WO2024087742A1 - 隔膜浆料及其制备方法和碱性水电解用隔膜 - Google Patents

隔膜浆料及其制备方法和碱性水电解用隔膜 Download PDF

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WO2024087742A1
WO2024087742A1 PCT/CN2023/107499 CN2023107499W WO2024087742A1 WO 2024087742 A1 WO2024087742 A1 WO 2024087742A1 CN 2023107499 W CN2023107499 W CN 2023107499W WO 2024087742 A1 WO2024087742 A1 WO 2024087742A1
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porous membrane
raw material
diaphragm
solvent
pore size
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PCT/CN2023/107499
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English (en)
French (fr)
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王海辉
丁力
廖益文
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清华大学
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Publication of WO2024087742A1 publication Critical patent/WO2024087742A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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

Definitions

  • the invention relates to the technical field of slurry preparation, and in particular to a diaphragm slurry and a preparation method thereof, and a diaphragm for alkaline water electrolysis.
  • an alkaline water electrolysis device includes an electrolyzer, electrodes and a diaphragm. When powered on, hydrogen is produced on the cathode side and oxygen is produced on the anode side.
  • alkaline water electrolysis diaphragms are usually prepared using a slurry including inorganic nanoparticles, organic high molecular polymers, and a binder.
  • the resulting alkaline water electrolysis diaphragms are difficult to simultaneously have good ion permeability, mechanical strength, air tightness, and electrical insulation.
  • the present invention provides a diaphragm slurry and a preparation method thereof, and a diaphragm for alkaline water electrolysis.
  • the present invention provides a method for preparing a diaphragm slurry, comprising the steps of mixing three streams of liquid formed by passing raw material A through a porous membrane A, raw material B through a porous membrane B, and raw material C through a porous membrane C,
  • the raw material A is a mixture of inorganic nanoparticles and solvent
  • the raw material B is a mixture of a binder and solvent
  • the raw material C is a mixture of an organic high molecular polymer and solvent
  • the pore size of the porous membrane A is 1000-2000 nm
  • the pore size of the porous membrane B is 500-1000 nm
  • the pore size of the porous membrane C is 400-800 nm.
  • a pressure of 5-10 MPa is applied to the feed side of the porous membrane.
  • the inorganic nanoparticles are zirconium dioxide and/or titanium dioxide, and the particle size of the inorganic nanoparticles is 10-200 nm.
  • the inorganic nanoparticles are composed of zirconium dioxide and titanium dioxide in a mass ratio of 1:150-200, the diameter of the zirconium dioxide is d1, the diameter of the titanium dioxide is d2, and the following conditions are satisfied:
  • the inorganic nanoparticles are composed of zirconium dioxide and titanium dioxide in a mass ratio of 350-400:1, the diameter of the zirconium dioxide is d1, the diameter of the titanium dioxide is d2, and the following conditions are satisfied:
  • the organic high molecular polymer is one or more of polyether sulfone, polyaryletherketone and chitosan.
  • the binder is one or more of polyvinyl pyrrolidone and polyvinyl alcohol.
  • the solvent is one or more of N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide.
  • the mass ratio of the inorganic nanoparticles, the organic high molecular polymer and the binder is 70-90:9-29:1.
  • the total mass of the solvent is 1-1.5 times the mass of the inorganic nanoparticles.
  • the present invention provides a diaphragm slurry prepared by the above-mentioned preparation method.
  • the present invention provides a diaphragm for alkaline water electrolysis, and the raw materials for preparing the diaphragm slurry include the above-mentioned diaphragm slurry.
  • the present invention provides a diaphragm slurry and a preparation method thereof and a diaphragm for alkaline water electrolysis.
  • the present invention adopts a porous membrane permeation technology to pass through a membrane with a certain pore size.
  • a certain pressure is applied to the feed side of the reactor so that each component liquid can form multiple tiny droplets before mixing with each other, and finally mix to form a uniform slurry.
  • the diaphragm prepared by using the slurry obtained by the present invention has a narrow pore size distribution and controllable pore size. When used in the alkaline water electrolysis process, it is beneficial to improve the bubble point of the diaphragm while maintaining a high ion permeability.
  • FIG. 1 is a schematic diagram of a method for preparing a diaphragm slurry according to an embodiment of the present invention.
