WO2022073305A1 - Non-ionized pbi/pvp film, preparation method therefor, and flow cell - Google Patents

Non-ionized pbi/pvp film, preparation method therefor, and flow cell Download PDF

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WO2022073305A1
WO2022073305A1 PCT/CN2020/140902 CN2020140902W WO2022073305A1 WO 2022073305 A1 WO2022073305 A1 WO 2022073305A1 CN 2020140902 W CN2020140902 W CN 2020140902W WO 2022073305 A1 WO2022073305 A1 WO 2022073305A1
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pvp
pbi
film
ionized
preparation
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Chinese (zh)
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谭青龙
韩银锋
李群
贾聪
禚林海
王昌安
程学礼
左健
王明娟
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泰山学院
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a membrane material for a flow battery, in particular to a non-ionized polymer ion-conducting membrane, a preparation method thereof and a flow battery comprising the non-ionized polymer ion-conducting membrane.
  • VRFBs All-vanadium redox flow batteries
  • VRFBs use different valence vanadium ions dissolved in sulfuric acid as the active species for the reaction between the positive electrode and the negative electrode of the battery, and realize the storage and release of energy through the change of the valence state of the reactive species.
  • the ion conductive membrane directly determines the battery. output performance, cost and life.
  • the research system of ion-conducting membrane for all-vanadium redox flow battery mainly includes cation exchange membrane and anion exchange membrane.
  • the advantages of cation exchange membranes are high ionic conductivity and good chemical stability, but the disadvantages are poor ion selectivity and high cost.
  • the advantages of anion exchange membranes are low cost and good vanadium resistance, while the disadvantages are poor ionic conductivity and poor chemical stability.
  • the present invention proposes the solution of the present invention starting from the non-ionized weak alkaline design of the membrane.
  • a method for preparing a non-ionized PBI/PVP membrane comprising the following steps:
  • Step A Preparation of PBI/PVP Casting Liquid:
  • Step B Film Formation:
  • the PBI/PVP film casting solution in step A is formed into a film, and the PBI/PVP film is obtained by heating and drying.
  • x is 30%-60%
  • the order of adding PBI/PVP Kn -x is: first weigh a certain mass of PBI, and then dope PVP Kn according to the mass fraction of 30%-60% into PBI, and dissolved in organic solvent to obtain polymer solution.
  • the organic solvent is N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) ) any of them.
  • DMAc N,N-dimethylacetamide
  • DMF N,N-dimethylformamide
  • NMP N-methylpyrrolidone
  • DMSO dimethylsulfoxide
  • the average molecular weight of PVP K16 is 8,000
  • the average molecular weight of PVP K18 is 10,000
  • the average molecular weight of PVP K23 is 24,000
  • the average molecular weight of PVP K30 is 58,000.
  • the film-forming method of the PBI/PVP casting solution is any one of the coating and casting method, the casting method or the pouring method.
  • the heating and drying temperature is 50-160°C.
  • a non-ionized PBI/PVP membrane is provided, which is prepared by the preparation method of any one of the above-mentioned non-ionized PBI/PVP membranes.
  • a flow battery comprising the above-mentioned non-ionized PBI/PVP membrane.
  • Non-ionized PBI/PVP films were prepared by doping hydrophilic PVP- Kn with different average molecular weights and contents into PBI with excellent mechanical properties and no ether bond in the main chain.
  • PBI has excellent mechanical properties and vanadium resistance. Strong and the main chain does not contain ether bonds;
  • PVP has weak base groups that can be protonated, and has strong hydrophilicity.
  • a series of non-ionized PBI/PVP were prepared by doping polyvinylpyrrolidone (PVP Kn ) with different molecular weights and different contents into polybenzimidazole (PBI) by physical blending method using the non-ionized weak basic design strategy Kn ion-conducting membrane is easy to operate, can be continuously produced in a large area, and is convenient for industrialization.
  • PVP Kn polyvinylpyrrolidone
  • PBI polybenzimidazole
  • the prepared polymer membrane has the following advantages: high ionic conductivity, low vanadium ion permeability and excellent chemical stability, taking into account the advantages of high ionic conductivity of traditional cation exchange membrane and strong vanadium resistance of anion exchange membrane, with excellent ion selectivity and chemical stability.
  • the cost of the prepared polymer membrane is low (800-2000 yuan/m 2 ), which is much lower than that of commercial perfluorosulfonic acid membrane (9500 yuan/m 2 ), and the assembled vanadium battery has excellent performance, showing great application prospects.
