WO2018214723A1 - 一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法 - Google Patents

一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法 Download PDF

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WO2018214723A1
WO2018214723A1 PCT/CN2018/085929 CN2018085929W WO2018214723A1 WO 2018214723 A1 WO2018214723 A1 WO 2018214723A1 CN 2018085929 W CN2018085929 W CN 2018085929W WO 2018214723 A1 WO2018214723 A1 WO 2018214723A1
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film
power generation
solvent
block copolymer
membrane
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French (fr)
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闻利平
张振
江雷
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北京赛特超润界面科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/02—Details
    • 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
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H02N11/002—Generators
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the field of ion channel films, in particular to a method for preparing a salt difference power generation film in which a block copolymer film and a functional pore film are hybridized.
  • Salt difference energy is a kind of renewable energy with huge reserves and clean and reliable. Its reasonable development and utilization can effectively solve the energy crisis facing human society.
  • research in the field of salt energy utilization mainly focuses on improving the energy density of membrane materials, simplifying the preparation process and reducing the material cost.
  • the salt differential energy conversion system based on the traditional commercial ion exchange membrane has problems such as high preparation cost, poor controllability, and low energy density efficiency (Menachem Elimelech). Et al. Nature 16, 313-319 (2012); K. Nijmeijer et al. J. Membr. Sci. 467, 279-291 (2014)).
  • the present invention aims to cope with the current energy shortage, the status quo of non-renewable fossil energy on the verge of exhaustion, and to seek new materials to utilize the renewable salt energy that is widespread in nature.
  • the invention provides a preparation method of a nanochannel film having chemical composition, geometry and charge asymmetry.
  • the film prepared by this method exhibits a high energy output.
  • the solvent annealing in the invention makes the random channel in the block copolymer film vertically penetrate, thereby reducing the effective distance of ion transmission, reducing the impedance, and increasing the effective functional zone length on the other hand.
  • the amplitude increases the performance of salt difference power generation.
  • the method for preparing a salt difference power generation membrane in which the block copolymer membrane of the present invention is hybridized with a functional pore membrane, as shown in FIG. 1, comprises the following steps:
  • step 2) The solution prepared in the step 2) is placed on the functional pore membrane after the pretreatment of the step 1), and the block copolymer is formed on the pretreated functional pore membrane to form a composite membrane;
  • the functional pore film is porous alumina having a functional group, porous polyethylene terephthalate or porous polyimide, and the functional group is One or more of a hydroxyl group, a carboxyl group, an amino group, and a sulfonic acid group.
  • the functional pore film has a pore diameter of 20 to 300 nm and a number of pores of 10 8 to 10 9 /cm 2 .
  • the functional pore film can be prepared by anodization, track etching or the like.
  • the material of the sacrificial layer is cellulose acetate or sodium polystyrene sulfonate.
  • the block polymer may be, but not limited to, poly(styrene-tetravinylpyridine), poly(styrene-acrylic acid), poly(styrene-methacrylic acid N, One or more of N-dimethylaminoethyl ester, poly(styrene-N-isopropylacrylamide), poly(styrene-ethylene oxide), and the like.
  • the solvent of the step 2) may be a single solvent, for example, dioxane, dichloromethane, chloroform, toluene, benzene, tetrahydrofuran or dimethylformamide; or A mixed solvent in which two solvents are mixed may be used, for example, a mixed solvent of tetrahydrofuran and dichloromethane, a mixed solvent of ethanol and toluene, or a mixed solvent of dioxane and dimethylformamide.
  • the block polymer solution disposed in step 2) has a block polymer mass concentration of from 2% to 8%.
  • the method according to the invention is characterized in that the step 3) filming on the pretreated functional pore film can be achieved in a number of ways.
  • it may be a suspension coating method, a immersion pulling method, or the like.
  • the selective solvent for dissolving the sacrificial layer in step 4) is selected according to the material of the sacrificial layer, and cannot affect the membrane system, and may be acetone which can dissolve cellulose acetate, or dissolve Water of sodium polystyrene sulfonate, etc.