  • the present invention provides a method for preparing a diaphragm slurry, comprising the steps of mixing three streams of liquid formed by passing raw material A through a porous membrane A, raw material B through a porous membrane B, and raw material C through a porous membrane C,
  • the raw material A is a mixture of inorganic nanoparticles and a solvent
  • the raw material B is a mixture of a binder and a solvent
  • the raw material C is a mixture of an organic high molecular polymer and a solvent
  • the pore size of the porous membrane A is 1000-2000 nm
  • the pore size of the porous membrane B is 500-1000 nm
  • the pore size of the porous membrane C is 400-800 nm.
  • the present invention has found that improving the slurry preparation method can make the slurry more evenly dispersed, which can also greatly improve the performance of the diaphragm, and the improved preparation method is more convenient to operate.
  • the porous membrane permeation technology is adopted, and the specific raw materials are passed through a porous membrane with a specific pore size, so that each component liquid forms a plurality of tiny droplets, which are finally mixed to form a uniform slurry.
  • the diaphragm prepared by using the slurry obtained by the present invention has a narrow pore size distribution and a controllable pore size. When used in the alkaline water electrolysis process, it is beneficial to improve the bubble point of the diaphragm while maintaining a high ion permeability.
  • raw material A, raw material B and raw material C may pass through their respective porous membranes simultaneously or at different times, but the interval should not be too long, and they are preferably passed through simultaneously.
  • a pressure of 5-10 MPa is applied on the feed side of the porous membrane.
  • the inorganic nanoparticles are zirconium dioxide and/or titanium dioxide, and the particle size of the inorganic nanoparticles is 10-200 nm.
  • the inorganic nanoparticles are zirconium dioxide nanoparticles.
  • the inorganic nanoparticles are titanium dioxide nanoparticles.
  • the inorganic nanoparticles are a mixture of zirconium dioxide nanoparticles and titanium dioxide nanoparticles.
  • the inorganic nanoparticles are composed of zirconium dioxide and titanium dioxide in a mass ratio of 1:150-200, the diameter of the zirconium dioxide is d1, the diameter of the titanium dioxide is d2, and the following conditions are satisfied:
  • the inorganic nanoparticles are composed of zirconium dioxide and titanium dioxide in a mass ratio of 350-400:1, the diameter of the zirconium dioxide is d1, and the The diameter of titanium dioxide is d2, which satisfies:
  • inorganic nanoparticles of zirconium dioxide and titanium dioxide can be embedded in the gaps between spherical particles, which can ensure the sufficient mixing of the nanoparticles, make the slurry more uniform, form a denser skin during phase transformation, and improve the performance of the diaphragm.
  • the organic high molecular polymer is one or more of polyethersulfone, polyaryletherketone, and chitosan.
  • the viscosity of chitosan can be low viscosity ( ⁇ 200 mPa ⁇ s), medium viscosity (200-400 mPa ⁇ s), or high viscosity (>400 mPa ⁇ s).
  • the organic high molecular polymer is a mixture of two or more of polyethersulfone, polyaryletherketone, and chitosan, they can be mixed in any proportion.
  • the binder is one or more of polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA).
  • PVP polyvinyl pyrrolidone
  • PVA polyvinyl alcohol
  • the polyvinyl alcohol used has a degree of alcoholysis of 87%-89 mol% and a viscosity of 3.2-3.6 mPa ⁇ s.
  • the average molecular weight of the polyvinyl pyrrolidone is 40,000.
  • the solvent is one or more of N-methylpyrrolidone NMP, N,N-dimethylformamide DMF, and dimethyl sulfoxide DMSO.
  • the mass ratio of the inorganic nanoparticles, the organic high polymer and the binder is 70-90:9-29:1.
  • the total mass of the solvent is 1-1.5 times the mass of the inorganic nanoparticles.
  • the distribution of the solvent in raw material A, raw material B, and raw material C is also based on the mass ratio of the inorganic nanoparticles, the organic high molecular polymer, and the binder.
  • the present invention provides a diaphragm slurry prepared by the above preparation method.
  • the diaphragm slurry is evenly dispersed and is used to make a diaphragm subsequently.
  • the present invention provides a diaphragm for alkaline water electrolysis, the preparation raw materials of which include the above-mentioned diaphragm slurry.
  • the above-mentioned diaphragm slurry is directly used to prepare a diaphragm for alkaline water electrolysis.
