and a pore-forming agent, the mass proportion 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 that of the inorganic oxide nanoparticles.
According to the slurry for the organic-inorganic composite separator 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 separator provided by the invention, the diameter of the inorganic oxide nano-particles is 10-200nm.
According to the slurry for the organic-inorganic composite diaphragm, the inorganic oxide nanoparticles consist of zirconium dioxide and titanium dioxide in a mass ratio of 1:
according to the slurry for the organic-inorganic composite diaphragm, the inorganic oxide nanoparticles consist of zirconium dioxide and titanium dioxide in a mass ratio of 350-400, wherein the diameter of the zirconium dioxide is d1, the diameter of the titanium dioxide is d2, and the following conditions are met:
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 percentage of the binder in the solid phase component is 9-29%.
According to the slurry for the organic-inorganic composite diaphragm, 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 diaphragm provided by the invention, 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 an organic-inorganic composite separator, including: and mixing the binder, the pore-forming agent and the liquid-phase component, and then mixing the obtained material with the inorganic oxide nano-particles.
In a third aspect, the present invention provides an organic-inorganic composite separator prepared from any one of the slurries for organic-inorganic composite separators described above.
In a fourth aspect, the present invention provides an alkaline water electrolysis apparatus comprising the above organic-inorganic composite separator.
The slurry of the invention controls the composition and the dosage of a solid phase component and a liquid phase component, so that the organic-inorganic composite membrane prepared by the slurry has the advantages of small surface resistance, high gas barrier property, good insulating property and the like, and can better reduce energy consumption and improve the hydrogen production purity when being used for an alkaline water electrolysis process.
Drawings
FIG. 1 is a flow chart showing the preparation of a slurry for an organic-inorganic composite separator in example 4;
FIG. 2 is a voltammogram of room temperature electrolyzed water of example 1 and comparative example ZIRFON separator with a membrane area of 1cm 2 。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 an embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In a first aspect, the invention provides slurry for an organic-inorganic composite diaphragm, which comprises a liquid-phase component and a solid-phase component, wherein the solid-phase component comprises inorganic oxide nanoparticles, a binder and a pore-forming agent, the mass proportion 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 that of the inorganic oxide nanoparticles.
The research of the invention finds that the composition of the solid phase component is regulated, the proportion of the inorganic oxide nano particles as the main component is controlled to be 70-90%, the dosage of the liquid phase component is regulated at the same time, more uniform slurry can be obtained and is made into the diaphragm, and the performance of the diaphragm can also meet the requirement of the 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 present 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 inorganic oxide nanoparticles have a diameter of 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 a subsequent diaphragm, and the research of the invention finds that the particle size is controlled within the range of 10-200nm better.
According to some embodiments of the present invention, the inorganic oxide nanoparticles are composed of zirconia and titania in a mass ratio of 1:
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 condition, the zirconium dioxide and titanium dioxide inorganic nanoparticles can be embedded between gaps of spherical particles, so that the mixing sufficiency of the nanoparticles can be ensured, the slurry is more uniform, a more compact skin layer can be formed during phase conversion, 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%.
Wherein, the polysulfone refers to common bisphenol A type polysulfone (PSF for short), and the polysulfone with the average molecular weight of about 8 ten thousand is preferred in the invention. Polyether sulfone (PES) and Polyarylsulfone (PASF). When the binder is a mixture of polysulfone, polyethersulfone and polyarylsulfone, the three can be mixed in any proportion.
The viscosity of the chitosan can be low (< 200mPa · s), medium viscosity (200-400 mPa · s), or high viscosity (> 400mPa · 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 mass ratio of the pore-forming agent is not high, but is not omitted, otherwise, the slurry is easy to disperse and is not uniform, and the powder falls off after phase conversion. And the pore-forming agent can also be beneficial to forming finger-shaped macropores of a loose porous layer, so that the surface resistance is reduced.
The polyvinyl alcohol used has an alcoholysis degree of 87 to 89mol% and a viscosity of 3.2 to 3.6 mPas.