  • a person skilled in the art can select a specific dissolution mode according to the actual situation, and the invention does not specifically limit it. For example, if only one sacrificial layer material on the surface is removed, a wiping method can be used, and if the final preparation is successful, the sacrificial layer in the hole is removed.
  • the material can be selected by the immersion method.
  • the annealing temperature of step 5 may be carried out at 20 to 30 ° C, for example, at normal temperature; and the annealing time may be 0.5 to 24 h. Specifically, the composite film from which the sacrificial layer is removed is left to be annealed in a saturated solvent vapor.
  • the present invention also provides a salt difference power generation film in which a block copolymer film is hybridized with a functional pore film, which is produced by any of the above-described production methods of the present invention.
  • the block copolymer film prepared by the invention and the functional pore film hybrid salt difference power generation film are a nano channel film.
  • the nanochannel membrane has an asymmetric pore structure, a non-uniform chemical composition and an opposite surface charge distribution, and has an ultra-high ion rectification property, which can be used for high-performance salt difference power generation, when we mix seawater and brine,
  • the energy density can be increased from 0.12 watts per square meter to about 0.36 watts per square meter, which greatly exceeds the energy of commercial ion exchange membranes under the same operating conditions. Density (about 0.1 watts per square meter). Annealing in a selective solvent allows the random block copolymer nanochannels to pass vertically, and the power density of the salt difference power generation can be increased to 0.7 watts per square meter or more.
  • the preparation method of the salt polymer-based salt difference power generation membrane provided by the invention overcomes the problems of complicated preparation process, poor controllability, low ion flux and low energy density of the existing commercial ion exchange membrane.
  • the energy density of the composite salt differential power generation membrane provided by the present invention can be increased from 0.12 watts per square meter to more than 0.7 watts per square meter, far exceeding the equivalent conditions.
  • FIG. 1 is a flow chart of a method for preparing a salt difference power generation membrane according to the present invention; wherein (1) is a coating of a sacrificial layer, (2) is a film formation of a block copolymer, (3) a sacrificial layer is dissolved; (4) selectivity Annealed in a solvent.
  • FIG. 2 is a schematic view of a salt difference power generation device used in a specific embodiment of the present invention; wherein, (1) a first container, (2) a second container, (3) a film, (4) an ammeter, and (5) a load resistance.
  • An asymmetric track etching method was used to prepare a porous polyethylene terephthalate substrate having a diameter of 500 nm and a small diameter of 50 nm.
  • the prepared porous film had a pore number of 10 7 cm -2 and a regular pore size distribution.
  • the water-soluble PSS is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • the surface PSS is then wiped with a cotton swab dipped in deionized water to expose a relatively smooth surface.
  • the dioxane was used as a solvent to dissolve the block copolymer (poly(styrene-acrylic acid)), the mass fraction was 7%, and the suspension coating (2000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in water, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt difference power generation power density of the above composite ion channel salt difference power generation film is 0.70 watt per square meter.
  • a porous alumina substrate having a channel diameter of 80 nm was prepared by anodization.
  • the prepared porous film had a pore number of 10 9 cm -2 and a regular pore size distribution.
  • the cellulose acetate is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • a cellulose acetate solution having a mass fraction of 7% was placed and suspended (1000 r, 60 s) on a porous alumina substrate.
  • the surface cellulose acetate was then wiped off with a cotton swab dipped in acetone to expose a relatively smooth surface.
  • Dichloromethane was used as a solvent to dissolve the block copolymer (poly(styrene-tetravinylpyridine)), the mass fraction was 4%, and suspension coating (1000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in acetone, sonicated for 15 minutes, and taken out and blown dry.
  • FIG. 2 A schematic diagram of the salt difference power generating device used in the test of the salt difference power generation performance in the above step (5) is shown in Fig. 2.