  • the above-mentioned diaphragm slurry is formed on the surface of a support to obtain a diaphragm for alkaline water electrolysis, wherein the support can be a polypropylene or polyethylene film.
  • the obtained diaphragm has a narrow pore size distribution and controllable pore size due to the uniform slurry.
  • An alkaline water electrolysis device generally includes an electrolytic cell, electrodes and a diaphragm.
  • an electrolytic cell When electricity is turned on, hydrogen is generated on the cathode side and oxygen is generated on the anode side.
  • the diaphragm of the present invention is used in an alkaline water electrolysis device to improve the electrolysis efficiency of the alkaline water electrolysis device.
  • the diaphragm can also withstand the friction between the electrodes and the diaphragm of the electrolytic cell.
  • the diaphragm has the performance of blocking gas. The gas generated by electrolysis cannot pass through the diaphragm.
  • the diaphragm cannot conduct electricity and is in an insulating state. In short, it is safe and efficient.
  • the average molecular weight of the polyvinyl pyrrolidone used is 40,000;
  • the diameters of the zirconium dioxide nanoparticles and titanium dioxide nanoparticles are both in the range of 10-200 nm.
  • This embodiment provides a method for preparing a diaphragm slurry, as shown in FIG1 , and the specific steps are as follows:
  • raw material A is a mixture of inorganic nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 1:200) and a solvent (NMP)
  • raw material B is a mixture of a binder (PVP) and a solvent (NMP)
  • raw material C is a mixture of an organic polymer (polyether sulfone) and a solvent (NMP);
  • the mass ratio of inorganic nanoparticles, organic polymer and binder is 70:29:1
  • the total mass of the solvent is 1.2 times the mass of the inorganic nanoparticles
  • the distribution of the solvent in raw materials A, B, and C is also distributed according to 70:29:1.
  • the pore size of the porous membrane A was 1000 nm
  • the pore size of the porous membrane B was 500 nm
  • the pore size of the porous membrane C was 400 nm.
  • This embodiment provides a method for preparing a diaphragm slurry, and the specific steps are as follows:
  • raw material A is a mixture of inorganic nanoparticles (zirconium dioxide and titanium dioxide in a mass ratio of 370:1) and a solvent (NMP)
  • raw material B is a mixture of a binder (PVP) and a solvent (NMP)
  • raw material C is a mixture of an organic polymer (chitosan) and a solvent (NMP);
  • the mass ratio of inorganic nanoparticles, organic polymers and binders is 75:24:1
  • the total solvent mass is 1.2 times the mass of inorganic nanoparticles
  • the distribution of the solvent in raw materials A, B, and C is also distributed according to 75:24:1.
  • the pore size of the porous membrane A is 2000 nm
  • the pore size of the porous membrane B is 1000 nm
  • the pore size of the porous membrane C is 800 nm.
  • This embodiment provides a method for preparing a diaphragm slurry.
  • This embodiment provides a method for preparing a diaphragm slurry.
  • This embodiment provides a method for preparing a diaphragm slurry, and the specific steps are as follows:
  • raw material A is a mixture of inorganic nanoparticles (zirconium dioxide and titanium dioxide with a mass ratio of 1:200) and a solvent (NMP)
  • raw material B is a mixture of a binder (PVP) and a solvent (NMP)
  • raw material C is a mixture of an organic polymer (polyether sulfone) and a solvent (NMP).
  • liquid; the mass ratio of inorganic nanoparticles, organic high polymer and binder is 65:32:3, the total solvent mass is 1.2 times the mass of inorganic nanoparticles, and the distribution of the solvent in raw materials A, B and C is also distributed according to 65:32:3.
  • the pore size of the porous membrane A is 1500 nm
  • the pore size of the porous membrane B is 700 nm
  • the pore size of the porous membrane C is 600 nm.
  • This comparative example provides a method for preparing a diaphragm slurry, which is different from Example 1 in that the pore size of porous membrane A is 500 nm, the pore size of porous membrane B is 300 nm, and the pore size of porous membrane C is 300 nm.
  • This comparative example provides a method for preparing a diaphragm slurry, wherein the raw material composition is the same as that of Example 1, except that raw material A, raw material B and raw material C are mixed together and then passed through a porous membrane, and the pore size of the porous membrane is 1000 nm.
  • This comparative example provides a method for preparing a diaphragm slurry, which is different from Example 1 in that the pore size of porous membrane A is 800 nm, the pore size of porous membrane B is 2000 nm, and the pore size of porous membrane C is 1000 nm.