  • Figure 1 is the infrared spectrum of PBI/PVP Kn -50% film (test temperature: 23°C, the mass fraction of PBI and PVP Kn each account for 50%).
  • a kind of non-ionized PBI/PVP membrane its preparation method comprises the following steps:
  • Step A Preparation of PBI/PVP Casting Liquid:
  • Step B Film Formation:
  • the PBI/PVP film casting solution in step A is formed into a film by a casting method, and the PBI/PVP film is obtained by heating and drying at 60°C.
  • This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
  • PVP K16 average molecular weight 8000
  • PVP K18 average molecular weight 10000
  • PVP K23 average molecular weight 24000
  • N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) instead of N,N-dimethylacetamide (DMAc).
  • a kind of non-ionized PBI/PVP membrane its preparation method comprises the following steps:
  • Step A Preparation of PBI/PVP Casting Liquid:
  • Step B Film Formation:
  • the PBI/PVP film casting solution in step A is formed into a film by a casting method, and the PBI/PVP film is obtained by heating and drying at 60°C.
  • This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
  • PVP K16 average molecular weight 8000
  • PVP K23 average molecular weight 24000
  • PVP K30 average molecular weight 58000
  • N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) instead of N,N-dimethylacetamide (DMAc).
  • a kind of non-ionized PBI/PVP membrane its preparation method comprises the following steps:
  • Step A Preparation of PBI/PVP Casting Liquid:
  • Step B Film Formation:
  • the PBI/PVP film casting solution in step A is formed into a film by a casting method, and the PBI/PVP film is obtained by heating and drying at 60°C.
  • This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
  • PVP K16 average molecular weight 8000
  • PVP K18 average molecular weight 10000
  • PVP K30 average molecular weight 58000
  • N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) instead of N,N-dimethylacetamide (DMAc).
  • a kind of non-ionized PBI/PVP membrane its preparation method comprises the following steps:
  • Step A Preparation of PBI/PVP Casting Liquid:
  • Step B Film Formation:
  • the PBI/PVP film casting solution in step A was formed into a film by a casting method, and the PBI/PVP film was obtained by heating and drying at 60°C.
  • This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
  • Step C Substitute comparison under the same conditions for PVP with different average molecular weights:
  • PVP K16 average molecular weight 8000
  • PVP K18 average molecular weight 10000
  • PVP K23 average molecular weight 24000
  • the heating and stirring temperature can be selected in the range of 20-60 °C.
  • the heating and stirring time can be selected in the range of 2-6h.
  • NMP N-methylpyrrolidone
  • DMSO dimethylsulfoxide
  • DMF N,N-dimethylformamide
  • the casting method is replaced by the casting method or the casting method.
  • the ion selectivity and chemical stability of the pure PBI membrane are improved, and an ion-conducting membrane for a flow battery and a preparation method and application thereof are provided.
  • the preparation method of the invention has simple operation and high efficiency, and the prepared non-ionized polymer ion conductive membrane takes into account the advantages of high ionic conductivity of the cation exchange membrane and strong vanadium resistance of the anion exchange membrane, and has high ion selectivity and chemical stability. sex.

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Abstract

Disclosed are a non-ionized PBI/PVP film, a preparation method therefor, and a flow cell. The preparation method comprises the following steps: step A: preparing a PBI/PVP casting solution: adding PBI/PVPKn-x and 10-1000 ml of an organic solvent to a container provided with a stirring device, heating and stirring same at 20-60 °C until the polymer is dissolved so as to form a uniform and transparent PBI/PVP solution; cooling the polymer solution to room temperature, and removing bubbles and insolubles to obtain a PBI/PVP casting solution, where n = 16, 18, 23 or 30, and x is the mass fraction of PVPKn; and step B: forming a film: forming a film by using the PBI/PVP casting solution in step A, and heating and drying same so as to obtain the PBI/PVP film. Hydrophilic PVPKn of different mass fractions and different average molecular weights is mixed into PBI to prepare the non-ionized PBI/PVP film. PBI has excellent mechanical properties, strong vanadium barrier capability and good chemical stability. PVP has a weak base group which can be protonated, and has a strong electrical conductivity. The prepared PBI/PVPKn-x film has an excellent ionic conductivity, vanadium barrier capability and cell properties.