  • the salt difference power generation device is a closed system, and the first container is filled with a high concentration or a low concentration electrolyte solution, corresponding to the second container containing a low concentration or a high concentration of the electrolyte solution.
  • the cathode or anode lead leads to the outside of the second container.
  • the circuit is connected by an external ammeter and a load resistor; the first container and the second container are separated by a salt difference power generation film.
  • the electrolyte is sodium chloride, lithium chloride or potassium chloride.
  • the electrode is a silver chloride silver electrode or a platinum electrode.
  • the salt ion power generation power density of the above composite ion channel salt difference power generation film is 0.18 watts per square meter.
  • a porous alumina substrate having a channel diameter of 40 nm was prepared by anodization.
  • the prepared porous film had a pore number of 10 9 cm -2 and a regular pore size distribution.
  • the cellulose acetate is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • a cellulose acetate solution having a mass fraction of 7% was placed and suspended (1000 r, 60 s) on a porous alumina substrate.
  • the surface cellulose acetate was then wiped off with a cotton swab dipped in acetone to expose a relatively smooth surface.
  • Dichloromethane was used as a solvent to dissolve the block copolymer (poly(styrene-tetravinylpyridine)), the mass fraction was 4%, and suspension coating (1000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in acetone, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt difference power generation power density of the above composite ion channel salt difference power generation film is 0.12 watt per square meter.
  • a porous alumina substrate having a channel diameter of 80 nm was prepared by anodization.
  • the prepared porous film had a pore number of 10 9 cm -2 and a regular pore size distribution.
  • the cellulose acetate is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • a cellulose acetate solution having a mass fraction of 7% was placed and suspended (1000 r, 60 s) on a porous alumina substrate.
  • the surface cellulose acetate was then wiped off with a cotton swab dipped in acetone to expose a relatively smooth surface.
  • Dichloromethane was used as a solvent to dissolve the block copolymer (poly(styrene-tetravinylpyridine)), the mass fraction was 4%, and suspension coating (2000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in acetone, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the composite ion channel salt difference power generation film has a salt difference power generation power density of 0.15 watts per square meter.
  • a porous alumina substrate having a channel diameter of 80 nm was prepared by anodization.
  • the prepared porous film had a pore number of 10 9 cm -2 and a regular pore size distribution.
  • the cellulose acetate is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • a cellulose acetate solution having a mass fraction of 7% was placed and suspended (1000 r, 60 s) on a porous alumina substrate.
  • the surface cellulose acetate was then wiped off with a cotton swab dipped in acetone to expose a relatively smooth surface.
  • Dichloromethane was used as a solvent to dissolve the block copolymer (poly(styrene-tetravinylpyridine)), the mass fraction was 4%, and suspension coating (1000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in acetone, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt difference power generation power density of the above composite ion channel salt difference power generation film is 0.68 watts per square meter.
  • a porous polyethylene terephthalate substrate with a channel diameter of 50 nm was prepared by symmetric track etching.
  • the prepared porous film had a pore number of 10 7 cm -2 and a regular pore size distribution.
  • the water-soluble PSS sodium polystyrene sulfonate
  • the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • the surface PSS is then wiped with a cotton swab dipped in deionized water to expose a relatively smooth surface.
  • the dioxane was used as a solvent to dissolve the block copolymer (poly(styrene-acrylic acid)), the mass fraction was 7%, and the suspension coating (2000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in water, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt difference power generation power density of the above composite ion channel salt difference power generation film is 0.30 watt per square meter.
  • a porous polyethylene terephthalate substrate with a channel diameter of 20 nm was prepared by symmetric track etching.
  • the prepared porous film had a pore number of 10 7 cm -2 and a regular pore size distribution.
  • the water-soluble PSS is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • the surface PSS is then wiped with a cotton swab dipped in deionized water to expose a relatively smooth surface.