  • phase inversion temperature is 20°C.
  • phase inversion solution is a mixed solution of water and NMP.
  • the phase inversion time is 1 hour to ensure that the phase inversion is relatively thorough.
  • the organic polymer resin in the casting solution solidifies, the solvent dissolves in the water, and the polymer resin and the solvent undergo phase separation, becoming a solid resin and forming a porous structure.
  • the test method of surface resistance is as follows:
  • the separator was cut into small pieces and immersed in 30 wt % KOH solution for 1 day, and then the resistance was tested using an electrochemical workstation.
  • the test method for bubble point is as follows:
  • the test method for tensile strength is as follows:
  • test method for insulation performance is as follows:
  • the present invention provides a diaphragm slurry and a preparation method thereof and a diaphragm for alkaline water electrolysis.
  • the preparation method of the diaphragm slurry comprises the step of mixing three liquids formed by passing raw material A through a porous membrane A, raw material B through a porous membrane B, and raw material C through a porous membrane C.
  • Raw material A is a mixed liquid of inorganic nanoparticles and a solvent
  • raw material B is a mixed liquid of a binder and a solvent
  • raw material C is a mixed liquid of an organic high molecular polymer and a solvent
  • the pore size of porous membrane A is 1000-2000nm
  • the pore size of porous membrane B is 500-1000nm
  • the pore size of porous membrane C is 400-800nm.
  • the present invention allows specific raw materials to pass through a porous membrane with a specific pore size, so that each component liquid forms multiple tiny droplets, which are finally mixed to form a uniform slurry.