Description

一种非离子化PBI/PVP膜及其制备方法和液流电池A kind of non-ionized PBI/PVP membrane and its preparation method and flow battery 技术领域technical field
本发明涉及一种液流电池用膜材料,特别涉及一种非离子化聚合物离子传导膜,并涉及其制备方法和包括该非离子化聚合物离子传导膜的液流电池。The present invention relates to a membrane material for a flow battery, in particular to a non-ionized polymer ion-conducting membrane, a preparation method thereof and a flow battery comprising the non-ionized polymer ion-conducting membrane.
背景技术Background technique
全钒液流电池(VRFBs)因其功率、容量可独立设计、可深度充放电、绿色环保、维护简单等优点，被视为最有前景的理想储能装置。All-vanadium redox flow batteries (VRFBs) are regarded as the most promising ideal energy storage devices due to their advantages of independent design of power and capacity, deep charge and discharge, green environmental protection, and simple maintenance.
VRFBs采用溶于硫酸的不同价态钒离子作为电池正极与负极反应的活性物种，通过反应活性物种的价态变化来实现能量的存储与释放，作为VRFBs的核心部件，离子传导膜直接决定了电池的输出性能、成本及寿命。VRFBs use different valence vanadium ions dissolved in sulfuric acid as the active species for the reaction between the positive electrode and the negative electrode of the battery, and realize the storage and release of energy through the change of the valence state of the reactive species. As the core component of VRFBs, the ion conductive membrane directly determines the battery. output performance, cost and life.
目前现有的商业化质子交换膜材料(如美国Dupont公司的
Figure PCTCN2020140902-appb-000001
系列膜)由于阻钒性欠佳、离子选择透过性较低且成本较高，严重制约了全钒液流电池的推广与应用，因此，高性能离子传导膜材料的研发仍然是VRFBs研究的重要任务之一。 Currently existing commercial proton exchange membrane materials (such as Dupont's
Figure PCTCN2020140902-appb-000001
Series membranes) due to poor vanadium resistance, low ion selective permeability and high cost, seriously restrict the promotion and application of all-vanadium redox flow batteries. Therefore, the research and development of high-performance ion-conducting membrane materials is still the focus of VRFBs research. one of the important tasks.
全钒液流电池用离子传导膜研究体系主要包括阳离子交换膜和阴离子交换膜。阳离子交换膜优点是离子电导率高，化学稳定性好，缺点是离子选择性差，成本高。阴离子子交换膜的优点是成本低，阻钒性好，缺点是离子电导率差，化学稳定性差。The research system of ion-conducting membrane for all-vanadium redox flow battery mainly includes cation exchange membrane and anion exchange membrane. The advantages of cation exchange membranes are high ionic conductivity and good chemical stability, but the disadvantages are poor ion selectivity and high cost. The advantages of anion exchange membranes are low cost and good vanadium resistance, while the disadvantages are poor ionic conductivity and poor chemical stability.
开发高效传质与阻钒协同兼顾的全钒液流电池离子传导膜成为一项科学挑战。It is a scientific challenge to develop an all-vanadium redox flow battery ion-conducting membrane with a synergistic balance between efficient mass transfer and vanadium resistance.
发明内容SUMMARY OF THE INVENTION
针对以上问题，本发明从膜的非离子化弱碱性设计出发，提出了本发明的解决方案。In view of the above problems, the present invention proposes the solution of the present invention starting from the non-ionized weak alkaline design of the membrane.
本发明为实现上述目的，通过以下技术方案实现：The present invention is achieved by the following technical solutions in order to achieve the above object:
根据本发明的一个方面，提供一种非离子化PBI/PVP膜的制备方法，包括以下步骤：According to one aspect of the present invention, there is provided a method for preparing a non-ionized PBI/PVP membrane, comprising the following steps:
步骤A：PBI/PVP铸膜液的制备：Step A: Preparation of PBI/PVP Casting Liquid:
在装有搅拌装置的容器中加入PBI/PVP Kn-x及10-1000ml有机溶剂； Add PBI/PVP Kn -x and 10-1000ml organic solvent to the container equipped with stirring device;
20-60℃下加热搅拌至聚合物溶解形成均匀透明的PBI/PVP聚合物溶液；作为可选方案，加热时长为2-6h。Heating and stirring at 20-60°C until the polymer dissolves to form a uniform and transparent PBI/PVP polymer solution; as an alternative, the heating time is 2-6h.