  • the dioxane was used as a solvent to dissolve the block copolymer (poly(styrene-acrylic acid)), the mass fraction was 7%, and the suspension coating (2000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in water, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt difference power generation power density of the above composite ion channel salt difference power generation film is 0.22 watts per square meter.
  • An asymmetric track etching method was used to prepare a porous polyethylene terephthalate substrate having a diameter of 500 nm and a small diameter of 50 nm.
  • the prepared porous film had a pore number of 10 7 cm -2 and a regular pore size distribution.
  • the water-soluble PSS is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • the surface PSS is then wiped with a cotton swab dipped in deionized water to expose a relatively smooth surface.
  • the dioxane was used as a solvent to dissolve the block copolymer (poly(styrene-acrylic acid)), the mass fraction was 7%, and the suspension coating (2000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite film was immersed in water, sonicated for 15 minutes, taken out and blown dry to obtain a salt difference power generation film.
  • Example 1 Test of salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt ion power generation power density of the above composite ion channel salt difference power generation film is 0.36 watts per square meter, and the energy conversion efficiency is 36%.
  • An asymmetric track etching method was used to prepare a porous polyethylene terephthalate substrate having a diameter of 500 nm and a small diameter of 50 nm.
  • the prepared porous film had a pore number of 10 7 cm -2 and a regular pore size distribution.
  • the water-soluble PSS is used as a plugging material, and the porous film in the step (1) is treated by a sacrificial layer method to prevent solution leakage.
  • the surface PSS is then wiped with a cotton swab dipped in deionized water to expose a relatively smooth surface.