The average molecular weight of the polyvinylpyrrolidone is 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 present invention, the inorganic oxide nanoparticles in the slurry are zirconia nanoparticles and titania nanoparticles at a mass ratio of 370.
In the scheme, the polysulfone has good mechanical strength, excellent acid and alkali resistance and excellent heat resistance, has the defect of strong hydrophobicity, and the membrane has good hydrophilicity by doping hydrophilic inorganic nanoparticles.
In a second aspect, the present invention also provides a method for preparing the slurry for an organic-inorganic composite separator, including: and mixing the binder, the pore-forming agent and the liquid-phase component, and then mixing the obtained material with the inorganic oxide nano-particles.
Further, it is preferable to mix the binder with the liquid-phase component and then add 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 components are added in portions and mixed uniformly.
In a third aspect, the present invention provides an organic-inorganic composite separator prepared from any one of the slurries for organic-inorganic composite separators described above.
Specifically, the method for preparing the organic-inorganic composite separator from the slurry comprises the following steps: (1) Fully stirring the slurry components for 3 hours, completely immersing the support body in the membrane casting solution, and then adopting a membrane scraping device and a double-sided scraper to control the distance between the support body and the scraper to be about 200 mu m so as to prepare the wet composite membrane. (2) And (3) putting the wet composite diaphragm into a phase inversion solution for phase inversion, wherein the phase inversion temperature is 20 ℃, the phase inversion solution is a mixed solution consisting of water and NMP, and the phase inversion time is 1h, so that the phase inversion is relatively 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 to become solid resin, so that a porous structure is formed. (3) After the phase inversion process is finished, the diaphragm is boiled for 10mins by boiling water, residual solvent in the diaphragm is removed, and then the diaphragm is put into deionized water for storage.
The organic-inorganic composite diaphragm prepared by adopting the slurry has low surface resistance under the optimal conditions, and the surface resistance is 0.12 omega cm in 30wt% of KOH at normal temperature 2 (ii) a And the gas barrier performance is high, 11.94bar, the breaking strength can reach 26MPa, and the gas barrier material is completely non-conductive, so that the requirement of further reducing energy consumption by alkaline water electrolysis can be met.
In a fourth aspect, the present invention provides an alkaline water electrolysis apparatus comprising the above organic-inorganic composite separator.
An alkaline water electrolysis apparatus generally comprises an electrolysis cell, electrodes and a diaphragm, and when energized, produces hydrogen on the cathode side and oxygen on the anode side. The alkaline water electrolysis device adopts the composite diaphragm which simultaneously has ion permeability, mechanical strength, air tightness and electrical insulation, so that the electrolysis efficiency of the alkaline water electrolysis device can be improved, the diaphragm can bear the friction between the electrodes of the electrolysis bath and the diaphragm, the diaphragm has the performance of gas barrier, the gas generated by electrolysis cannot permeate the diaphragm, the diaphragm cannot conduct electricity and is in an insulation state. In conclusion, it is safe and efficient.
The following are specific examples, and all of the raw materials used are obtained from normal commercial sources unless otherwise specified.
In the following examples, the polysulfone used had an average molecular weight of 8 ten thousand;
the average molecular weight of the polyvinylpyrrolidone is 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 slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (1 mass ratio of zirconium dioxide to titanium dioxide of 190, d1=10nm, d2= 70nm) 70%, a binder (polysulfone) 29%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: n-methyl pyrrolidone with the mass 1.2 times of that of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following specific steps:
dissolving polysulfone in N-methyl pyrrolidone, heating and stirring for 1.5h until the polysulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, then adding inorganic oxide nanoparticles, stirring for 3h until the inorganic oxide nanoparticles are uniformly mixed, and performing degassing treatment according to the situation to obtain the slurry for the organic-inorganic composite diaphragm.
Example 2
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370, d1=70nm, d2= 10nm) 70%, a binder (polysulfone) 29%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: n-methyl pyrrolidone with the mass 1.2 times of that of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following specific steps:
dissolving polysulfone in N-methyl pyrrolidone, heating and stirring for 1.5h until the polysulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, then adding inorganic oxide nanoparticles, stirring for 3h until the inorganic oxide nanoparticles are uniformly mixed, and performing degassing treatment according to the situation to obtain the slurry for the organic-inorganic composite diaphragm.