待所述PBI/PVP Kn-x聚合物溶液冷却至室温，去除气泡、不溶物，得到PBI/PVP铸膜液，其中，n＝16、18、23或30，x为PVP Kn的质量分数； After the PBI/PVP Kn -x polymer solution is cooled to room temperature, air bubbles and insolubles are removed to obtain a PBI/PVP film casting solution, wherein n=16, 18, 23 or 30, and x is the mass fraction of PVP Kn ;
步骤B：成膜：Step B: Film Formation:
将步骤A中的PBI/PVP铸膜液成膜，加热烘干即得PBI/PVP膜。The PBI/PVP film casting solution in step A is formed into a film, and the PBI/PVP film is obtained by heating and drying.
优选的,步骤A中x为30％-60％，PBI/PVP Kn-x的添加顺序为：先称取一定质量的PBI，再按照质量分数为30％-60％的比例将PVP Kn掺杂到PBI中，并溶解于有机溶剂得聚合物溶液。 Preferably, in step A, x is 30%-60%, and the order of adding PBI/PVP Kn -x is: first weigh a certain mass of PBI, and then dope PVP Kn according to the mass fraction of 30%-60% into PBI, and dissolved in organic solvent to obtain polymer solution.
优选的，所述有机溶剂为N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)或二甲基亚砜(DMSO)中任意一种。Preferably, the organic solvent is N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) ) any of them.
优选的，PVP K16平均分子量为8000，PVP K18平均分子量为10000，PVP K23平均分子量为24000，PVP K30平均分子量为58000。 Preferably, the average molecular weight of PVP K16 is 8,000, the average molecular weight of PVP K18 is 10,000, the average molecular weight of PVP K23 is 24,000, and the average molecular weight of PVP K30 is 58,000.
优选的，PBI/PVP铸膜液成膜方法为涂铸法、流延法或浇筑法中任意的一种。Preferably, the film-forming method of the PBI/PVP casting solution is any one of the coating and casting method, the casting method or the pouring method.
优选的，所述的加热烘干温度为50-160℃。Preferably, the heating and drying temperature is 50-160°C.
根据本发明的一个方面，提供一种非离子化PBI/PVP膜，用上述任一一项所述的非离子化PBI/PVP膜的制备方法制备而成。According to one aspect of the present invention, a non-ionized PBI/PVP membrane is provided, which is prepared by the preparation method of any one of the above-mentioned non-ionized PBI/PVP membranes.
根据本发明的一个方面，提供一种液流电池，包括上述的非离子化PBI/PVP膜。According to one aspect of the present invention, there is provided a flow battery comprising the above-mentioned non-ionized PBI/PVP membrane.
对比现有技术，本发明有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
将不同平均分子量不同含量的亲水性PVP- Kn掺杂到机械性能优异且主链不含醚键的PBI中，制备了非离子化的PBI/PVP膜，PBI的机械性能优异、阻钒能力强且主链不含醚键；PVP带有可被质子化的弱碱基团，亲水性强。 Non-ionized PBI/PVP films were prepared by doping hydrophilic PVP- Kn with different average molecular weights and contents into PBI with excellent mechanical properties and no ether bond in the main chain. PBI has excellent mechanical properties and vanadium resistance. Strong and the main chain does not contain ether bonds; PVP has weak base groups that can be protonated, and has strong hydrophilicity.
利用非离子化弱碱性设计策略，通过物理共混手段将不同分子量、不同含量的聚乙烯吡咯烷酮(PVP Kn)掺杂到聚苯并咪唑(PBI)中，制备系列非离子化的PBI/PVP Kn离子传导膜，操作简单、可大面积连续化生产、便于产业化。 A series of non-ionized PBI/PVP were prepared by doping polyvinylpyrrolidone (PVP Kn ) with different molecular weights and different contents into polybenzimidazole (PBI) by physical blending method using the non-ionized weak basic design strategy Kn ion-conducting membrane is easy to operate, can be continuously produced in a large area, and is convenient for industrialization.
所制备的聚合物膜具有以下优点：高离子电导率、低钒离子渗透率和优异的化学稳定性，兼顾了传统阳离子交换膜离子电导率高和阴离子交换膜阻钒能力强的优势，具有优异的离子选择性和化学稳定性。The prepared polymer membrane has the following advantages: high ionic conductivity, low vanadium ion permeability and excellent chemical stability, taking into account the advantages of high ionic conductivity of traditional cation exchange membrane and strong vanadium resistance of anion exchange membrane, with excellent ion selectivity and chemical stability.