  • the dioxane was used as a solvent to dissolve the block copolymer (poly(styrene-acrylic acid)), the mass fraction was 7%, and the suspension coating (2000r, 45s) was carried out on the porous substrate prepared in the step (2). Finally, the sacrificial layer in the channel was dissolved, the composite membrane was immersed in water, sonicated for 15 minutes, and taken out and blown dry.
  • Example 1 Test for salt difference power generation performance, and the apparatus used for the test was referred to Example 1.
  • the salt difference power generation power density of the above composite ion channel salt difference power generation film is 0.70 watt per square meter.
  • the method of the invention has the advantages of simple operation, easy control, simple equipment and large-scale production, and has wide application prospects.

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Abstract

一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法及其制得的膜。制备方法包括以下步骤：1）用牺牲层堵住功能性孔膜的孔道；2）将嵌段共聚物溶解于溶剂中制得溶液；3）将制得的溶液置于预处理后的功能性孔膜上，使嵌段共聚物在预处理的功能性孔膜上成膜；4）使用选择性溶剂溶解牺牲层；5）在步骤2）的溶剂的饱和气氛中退火，使嵌段聚合物的孔道垂直贯通。

Description

一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法 技术领域
本发明涉及离子通道薄膜领域，具体地，涉及一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法。
 背景技术
盐差能是一种储量巨大、清洁可靠的可再生能源，其合理的开发和利用能够有效地解决人类社会面临的能源危机。目前在盐差能利用领域的研究主要集中在提高膜材料的能量密度、简化制备工艺及降低材料成本等方面。然而基于传统商业离子交换膜的盐差能转换体系存在制备成本高，可调控性差，能量密度效率低等问题（Menachem Elimelech et al. Nature 16，313-319（2012）；K. Nijmeijer et al. J. Membr. Sci. 467，279-291（2014））。近年来，固态纳米通道的出现为构筑高性能的膜材料和能源转换器件提供了条件（Arun Majumdar et al. Microfluid. Nanofluid. 9，1215–1224 (2010)； Alessandro Siria et al. Nature 28，455-458（2013））。与传统的离子交换膜相比，仿生固态纳米通道薄膜有着无可比拟的优越性，由于表面电荷的作用，可以在保留高选择性的基础上大幅度地提高离子通量，进而提高输出的能源密度。
 技术问题
然而，当前基于离子通道膜的盐差发电研究主要局限于单孔体系，能源密度比较低，距离实际应用有很大的差距。现有文献（Zhen Zhang，et al，J. Am. Chem. Soc. 2015，137，14765-14772）描述了一种复合体系表层嵌段共聚物膜，该膜的孔道结构不规则，离子传输的有效距离较大，阻抗较大，同时有效的功能区较短，导致盐差发电效率低。因此急需发展一种具有高能源密度的纳米通道薄膜来应对当前严重的的能源危机。
 技术解决方案
本发明目的在于应对当前能源短缺，不可再生的化石能源濒临枯竭的现状，寻求新材料来利用自然界广泛存在的可再生盐差能。
本发明提供了一种具有化学组成，几何，电荷非对称性的纳米通道薄膜的制备方法。该方法制备出的薄膜表现出了较高的能源输出功率。本发明通过溶剂退火，使嵌段共聚物膜中的无规通道垂直贯通，一方面减小了离子传输的有效距离，减小了阻抗，另一方面也增大了有效的功能区长度，大幅度提高了盐差发电性能。
本发明的具体技术方案如下：
本发明的嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法，如图1所示，包括以下步骤：
    1）将功能性孔膜预处理：用牺牲层堵住功能性孔膜的孔道；
2）将嵌段共聚物溶解于溶剂中，制得溶液；