  • the diaphragm prepared by the slurry obtained by the present invention has a narrow pore size distribution, controllable pore size, high ion permeability and bubble point, and good economic value and application prospects.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明提供一种隔膜浆料及其制备方法和碱性水电解用隔膜，所述隔膜浆料的制备方法包括将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合的步骤，原料A为无机纳米颗粒与溶剂的混合液，原料B为粘结剂与溶剂的混合液，原料C为有机高分子聚合物与溶剂的混合液；多孔膜A的孔尺寸为1000～2000nm，多孔膜B的孔尺寸为500～1000nm，多孔膜C的孔尺寸为400～800nm。本发明通过将特定原料通过特定孔径的多孔膜，使得各组分料液形成多股微小的液滴，最终混合形成均匀的浆料。利用本发明所得浆料制备的隔膜，其孔径分布较窄，孔径大小可控，具有较高的离子透过性和泡点。

Description

隔膜浆料及其制备方法和碱性水电解用隔膜
交叉引用
本申请要求2022年10月25日提交的专利名称为“隔膜浆料及其制备方法和碱性水电解用隔膜”的第202211314154.9号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。
技术领域
本发明涉及浆料制备技术领域，尤其涉及一种隔膜浆料及其制备方法和碱性水电解用隔膜。
背景技术
清洁型能源氢能作为未来重要的能源载体之一，具有广泛的应用前景。碱性水电解作为一种成熟的绿氢制备技术，能耗有进一步降低的空间。通常，碱性水电解装置包括电解槽、电极和隔膜，通电时在阴极侧产生氢气，阳极侧产生氧气。
现有技术中，碱性水电解用隔膜通常采用包括无机纳米颗粒、有机高分子聚合物、粘结剂的浆料制备得到。但所得碱性水电解用隔膜很难同时具备良好的离子透过性、机械强度、气密性和电气绝缘性。
发明内容
针对现有技术存在的问题，本发明提供一种隔膜浆料及其制备方法和碱性水电解用隔膜。
第一方面，本发明提供一种隔膜浆料的制备方法，包括将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合的步骤，
其中，所述原料A为无机纳米颗粒与溶剂的混合液，所述原料B为粘结剂与溶剂的混合液，所述原料C为有机高分子聚合物与溶剂的混合液；
所述多孔膜A的孔尺寸为1000～2000nm，所述多孔膜B的孔尺寸为500～1000nm，所述多孔膜C的孔尺寸为400～800nm。
根据本发明提供的隔膜浆料的制备方法，原料通过多孔膜的过程中，在多孔膜的进料侧施加5-10MPa的压力。
根据本发明提供的隔膜浆料的制备方法，所述无机纳米颗粒为二氧化锆和/或二氧化钛，所述无机纳米颗粒的粒径为10-200nm。
根据本发明提供的隔膜浆料的制备方法，所述无机纳米颗粒由质量比为1:150-200的二氧化锆和二氧化钛组成，所述二氧化锆的直径为d1，所述二氧化钛的直径为d2，满足：
根据本发明提供的隔膜浆料的制备方法，所述无机纳米颗粒由质量比为350-400:1的二氧化锆和二氧化钛组成，所述二氧化锆的直径为d1，所述二氧化钛的直径为d2，满足：
根据本发明提供的隔膜浆料的制备方法，所述有机高分子聚合物为聚醚砜、聚芳醚酮、壳聚糖中的一种或多种。
根据本发明提供的隔膜浆料的制备方法，所述粘结剂为聚乙烯吡咯烷酮、聚乙烯醇中的一种或多种。
根据本发明提供的隔膜浆料的制备方法，所述溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种。
根据本发明提供的隔膜浆料的制备方法，所述无机纳米颗粒、所述有机高分子聚合物和所述粘结剂的质量比为70-90:9-29:1。
根据本发明提供的隔膜浆料的制备方法，所述溶剂的总质量为所述无机纳米颗粒质量的1-1.5倍。
第二方面，本发明提供一种隔膜浆料，由上述制备方法制备得到。
第三方面，本发明提供一种碱性水电解用隔膜，制备原料包括上述隔膜浆料。
本发明提供了一种隔膜浆料及其制备方法和碱性水电解用隔膜。本发明在隔膜浆料的制备过程中，采用多孔膜渗透技术，通过在一定孔径的膜 的进料侧施加一定压力，使得各组分料液在互相混合之前能够形成多股微小的液滴，最终混合形成均匀的浆料。利用本发明所得浆料制备的隔膜，其孔径分布较窄，孔径大小可控，用于碱性水电解过程时，在保持较高的离子透过性的同时，有利于提升隔膜的泡点。
附图说明
图1为本发明实施例制备隔膜浆料的方法示意图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明实施例的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
第一方面，本发明提供一种隔膜浆料的制备方法，包括将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合的步骤，