所制备的聚合物膜成本低廉(800-2000元/m 2),远低于商业化全氟磺酸
Figure PCTCN2020140902-appb-000002
膜(9500元/m 2)，且所组装的钒电池性能优异，展现出巨大的应用前景。 The cost of the prepared polymer membrane is low (800-2000 yuan/m 2 ), which is much lower than that of commercial perfluorosulfonic acid
Figure PCTCN2020140902-appb-000002
membrane (9500 yuan/m 2 ), and the assembled vanadium battery has excellent performance, showing great application prospects.
附图说明Description of drawings
图1为PBI/PVP Kn-50％膜的红外谱图(测试温度：23℃,PBI和PVP Kn的质量分数各占50％)。 Figure 1 is the infrared spectrum of PBI/PVP Kn -50% film (test temperature: 23°C, the mass fraction of PBI and PVP Kn each account for 50%).
图2为PBI/PVP K30-x(x＝30％，40％，50，60％)和Nafion 212膜的离子电导率。 Figure 2 shows the ionic conductivity of PBI/PVP K30 -x (x=30%, 40%, 50, 60%) and Nafion 212 membranes.
图3为PBI/PVP-x(x＝30％，40％，50，60％)和Nafion 212膜的钒离子渗透率。Figure 3 is the vanadium ion permeability of PBI/PVP-x (x=30%, 40%, 50, 60%) and Nafion 212 membranes.
图4为PBI/PVP-x(x＝40％，50，60％)和Nafion 212膜不同电流密度下的钒电池能量效率。Figure 4 shows the energy efficiency of vanadium cells at different current densities for PBI/PVP-x (x=40%, 50, 60%) and Nafion 212 films.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行 清楚、完整地描述，显然，所描述的实施例仅仅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它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1：Example 1:
一种非离子化PBI/PVP膜，其制备方法包括以下步骤：A kind of non-ionized PBI/PVP membrane, its preparation method comprises the following steps:
步骤A：PBI/PVP铸膜液的制备：Step A: Preparation of PBI/PVP Casting Liquid:
在装有搅拌装置的50ml烧杯中加入0.5g PBI/PVP K30-30％及20ml N,N-二甲基乙酰胺，x为30％指PVP K30的质量分数； Add 0.5g PBI/PVP K30-30 % and 20ml N,N-dimethylacetamide to a 50ml beaker equipped with a stirring device, x being 30% refers to the mass fraction of PVP K30 ;
20℃下加热搅拌6h，使聚合物溶解形成均匀透明的PBI/PVP聚合物溶液；Heating and stirring at 20 °C for 6 h to dissolve the polymer to form a uniform and transparent PBI/PVP polymer solution;
待所述PBI/PVP聚合物溶液冷却至室温，抽滤后除掉气泡及不溶物，得到PBI/PVP铸膜液；After the PBI/PVP polymer solution is cooled to room temperature, air bubbles and insolubles are removed after suction filtration to obtain a PBI/PVP film casting solution;
步骤B：成膜：Step B: Film Formation:
将步骤A中的PBI/PVP铸膜液利用浇筑法成膜，于60℃加热烘干即得PBI/PVP膜。The PBI/PVP film casting solution in step A is formed into a film by a casting method, and the PBI/PVP film is obtained by heating and drying at 60°C.
本实施例提供一种液流电池，包括上述的非离子化PBI/PVP膜。This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
对本实施例采用以下替代条件均可得到性质类似的膜:Films with similar properties can be obtained using the following alternative conditions for this example:
(1)PVP K16(平均分子量8000)、PVP K18(平均分子量10000)或PVP K23(平均分子量24000)代替PVP K30。 (1) PVP K16 (average molecular weight 8000), PVP K18 (average molecular weight 10000) or PVP K23 (average molecular weight 24000) instead of PVP K30 .
(2)N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)或二甲基亚砜(DMSO)代替N,N-二甲基乙酰胺(DMAc)。(2) N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) instead of N,N-dimethylacetamide (DMAc).
(3)用涂铸法或流延法代替浇筑法。(3) The casting method is replaced by the casting method or the casting method.