3）将步骤2）制得的溶液置于步骤1）预处理后的功能性孔膜上，使嵌段共聚物在预处理的功能性孔膜上成膜，形成复合膜；
4）使用选择性溶剂溶解复合膜上的牺牲层；
5）将除去牺牲层的复合膜在步骤2）所述溶剂的饱和气氛中退火，使嵌段聚合物的孔道垂直贯通，制得盐差发电膜。
根据本发明所述的方法，其中，所述功能性孔膜为具有功能性基团的多孔氧化铝、多孔聚对苯二甲酸乙二醇酯或多孔聚酰亚胺，所述功能性集团为羟基、羧基、氨基和磺酸基中的一种或几种。
根据本发明所述的方法，其中，所述功能性孔膜的孔径为20～300 nm，孔数为10 8～10 9 个/cm 2。
根据本发明所述的方法，所述功能性孔膜可以通过阳极氧化、径迹刻蚀等方式制备获得。
根据本发明所述的方法，其中，所述牺牲层的材料为醋酸纤维素或聚苯乙烯磺酸钠。
根据本发明所述的方法，其中，所述嵌段聚合物可以但不限于是聚（苯乙烯-四乙烯基吡啶），聚（苯乙烯-丙烯酸），聚（苯乙烯-甲基丙烯酸N,N-二甲基氨基乙酯），聚（苯乙烯-N-异丙基丙烯酰胺），聚（苯乙烯-氧化乙烯）等中的一种或几种。
根据本发明所述的方法，其中，步骤2）所述溶剂可以为单一溶剂，例如，二氧六环、二氯甲烷、三氯甲烷、甲苯、苯、四氢呋喃或二甲基甲酰胺；或者，也可以两种溶剂混合的混合溶剂，例如，四氢呋喃与二氯甲烷的混合溶剂，乙醇与甲苯混合溶剂，或者，二氧六环与二甲基甲酰胺混合溶剂。优选地，步骤2）中配置的嵌段聚合物溶液的嵌段聚合物质量浓度为2%～8%。
根据本发明所述的方法，其特征在于，步骤3）所述在预处理后的功能性孔膜上成膜可以通过多种方式实现。例如，可以为悬涂法、浸渍提拉法等等。
根据本发明所述的方法，其中，步骤4）所述溶解牺牲层的选择性溶剂要根据牺牲层的材料选择，不能对膜体系产生影响，可以是可溶解醋酸纤维素的丙酮，或者，溶解聚苯乙烯磺酸钠的水等。本领域技术人员可以根据实际情况选择具体溶解方式，本发明不做具体限定，例如，如果只去除表面一层牺牲层材料时可以采用擦拭方式，如果是在最后制备成功后去除孔内的牺牲层材料时可以选用浸泡法方式。
根据本发明所述的方法，其中优选地，步骤5）所述退火温度可以在20～30℃，例如在常温下进行；退火时间可以为0.5～24 h。具体地，将除去牺牲层的复合膜静置于饱和溶剂蒸汽中退火。
本发明还提供给了一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜，所述盐差发电膜由本发明上述的任一的制备方法制得。
本发明制得的嵌段共聚物膜与功能性孔膜杂化的盐差发电膜，为一种纳米通道膜。该纳米通道膜具有非对称的孔结构，不均一的化学组成以及相反的表面电荷分布，具有超高的离子整流性，可用于高性能的盐差发电，当我们混合海水和盐水时，在不进行退火操作时，通过优化有机多孔膜基底的结构与组成，能源密度可以从0.12瓦特每平方米提高到约0.36瓦每平方米以上，这大大超过了同等操作条件下的商业离子交换膜的能源密度（约0.1瓦每平方米）。在选择性溶剂中退火处理，使无规的嵌段共聚物纳米通道垂直贯通，盐差发电的功率密度可以提高到0.7瓦每平方米以上。
 有益效果
本发明提供的基于嵌段聚合物的盐差发电膜的制备方法，克服了现有商用离子交换膜制备工艺复杂，可控性差，离子通量低，能源密度低等问题。通过控制大孔基底的结构，组成以及厚度，结合溶剂退火操作，本发明提供的复合盐差发电膜的能源密度可以从0.12瓦特每平方米提高到0.7瓦每平方米以上，远超过了同等条件下的商业离子交换膜。
 附图说明
图1为本发明盐差发电膜的制备方法的流程图；其中，（1）为涂覆牺牲层，（2）为嵌段共聚物成膜，（3）溶解牺牲层；（4）选择性溶剂中退火。
图2为本发明具体实施方式中使用的盐差发电装置示意图；其中，（1）第一容器，（2）第二容器，（3）膜，（4）电流表，（5）负载电阻。
 本发明的最佳实施方式
实施例 8
（1）功能性的多孔膜基底的制备。
非对称径迹刻蚀法制备通道大口端直径500nm，小口端直径为50 nm 的多孔聚对苯二甲酸乙二醇酯基底。制备的多孔膜的孔数为10 7 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用水溶性的PSS为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为5%的醋酸纤维素的丙酮溶液，悬涂（1600 r，30 s）于多孔聚对苯二甲酸乙二醇酯基底的小口端。然后用蘸有去离子水的棉签擦除表面的PSS，暴露出一个相对光滑的表面。
（3）嵌段共聚物的在选择性溶剂中的溶解及成膜。
选取二氧六环为溶剂溶解嵌段共聚物（聚（苯乙烯-丙烯酸）），质量分数为7%，悬涂（2000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于水中，超声15分钟，取出吹干。
（4）在二氧六环饱和气氛中进行溶剂退火2h，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.70瓦特每平方米。
 本发明的实施方式
实施例 1
（1）功能性的多孔膜基底的制备。