Example 3
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (1 mass ratio of zirconium dioxide to titanium dioxide of 1;
liquid phase components: n-methyl pyrrolidone with the mass being 1.2 times of the mass of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following specific steps:
dissolving polysulfone in N-methyl pyrrolidone, heating and stirring for 1.5h until the polysulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, then adding inorganic oxide nanoparticles, stirring for 3h until the inorganic oxide nanoparticles are uniformly mixed, and performing degassing treatment according to the situation to obtain the slurry for the organic-inorganic composite diaphragm.
Example 4
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370, d1=200nm, d2= 10nm) 70%, a binder (polyether sulfone) 29%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: n-methyl pyrrolidone with the mass 1.2 times of that of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, and the flow schematic diagram is shown in fig. 1, and specifically includes the following steps:
dissolving polyether sulfone in N-methyl pyrrolidone, heating and stirring for 1.5h until the polyether sulfone is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, then adding inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide particles are mixed in advance), stirring for 3h until the inorganic oxide nanoparticles are uniformly mixed, and optionally performing degassing treatment to obtain the slurry for the organic-inorganic composite diaphragm.
Example 5
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (1 mass ratio of zirconia to titania, d1=10nm, d2= 70nm) 70%, a binder (polyarylsulfone) 29%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: n-methyl pyrrolidone with the mass being 1.2 times of the mass of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following specific steps:
firstly, dissolving polyarylsulfone in N-methyl pyrrolidone, heating and stirring for 1.5h until the polyarylsulfone is completely dissolved, then adding the polyvinylpyrrolidone, stirring until the solution is clear and transparent, then adding inorganic oxide nano particles, stirring for 3h until the mixture is uniformly mixed, and degassing according to the situation to obtain the slurry for the organic-inorganic composite diaphragm.
Example 6
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370, d1=70nm, d2= 10nm) 70%, a binder (chitosan) 29%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: n-methyl pyrrolidone with the mass being 1.2 times of the mass of the inorganic oxide nano particles.
The embodiment also provides a preparation method of the slurry, which comprises the following specific steps:
dissolving chitosan in N-methyl pyrrolidone, heating and stirring for 1.5h until the chitosan is completely dissolved, adding polyvinylpyrrolidone, stirring until the solution is clear and transparent, then adding inorganic oxide nanoparticles, stirring for 3h until the inorganic oxide nanoparticles are uniformly mixed, and degassing according to the situation to obtain the slurry for the organic-inorganic composite diaphragm.
Example 7
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370, d1=100nm, d2= 150nm) 70%, a binder (polysulfone) 29%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: n-methyl pyrrolidone with the mass being 1.2 times of the mass of the inorganic oxide nano particles.
The preparation method is the same as that of example 1.
Example 8
The embodiment provides slurry for an organic-inorganic composite diaphragm, which comprises the following components:
solid phase component: inorganic oxide nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370, d1=70nm, d2= 10nm) 90%, a binder (polysulfone) 9%, and a pore-forming agent (polyvinylpyrrolidone) 1%;
liquid phase components: and the mass of the N-methyl pyrrolidone is 2 times of that of the inorganic oxide nano particles.
The preparation method is the same as that of example 1.
Example 9
The embodiment provides slurry for an organic-inorganic composite diaphragm, 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 components: n-methyl pyrrolidone with the mass 1.2 times of that of the inorganic oxide nano particles.
The preparation method is the same as that of example 1.
Performance testing
The slurries obtained in the respective examples were prepared into separators and compared with commercial ZIRFON separators (comparative example) for performance tests, and the results are shown in table 1.
The method for preparing the diaphragm from the slurry comprises the following steps: (1) Fully stirring the slurry components for 3 hours, completely immersing the support body in the casting solution, and then adopting a film scraping device and a double-sided scraper to control the distance between the support body and the scraper to be about 200 mu m so as to prepare the wet composite diaphragm. (2) And (3) putting the wet composite diaphragm into a phase inversion solution for phase inversion, wherein the phase inversion temperature is 20 ℃, the phase inversion solution is a mixed solution consisting of water and NMP, and the phase inversion time is 1h, so that the phase inversion is relatively 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 to become solid resin, so that a porous structure is formed. (3) After the phase inversion process is finished, the diaphragm is boiled for 10mins by boiling water, residual solvent in the diaphragm is removed, and then the diaphragm is put into deionized water for storage.