实施例2：Example 2:
一种非离子化PBI/PVP膜，其制备方法包括以下步骤：A kind of non-ionized PBI/PVP membrane, its preparation method comprises the following steps:
步骤A：PBI/PVP铸膜液的制备：Step A: Preparation of PBI/PVP Casting Liquid:
在装有搅拌装置的50ml烧杯中加入0.5g的PBI/PVP K18-40％及20ml N,N-二甲基乙酰胺，x为40％指PVP K18的质量分数； Add 0.5g of PBI/PVP K18-40 % and 20ml of N,N-dimethylacetamide to a 50ml beaker equipped with a stirring device, x being 40% refers to the mass fraction of PVP K18 ;
40℃下加热搅拌6h，使聚合物溶解形成均匀透明的PBI/PVP聚合物溶液；Heating and stirring at 40 °C for 6 h to dissolve the polymer to form a uniform and transparent PBI/PVP polymer solution;
待所述PBI/PVP聚合物溶液冷却至室温，抽滤后除掉气泡、不溶物，得到PBI/PVP铸膜液；After the PBI/PVP polymer solution is cooled to room temperature, air bubbles and insolubles are removed after suction filtration to obtain a PBI/PVP film casting solution;
步骤B：成膜：Step B: Film Formation:
将步骤A中的PBI/PVP铸膜液利用浇筑法成膜，于60℃加热烘干即得PBI/PVP膜。The PBI/PVP film casting solution in step A is formed into a film by a casting method, and the PBI/PVP film is obtained by heating and drying at 60°C.
本实施例提供一种液流电池，包括上述的非离子化PBI/PVP膜。This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
对本实施例采用以下替代条件均可得到性质类似的膜:Films with similar properties can be obtained using the following alternative conditions for this example:
(1)PVP K16(平均分子量8000)、PVP K23(平均分子量24000)或PVP K30(平均分子量58000)代替PVP K18。 (1) PVP K16 (average molecular weight 8000), PVP K23 (average molecular weight 24000) or PVP K30 (average molecular weight 58000) instead of PVP K18 .
(2)N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)或二甲基亚砜(DMSO)代替N,N-二甲基乙酰胺(DMAc)。(2) N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) instead of N,N-dimethylacetamide (DMAc).
(3)用涂铸法或流延法代替浇筑法。(3) The casting method is replaced by the casting method or the casting method.
实施例3：Example 3:
一种非离子化PBI/PVP膜，其制备方法包括以下步骤：A kind of non-ionized PBI/PVP membrane, its preparation method comprises the following steps:
步骤A：PBI/PVP铸膜液的制备：Step A: Preparation of PBI/PVP Casting Liquid:
在装有搅拌装置的50ml烧杯中加入0.5g的PBI/PVP K23-60％及20ml N,N-二甲基乙酰胺得聚合物，x为60％指PVP K23的质量分数； Add 0.5g of PBI/PVP K23-60 % and 20ml of N,N-dimethylacetamide to a 50ml beaker equipped with a stirring device to obtain a polymer, where x is 60% and refers to the mass fraction of PVP K23 ;
50℃下加热搅拌6h，使聚合物溶解形成均匀透明的PBI/PVP聚合物溶 液；Heating and stirring at 50°C for 6h to dissolve the polymer to form a uniform and transparent PBI/PVP polymer solution;
待所述PBI/PVP聚合物溶液冷却至室温，抽滤后除掉气泡、不溶物，得到PBI/PVP铸膜液；After the PBI/PVP polymer solution is cooled to room temperature, air bubbles and insolubles are removed after suction filtration to obtain a PBI/PVP film casting solution;
步骤B：成膜：Step B: Film Formation:
将步骤A中的PBI/PVP铸膜液利用浇筑法成膜，于60℃加热烘干即得PBI/PVP膜。The PBI/PVP film casting solution in step A is formed into a film by a casting method, and the PBI/PVP film is obtained by heating and drying at 60°C.
本实施例提供一种液流电池，包括上述的非离子化PBI/PVP膜。This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
对本实施例采用以下替代条件均可得到性质类似的膜:Films with similar properties can be obtained using the following alternative conditions for this example:
(1)PVP K16(平均分子量8000)、PVP K18(平均分子量10000)或PVP K30(平均分子量58000)代替PVP K23。 (1) PVP K16 (average molecular weight 8000), PVP K18 (average molecular weight 10000) or PVP K30 (average molecular weight 58000) instead of PVP K23 .
(2)N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)或二甲基亚砜(DMSO)代替N,N-二甲基乙酰胺(DMAc)。(2) N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethylsulfoxide (DMSO) instead of N,N-dimethylacetamide (DMAc).
(3)用涂铸法或流延法代替浇筑法。(3) The casting method is replaced by the casting method or the casting method.