阳极氧化法制备通道直径为80 nm 的多孔氧化铝基底。制备的多孔膜的孔数为10 9 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用醋酸纤维素为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为7%的醋酸纤维素的丙酮溶液，悬涂（1000 r，60 s）于多孔氧化铝基底上。然后用蘸有丙酮的棉签擦除表面的醋酸纤维素，暴露出一个相对光滑的表面。
（3）嵌段共聚物在选择性溶剂中的溶解及成膜。
选取二氯甲烷为溶剂溶解嵌段共聚物（聚（苯乙烯-四乙烯基吡啶）），质量分数为4%，悬涂（1000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于丙酮中，超声15分钟，取出吹干。
（4）不进行溶剂退火处理，制得盐差发电膜。
（5）盐差发电性能的测试。
上述步骤（5）的盐差发电性能的测试所用的盐差发电装置示意图见图2。所述盐差发电装置是一个封闭体系，第一容器中装有高浓度或低浓度的电解质溶液，对应于第二容器中装有低浓度或高浓度的电解质溶液。在第一容器中设置有阳极或阴极，对应于在第二容器中设置有阳极或阴极；并且第一容器中设置的阳极或阴极的导线通向第一容器外，对应于第二容器中设置的阴极或阳极的导线通向第二容器外。通过外接电流表以及负载电阻将电路连通；所述第一容器与第二容器之间由盐差发电膜相隔。
所述的电解质为氯化钠，氯化锂或氯化钾。
所述的电极为银氯化银电极或者铂电极。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.18瓦特每平方米。
实施例 2
（1）功能性的多孔膜基底的制备。
阳极氧化法制备通道直径为40 nm 的多孔氧化铝基底。制备的多孔膜的孔数为10 9 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用醋酸纤维素为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为7%的醋酸纤维素的丙酮溶液，悬涂（1000 r，60 s）于多孔氧化铝基底上。然后用蘸有丙酮的棉签擦除表面的醋酸纤维素，暴露出一个相对光滑的表面。
（3）嵌段共聚物在选择性溶剂中的溶解及成膜。
选取二氯甲烷为溶剂溶解嵌段共聚物（聚（苯乙烯-四乙烯基吡啶）），质量分数为4%，悬涂（1000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于丙酮中，超声15分钟，取出吹干。
（4）不进行溶剂退火处理，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.12瓦特每平方米。
实施例 3
（1）功能性的多孔膜基底的制备。
阳极氧化法制备通道直径为80 nm 的多孔氧化铝基底。制备的多孔膜的孔数为10 9 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用醋酸纤维素为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为7%的醋酸纤维素的丙酮溶液，悬涂（1000 r，60 s）于多孔氧化铝基底上。然后用蘸有丙酮的棉签擦除表面的醋酸纤维素，暴露出一个相对光滑的表面。
（3）嵌段共聚物在选择性溶剂中的溶解及成膜。
选取二氯甲烷为溶剂溶解嵌段共聚物（聚（苯乙烯-四乙烯基吡啶）），质量分数为4%，悬涂（2000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于丙酮中，超声15分钟，取出吹干。
（4）不进行溶剂退火处理，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.15瓦特每平方米。
实施例 4
（1）功能性的多孔膜基底的制备。
阳极氧化法制备通道直径为80 nm 的多孔氧化铝基底。制备的多孔膜的孔数为10 9 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用醋酸纤维素为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为7%的醋酸纤维素的丙酮溶液，悬涂（1000 r，60 s）于多孔氧化铝基底上。然后用蘸有丙酮的棉签擦除表面的醋酸纤维素，暴露出一个相对光滑的表面。
（3）嵌段共聚物在选择性溶剂中的溶解及成膜。
选取二氯甲烷为溶剂溶解嵌段共聚物（聚（苯乙烯-四乙烯基吡啶）），质量分数为4%，悬涂（1000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于丙酮中，超声15分钟，取出吹干。
（4）在二氯甲烷饱和气氛中进行溶剂退火2h，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.68瓦特每平方米。
实施例 5
（1）功能性的多孔膜基底的制备。