其中，所述原料A为无机纳米颗粒与溶剂的混合液，原料B为粘结剂与溶剂的混合液，原料C为有机高分子聚合物与溶剂的混合液；
所述多孔膜A的孔尺寸为1000～2000nm，所述多孔膜B的孔尺寸为500～1000nm，所述多孔膜C的孔尺寸为400～800nm。
现有技术中，当采用包括无机纳米颗粒、有机高分子聚合物、粘结剂的浆料制备得到的碱性水电解用隔膜难以满足性能要求时，本领域技术人员往往更倾向于对浆料组成进行改进，例如添加纳米纤维以增加隔膜机械性能。
本发明研究发现，对浆料制备方法进行改进，使浆料分散更均匀，也能很好地改善隔膜性能，而且改进制备方法操作起来更方便。具体地，采用多孔膜渗透技术，通过将特定原料通过特定孔径的多孔膜，使得各组分料液形成多股微小的液滴，最终混合形成均匀的浆料。利用本发明所得浆料制备的隔膜，其孔径分布较窄，孔径大小可控，用于碱性水电解过程时，在保持较高的离子透过性的同时，有利于提升隔膜的泡点。
需要说明的是，上述方案中原料A、原料B、原料C通过各自对应的多孔膜，可以同时进行，也可以不同时进行，但间隔时间不宜过长，优选同时进行。
在本发明的一些实施例中，原料通过多孔膜的过程中，在多孔膜的进料侧施加5-10MPa的压力。
在本发明的一些实施例中，所述无机纳米颗粒为二氧化锆和/或二氧化钛，所述无机纳米颗粒的粒径为10-200nm。
也就是说，在本发明的一些实施例中，所述无机纳米颗粒为二氧化锆纳米颗粒。在本发明的一些实施例中，所述无机纳米颗粒为二氧化钛纳米颗粒。在本发明的一些实施例中，所述无机纳米颗粒为二氧化锆纳米颗粒和二氧化钛纳米颗粒的混合物。
进一步优选地，所述无机纳米颗粒由质量比为1:150-200的二氧化锆和二氧化钛组成，所述二氧化锆的直径为d1，所述二氧化钛的直径为d2，满足：
根据本发明提供的隔膜浆料的制备方法，所述无机纳米颗粒由质量比为350-400:1的二氧化锆和二氧化钛组成，所述二氧化锆的直径为d1，所 述二氧化钛的直径为d2，满足：
在上述条件下，二氧化锆和二氧化钛无机纳米颗粒可以互相嵌在球形颗粒的缝隙之间，能够保证纳米颗粒相互混合的充分性，使得浆料更均一，在相转化时能形成更为致密的皮层，提升隔膜性能。
在本发明的一些实施例中，所述有机高分子聚合物为聚醚砜、聚芳醚酮、壳聚糖中的一种或多种。
其中，壳聚糖的粘度可以为低粘度(<200mPa·s)，中粘度(200-400mPa·s)，或高粘度(>400mPa·s)。当有机高分子聚合物为聚醚砜、聚芳醚酮、壳聚糖中两种以上的混合物时，可以以任意比例混合。
在本发明的一些实施例中，所述粘结剂为聚乙烯吡咯烷酮PVP、聚乙烯醇PVA中的一种或多种。
优选地，所用聚乙烯醇的醇解度为87％-89mol％，粘度为3.2-3.6mPa·s。
所述聚乙烯吡咯烷酮的平均分子量为40000。
在本发明的一些实施例中，所述溶剂为N-甲基吡咯烷酮NMP、N,N-二甲基甲酰胺DMF、二甲基亚砜DMSO中的一种或多种。
在本发明的一些实施例中，所述无机纳米颗粒、所述有机高分子聚合物和所述粘结剂的质量比为70-90:9-29:1。
在本发明的一些实施例中，所述溶剂的总质量为所述无机纳米颗粒质量的1-1.5倍。溶剂在原料A、原料B、原料C中的分配也按照所述无机纳米颗粒、所述有机高分子聚合物和所述粘结剂的质量比进行分配。
第二方面，本发明提供一种由上述制备方法制得的隔膜浆料。该隔膜浆料分散均匀，利用后续制作隔膜。
第三方面，本发明提供一种碱性水电解用隔膜，制备原料包括上述隔膜浆料。
在本发明的一些实施例中，直接采用上述隔膜浆料制备碱性水电解用隔膜。
在本发明的另一些实施例中，采用上述隔膜浆料形成在支撑体表面从而得到碱性水电解用隔膜。其中，支撑体可以采用聚丙烯或聚乙烯薄膜。
上述实施例中，不管是单独使用浆料制备隔膜，还是结合支撑体制备隔膜，所得隔膜均由于浆料均一，故而隔膜的孔径分布较窄，孔径大小可控，用于碱性水电解过程时，在保持较高的离子透过性的同时，有利于提升隔膜的泡点。
碱性水电解装置一般包括电解槽、电极和隔膜，通电时在阴极侧产生氢气，阳极侧产生氧气。本发明的隔膜用于碱性水电解装置，可以提高碱性水电解装置的电解效率，隔膜也能够经受电解槽的电极与隔膜之间的摩擦，隔膜具备阻隔气体的性能，电解生成的气体无法透过隔膜，隔膜也不能导电，处于绝缘状态。总而言之，安全又高效。
以下为具体实施例，所用原料若无特别说明，均为通过正规商业渠道获得。
以下实施例中，所用聚乙烯吡咯烷酮的平均分子量为40000；
二氧化锆纳米颗粒和二氧化钛纳米颗粒的直径均在10-200nm范围内。
实施例1
本实施例提供一种隔膜浆料的制备方法，如图1所示，具体步骤如下：