实施例4：Example 4:
一种非离子化PBI/PVP膜，其制备方法包括以下步骤：A kind of non-ionized PBI/PVP membrane, its preparation method comprises the following steps:
步骤A：PBI/PVP铸膜液的制备：Step A: Preparation of PBI/PVP Casting Liquid:
在装有搅拌装置的50ml烧杯中加入0.5g PBI/PVP K30-50％及20ml N,N-二甲基乙酰胺，x为50％指PVP K30的质量分数； Add 0.5g PBI/PVP K30-50 % and 20ml N,N-dimethylacetamide to a 50ml beaker equipped with a stirring device, where x is 50% and refers to the mass fraction of PVP K30 ;
20℃下加热搅拌6h，使聚合物溶解形成均匀透明的PBI/PVP聚合物溶液；Heating and stirring at 20 °C for 6 h to dissolve the polymer to form a uniform and transparent PBI/PVP polymer solution;
待所述PBI/PVP聚合物溶液冷却至室温，抽滤后除掉气泡、不溶物，得到PBI/PVP铸膜液；After the PBI/PVP polymer solution is cooled to room temperature, air bubbles and insolubles are removed after suction filtration to obtain a PBI/PVP film casting solution;
步骤B：成膜：Step B: Film Formation:
将步骤A中的PBI/PVP铸膜液利用浇筑法成膜，于60℃加热烘干即得 PBI/PVP膜。The PBI/PVP film casting solution in step A was formed into a film by a casting method, and the PBI/PVP film was obtained by heating and drying at 60°C.
本实施例提供一种液流电池，包括上述的非离子化PBI/PVP膜。This embodiment provides a flow battery including the above-mentioned non-ionized PBI/PVP membrane.
步骤C：不同平均分子量PVP相同条件下替代对比：Step C: Substitute comparison under the same conditions for PVP with different average molecular weights:
采用PVP K16(平均分子量8000)、PVP K18(平均分子量10000)或PVP K23(平均分子量24000)代替PVP K30进行PBI/PVP铸膜液的制备、成膜以及液流电池制备。 Using PVP K16 (average molecular weight 8000), PVP K18 (average molecular weight 10000) or PVP K23 (average molecular weight 24000) instead of PVP K30 for the preparation of PBI/PVP casting solution, film formation and flow battery preparation.
对本实施例采用以下替代条件均可得到性质类似的膜:Films with similar properties can be obtained using the following alternative conditions for this example:
(1)加热搅拌温度可在20-60℃范围选择。(1) The heating and stirring temperature can be selected in the range of 20-60 °C.
(2)加热搅拌时间可在2-6h范围选择。(2) The heating and stirring time can be selected in the range of 2-6h.
(3)N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)代替N,N-二甲基乙酰胺(DMAc)。(3) N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) instead of N,N-dimethylacetamide (DMAc).
(4)用涂铸法或流延法代替浇筑法。(4) The casting method is replaced by the casting method or the casting method.
本发明的优点和有益效果包括:The advantages and beneficial effects of the present invention include:
提升了纯PBI膜的离子选择性和化学稳定性，并提供了一种液流电池用离子传导膜及其制备方法和应用。The ion selectivity and chemical stability of the pure PBI membrane are improved, and an ion-conducting membrane for a flow battery and a preparation method and application thereof are provided.
本发明的制备方法操作简单、高效，所制备的非离子化聚合物离子传导膜兼顾了阳离子交换膜离子电导率高和阴离子交换膜阻钒性强的优势，具有高的离子选择性和化学稳定性。The preparation method of the invention has simple operation and high efficiency, and the prepared non-ionized polymer ion conductive membrane takes into account the advantages of high ionic conductivity of the cation exchange membrane and strong vanadium resistance of the anion exchange membrane, and has high ion selectivity and chemical stability. sex.
尽管本发明的实施方案已公开如上,但其并不仅仅限此说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领城，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明井不限于所列出的特定的细节。以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。Although the embodiment of the present invention has been disclosed as above, it is not limited to the application listed in this description and the embodiment, and it can be applied to various fields suitable for the present invention. For those skilled in the art, Additional modifications may readily be implemented, therefore the invention is not limited to the specific details set forth without departing from the general concept defined by the claims and the scope of equivalents. The above description is only a preferred embodiment of the present application and an illustration of the applied technical principles.
本领域技术人员应当理解，本申请中所涉及的发明范围，并不限于上述 技术特征的特定组合而成的技术方案，同时也应涵盖在不脱离所述发明构思的情况下，由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能。Those skilled in the art should understand that the scope of the invention involved in this application is not limited to the technical solution formed by the specific combination of the above technical features, and should also cover the above technical features without departing from the inventive concept. Other technical solutions formed by any combination of its equivalent features. For example, the above features have similar functions to those disclosed in this application (but not limited to).