The performance test comprises test items such as surface resistance, bubble point and the like, and the specific method comprises the following steps:
the test method of the surface resistance is as follows:
the membrane was cut into small pieces and after 1 day immersion in 30wt% KOH solution, the resistance was tested with an electrochemical workstation.
The bubble point test method is as follows:
cutting the diaphragm into small blocks, soaking the small blocks by using high-purity water, placing the small blocks into a bubble pressure method membrane aperture analyzer (BSD-PB) for testing, applying gas pressure on one side of the membrane, and regarding the pressure as a bubble point of the diaphragm when gas flow of 1mL/min is detected on the other side of the membrane. The bubble point is calculated as follows:
wherein D = pore diameter, unit μm; γ = surface tension of the liquid, unit: dny/cm; θ = contact angle, unit: degree; Δ P = pressure difference, unit KPa.
The tensile strength was measured as follows:
and cutting a 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 clamped between two stainless steel plates, and the resistance was measured using an electrochemical workstation.
TABLE 1
FIG. 2 is a voltammogram of room temperature electrolyzed water of example 1 and comparative example ZIRFON membranes, with a membrane area of 1cm 2 It is shown that the electrolytic water performance of the separator prepared in this example is superior to that of the comparative example.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The slurry for the organic-inorganic composite diaphragm is characterized by comprising a liquid-phase component and a solid-phase component, wherein the solid-phase component comprises inorganic oxide nanoparticles, a binder and a pore-forming agent, the mass proportion 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 that of the inorganic oxide nanoparticles.
2. The slurry for an organic-inorganic composite separator according to claim 1, wherein the inorganic oxide nanoparticles comprise zirconium dioxide nanoparticles and/or titanium dioxide nanoparticles.
3. The slurry for an organic-inorganic composite separator according to claim 2, wherein the inorganic oxide nanoparticles have a diameter of 10 to 200nm.
4. The slurry for an organic-inorganic composite separator according to claim 3, wherein the inorganic oxide nanoparticles are composed of zirconium dioxide and titanium dioxide at a mass ratio of 1 to 150-200, the zirconium dioxide has a diameter d1, and the titanium dioxide has a diameter d2, and satisfy:
5. the slurry for an organic-inorganic composite separator according to claim 3, wherein the inorganic oxide nanoparticles are composed of zirconium dioxide and titanium dioxide at a mass ratio of 350-400, the zirconium dioxide has a diameter d1, and the titanium dioxide has a diameter d2, and satisfy:
6. the slurry for organic-inorganic composite membranes according to any one of claims 1 to 5, characterized in that the binder is at least one of polysulfone, polyethersulfone, polyarylsulfone and chitosan, and the mass proportion of the binder in the solid phase component is 9-29%;
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%.
7. The slurry for an organic-inorganic composite separator according to any one of claims 1 to 5, wherein the liquid phase component is at least one of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, and water.
8. The method for producing the slurry for an organic-inorganic composite separator according to any one of claims 1 to 7, comprising:
and mixing the binder, the pore-forming agent and the liquid-phase component, and then mixing the obtained material with the inorganic oxide nano-particles.
9. An organic-inorganic composite separator produced from the slurry for organic-inorganic composite separators according to any one of claims 1 to 7.
10. An alkaline water electrolysis apparatus comprising the organic-inorganic composite separator according to claim 9.
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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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Cited By (2)
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| CN117512692A (en) * | 2023-11-17 | 2024-02-06 | 武汉理工大学 | Coating type alkaline water electrolysis hydrogen production diaphragm |
| WO2024087748A1 (en) * | 2022-10-25 | 2024-05-02 | 清华大学 | Organic-inorganic composite separator and slurry for preparing same, and alkaline water electrolysis device |
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