将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合。其中，每个多孔膜进料侧施加5MPa的压力。
其中，原料A为无机纳米颗粒(质量比为1:200的二氧化锆和二氧化钛)与溶剂(NMP)的混合液，原料B为粘结剂(PVP)与溶剂(NMP)的混合液，原料C为有机高分子聚合物(聚醚砜)与溶剂(NMP)的混合液；无机纳米颗粒、有机高分子聚合物和粘结剂的质量比为70:29:1，溶剂总质量是无机纳米颗粒质量的1.2倍，溶剂在原料A、B、C中的分配也按照70:29:1进行分配。
多孔膜A的孔尺寸为1000nm，多孔膜B的孔尺寸为500nm，多孔膜C的孔尺寸为400nm。
实施例2
本实施例提供一种隔膜浆料的制备方法，具体步骤如下：
将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合。其中，每个多孔膜进料侧施加10MPa的压力。
其中，原料A为无机纳米颗粒(质量比为370:1的二氧化锆和二氧化钛)与溶剂(NMP)的混合液，原料B为粘结剂(PVP)与溶剂(NMP)的混合液，原料C为有机高分子聚合物(壳聚糖)与溶剂(NMP)的混合液；无机纳米颗粒、有机高分子聚合物和粘结剂的质量比为75:24:1，总溶剂质量是无机纳米颗粒质量的1.2倍，溶剂在原料A、B、C中的分配也按照75:24:1进行分配。
多孔膜A的孔尺寸为2000nm，多孔膜B的孔尺寸为1000nm，多孔膜C的孔尺寸为800nm。
实施例3
本实施例提供一种隔膜浆料的制备方法，其在实施例1的基础上，二氧化锆纳米颗粒和二氧化钛纳米颗粒的粒径还满足具体地，二氧化锆纳米颗粒d1＝20nm，二氧化钛纳米颗粒d2＝150nm。
实施例4
本实施例提供一种隔膜浆料的制备方法，其在实施例2的基础上，二氧化锆纳米颗粒和二氧化钛纳米颗粒的粒径还满足具体地，二氧化锆纳米颗粒d1＝200nm，二氧化钛纳米颗粒d2＝30nm。
实施例5
本实施例提供一种隔膜浆料的制备方法，具体步骤如下：
将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合。
其中，原料A为无机纳米颗粒(质量比为1:200的二氧化锆和二氧化钛)与溶剂(NMP)的混合液，原料B为粘结剂(PVP)与溶剂(NMP)的混合液，原料C为有机高分子聚合物(聚醚砜)与溶剂(NMP)的混合 液；无机纳米颗粒、有机高分子聚合物和粘结剂的质量比为65:32:3，总溶剂质量是无机纳米颗粒质量的1.2倍，溶剂在原料A、B、C中的分配也按照65:32:3进行分配。
多孔膜A的孔尺寸为1500nm，多孔膜B的孔尺寸为700nm，多孔膜C的孔尺寸为600nm。
对比例1
本对比例提供一种隔膜浆料的制备方法，其与实施例1的区别在于，多孔膜A的孔尺寸为500nm，多孔膜B的孔尺寸为300nm，多孔膜C的孔尺寸为300nm。
对比例2
本对比例提供一种隔膜浆料的制备方法，其中原料组成与实施例1相同，区别在于，将原料A、原料B和原料C一起混合后，再通过多孔膜，多孔膜的孔径为1000nm。
对比例3
本对比例提供一种隔膜浆料的制备方法，其与实施例1的区别在于，多孔膜A的孔尺寸为800nm，多孔膜B的孔尺寸为2000nm，多孔膜C的孔尺寸为1000nm。
按照下述方法将各实施例和对比例所得的浆料制成隔膜：
(1)先将浆料组分充分搅拌3h，再将支撑体完全浸没在铸膜液(浆料)中，随后采用刮膜装置，采用双面刮刀，控制支撑体距离刮刀距离约为200μm，制备出湿润状态的复合隔膜。
(2)将上述湿润状态的复合隔膜放入相转化液中进行相转化，相转化温度为20℃，相转化液为水和NMP组成的混合溶液，相转化时间为1h，保证相转化较为彻底。在此过程中，铸膜液中的有机高分子树脂发生凝固，溶剂溶于水中，高分子树脂和溶剂则会发生相分离，变成固态树脂，形成多孔结构。
(3)相转化过程完成后，将隔膜用沸水煮10mins，清除隔膜内残留的 溶剂，然后放入无离子水中保存。
对上述所得隔膜进行性能测试，具体项目和方法如下：
面电阻的测试方法如下：
将隔膜切割成小块，在30wt％的KOH溶液下浸泡1天后，用电化学工作站测试电阻。
泡点的测试方法如下：
将隔膜切割成小块，用高纯水浸润，放入泡压法膜孔径分析仪(BSD-PB)测试，在膜的一侧施加气体压强，待膜的另一侧检测到1mL/min的气流时，该压强视作隔膜的泡点。泡点的计算公式如下：
式中，D＝孔隙直径，单位μm；γ＝液体的表面张力，单位：dny/cm；θ＝接触角，单位：度；△P＝压差，单位KPa。
拉伸强度的测试方法如下：
剪长方形的小块隔膜，置于拉伸试验机上进行测试。
绝缘性能的测试方法如下：
取5cm宽的方形隔膜，用两块不锈钢板夹住，用电化学工作站测试电阻。
结果如表1所示。
表1