Claims (8)

  1. 一种非离子化PBI/PVP膜的制备方法，其特征在于，包括以下步骤：A kind of preparation method of non-ionized PBI/PVP film, is characterized in that, comprises the following steps:
    步骤A：PBI/PVP铸膜液的制备：Step A: Preparation of PBI/PVP Casting Liquid:
    在装有搅拌装置的容器中加入PBI/PVP Kn-x及10-1000ml有机溶剂； Add PBI/PVP Kn -x and 10-1000ml organic solvent to the container equipped with stirring device;
    20-60℃下加热搅拌至聚合物溶解形成均匀透明的PBI/PVP聚合物溶液；Heating and stirring at 20-60°C until the polymer dissolves to form a uniform and transparent PBI/PVP polymer solution;
    待所述聚合物溶液冷却至室温，去除气泡、不溶物，得到PBI/PVP铸膜液，其中，n＝16、18、23或30，x为PVP Kn的质量分数； After the polymer solution is cooled to room temperature, air bubbles and insolubles are removed to obtain a PBI/PVP casting solution, wherein n=16, 18, 23 or 30, and x is the mass fraction of PVP Kn ;
    步骤B：成膜：Step B: Film Formation:
    将步骤A中的PBI/PVP铸膜液成膜，加热烘干即得PBI/PVP膜。The PBI/PVP film casting solution in step A is formed into a film, and the PBI/PVP film is obtained by heating and drying.
  2. 如权利要求1中所述的非离子化PBI/PVP膜的制备方法，其特征在于,步骤A中x为30％-60％，PBI/PVP Kn-x的添加顺序为：先称取一定质量的PBI，再按照质量分数为30％-60％的比例将PVP Kn掺杂到PBI中，并溶解于有机溶剂得聚合物。 The method for preparing a non-ionized PBI/PVP membrane as claimed in claim 1, wherein in step A, x is 30%-60%, and the order of adding PBI/PVP Kn -x is: first weigh a certain mass PBI, and then doped PVP Kn into PBI according to the mass fraction of 30%-60%, and dissolved in an organic solvent to obtain a polymer.
  3. 如权利要求1-2任一所述的非离子化PBI/PVP膜的制备方法，其特征在于，所述有机溶剂为N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)或二甲基亚砜(DMSO)中任意一种。The method for preparing a non-ionized PBI/PVP membrane according to any one of claims 1-2, wherein the organic solvent is N,N-dimethylacetamide (DMAc), N,N-dimethylacetamide Any of dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO).
  4. 如权利要求1-2任一所述的非离子化PBI/PVP膜的制备方法，其特征在于，PVP K16平均分子量为8000，PVP K18平均分子量为10000，PVP K23平均分子量为24000，PVP K30平均分子量为58000。 The method for preparing a non-ionized PBI/PVP membrane according to any one of claims 1-2, wherein the average molecular weight of PVP K16 is 8,000, the average molecular weight of PVP K18 is 10,000, the average molecular weight of PVP K23 is 24,000, and the average molecular weight of PVP K30 is 24,000. The molecular weight is 58,000.
  5. 如权利要求1-2任一所述的非离子化PBI/PVP膜的制备方法，其特征在于，PBI/PVP铸膜液成膜方法为涂铸法、流延法或浇筑法中任意的一种。The method for preparing a non-ionized PBI/PVP film according to any one of claims 1-2, wherein the PBI/PVP casting solution film-forming method is any one of coating method, casting method or pouring method. kind.
  6. 如权利要求1-2任一所述的非离子化PBI/PVP膜的制备方法，其特征在于，所述的加热烘干温度为50-160℃。The method for preparing a non-ionized PBI/PVP membrane according to any one of claims 1-2, wherein the heating and drying temperature is 50-160°C.
  7. 一种非离子化PBI/PVP膜，其特征在于，用如权利要求1-6任一一项所述的非离子化PBI/PVP膜的制备方法制备而成。A non-ionized PBI/PVP membrane is characterized in that, it is prepared by the preparation method of the non-ionized PBI/PVP membrane according to any one of claims 1-6.
  8. 一种液流电池，其特征在于，包括权利要求8所述的非离子化PBI/PVP膜。A liquid flow battery, characterized in that it comprises the non-ionized PBI/PVP membrane of claim 8 .
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