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对 其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
工业实用性
本发明提供一种隔膜浆料及其制备方法和碱性水电解用隔膜，所述隔膜浆料的制备方法包括将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合的步骤，原料A为无机纳米颗粒与溶剂的混合液，原料B为粘结剂与溶剂的混合液，原料C为有机高分子聚合物与溶剂的混合液；多孔膜A的孔尺寸为1000～2000nm，多孔膜B的孔尺寸为500～1000nm，多孔膜C的孔尺寸为400～800nm。本发明通过将特定原料通过特定孔径的多孔膜，使得各组分料液形成多股微小的液滴，最终混合形成均匀的浆料。利用本发明所得浆料制备的隔膜，其孔径分布较窄，孔径大小可控，具有较高的离子透过性和泡点，具有较好的经济价值和应用前景。

Claims (10)

  1. 一种隔膜浆料的制备方法，其特征在于，包括将原料A通过多孔膜A、原料B通过多孔膜B、原料C通过多孔膜C后形成的三股料液混合的步骤，
    其中，所述原料A为无机纳米颗粒与溶剂的混合液，所述原料B为粘结剂与溶剂的混合液，所述原料C为有机高分子聚合物与溶剂的混合液；
    所述多孔膜A的孔尺寸为1000～2000nm，所述多孔膜B的孔尺寸为500～1000nm，所述多孔膜C的孔尺寸为400～800nm。
  2. 根据权利要求1所述的隔膜浆料的制备方法，其特征在于，原料通过多孔膜的过程中，在多孔膜的进料侧施加5-10MPa的压力。
  3. 根据权利要求1或2所述的隔膜浆料的制备方法，其特征在于，所述无机纳米颗粒为二氧化锆和/或二氧化钛，所述无机纳米颗粒的粒径为10-200nm。
  4. 根据权利要求3所述的隔膜浆料的制备方法，其特征在于，所述无机纳米颗粒由质量比为1:150-200的二氧化锆和二氧化钛组成，所述二氧化锆的直径为d1，所述二氧化钛的直径为d2，满足：
  5. 根据权利要求3所述的隔膜浆料的制备方法，其特征在于，所述无机纳米颗粒由质量比为350-400:1的二氧化锆和二氧化钛组成，所述二氧化锆的直径为d1，所述二氧化钛的直径为d2，满足：
  6. 根据权利要求1或2所述的隔膜浆料的制备方法，其特征在于，所述有机高分子聚合物为聚醚砜、聚芳醚酮、壳聚糖中的一种或多种；
    和/或，所述粘结剂为聚乙烯吡咯烷酮、聚乙烯醇中的一种或多种。
  7. 根据权利要求1或2所述的隔膜浆料的制备方法，其特征在于，所述溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种。
  8. 根据权利要求1或2所述的隔膜浆料的制备方法，其特征在于，所述无机纳米颗粒、所述有机高分子聚合物和所述粘结剂的质量比为70-90:9-29:1；
    和/或，所述溶剂的总质量为所述无机纳米颗粒质量的1-1.5倍。
  9. 一种隔膜浆料，其特征在于，由权利要求1-8任一项所述的制备方法制备得到。
  10. 一种碱性水电解用隔膜，其特征在于，制备原料包括权利要求9所述的隔膜浆料。
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CN110023542A (zh) * 2017-01-26 2019-07-16 旭化成株式会社 复极式电解槽、碱水电解用复极式电解槽以及氢制造方法
CN107895765A (zh) * 2017-10-13 2018-04-10 深圳市旭然电子有限公司 无机/有机复合多孔性隔离膜、制备方法及其锂离子电池
WO2019157695A1 (en) * 2018-02-14 2019-08-22 Shanghai Energy New Materials Technology Co., Ltd. Separator and preparation method therefor and electrochemical device comprising separator
WO2020066911A1 (ja) * 2018-09-26 2020-04-02 株式会社日本触媒 アルカリ水電解用隔膜
CN115029732A (zh) * 2022-06-06 2022-09-09 清华大学 碱性水电解用隔膜及其制备方法与应用
CN115693017A (zh) * 2022-10-25 2023-02-03 清华大学 隔膜浆料及其制备方法和碱性水电解用隔膜

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