对称径迹刻蚀法制备通道直径为50 nm 的多孔聚对苯二甲酸乙二醇酯基底。制备的多孔膜的孔数为10 7 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用水溶性的PSS（聚苯乙烯磺酸钠）为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为5%的醋酸纤维素的丙酮溶液，悬涂（1600 r，30 s）于多孔聚对苯二甲酸乙二醇酯基底上。然后用蘸有去离子水的棉签擦除表面的PSS，暴露出一个相对光滑的表面。
（3）嵌段共聚物在选择性溶剂中的溶解及成膜。
选取二氧六环为溶剂溶解嵌段共聚物（聚（苯乙烯-丙烯酸）），质量分数为7%，悬涂（2000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于水中，超声15分钟，取出吹干。
（4）不进行溶剂退火处理，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.30瓦特每平方米。
实施例 6
（1）功能性的多孔膜基底的制备。
对称径迹刻蚀法制备通道直径为20 nm 的多孔聚对苯二甲酸乙二醇酯基底。制备的多孔膜的孔数为10 7 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用水溶性的PSS为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为5%的醋酸纤维素的丙酮溶液，悬涂（1600 r，30 s）于多孔聚对苯二甲酸乙二醇酯基底上。然后用蘸有去离子水的棉签擦除表面的PSS，暴露出一个相对光滑的表面。
（3）嵌段共聚物在选择性溶剂中的溶解及成膜。
选取二氧六环为溶剂溶解嵌段共聚物（聚（苯乙烯-丙烯酸）），质量分数为7%，悬涂（2000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于水中，超声15分钟，取出吹干。
（4）不进行溶剂退火处理，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.22瓦特每平方米。
实施例 7
（1）功能性的多孔膜基底的制备。
非对称径迹刻蚀法制备通道大口端直径500nm，小口端直径为50 nm 的多孔聚对苯二甲酸乙二醇酯基底。制备的多孔膜的孔数为10 7 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用水溶性的PSS为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为5%的醋酸纤维素的丙酮溶液，悬涂（1600 r，30 s）于多孔聚对苯二甲酸乙二醇酯基底的小口端。然后用蘸有去离子水的棉签擦除表面的PSS，暴露出一个相对光滑的表面。
（3）嵌段共聚物的在选择性溶剂中的溶解及成膜。
选取二氧六环为溶剂溶解嵌段共聚物（聚（苯乙烯-丙烯酸）），质量分数为7%，悬涂（2000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于水中，超声15分钟，取出吹干，制得盐差发电膜。
（4）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.36瓦特每平方米，能源转化效率为36%。
实施例 8
（1）功能性的多孔膜基底的制备。
非对称径迹刻蚀法制备通道大口端直径500nm，小口端直径为50 nm 的多孔聚对苯二甲酸乙二醇酯基底。制备的多孔膜的孔数为10 7 cm -2，具有规则的孔径分布。
（2）大孔基底的预处理。
用水溶性的PSS为堵孔材料，用牺牲层法处理步骤（1）中的多孔膜防止溶液渗漏。首先配置质量分数为5%的醋酸纤维素的丙酮溶液，悬涂（1600 r，30 s）于多孔聚对苯二甲酸乙二醇酯基底的小口端。然后用蘸有去离子水的棉签擦除表面的PSS，暴露出一个相对光滑的表面。
（3）嵌段共聚物的在选择性溶剂中的溶解及成膜。
选取二氧六环为溶剂溶解嵌段共聚物（聚（苯乙烯-丙烯酸）），质量分数为7%，悬涂（2000r，45s）于步骤（2）制备出的多孔基底上。最后溶解掉通道内的牺牲层，将复合膜浸没于水中，超声15分钟，取出吹干。
（4）在二氧六环饱和气氛中进行溶剂退火2h，制得盐差发电膜。
（5）盐差发电性能的测试，测试所用装置参照实施例1。
上述复合离子通道盐差发电薄膜的盐差发电功率密度为0.70瓦特每平方米。
 工业实用性
本发明的方法操作简便、易于控制、所需设备简单、能够大规模生产，有着广泛的应用前景。

Claims (10)

  1. 一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法，包括以下步骤：
        1）将功能性孔膜预处理：用牺牲层堵住功能性孔膜的孔道；
    2）将嵌段共聚物溶解于溶剂中，制得溶液；
    3）将步骤2）制得的溶液置于步骤1）预处理后的功能性孔膜上，使嵌段共聚物在预处理的功能性孔膜上成膜，形成复合膜；
    4）使用选择性溶剂溶解复合膜上的牺牲层；
    5）将除去牺牲层的复合膜在步骤2）所述溶剂的饱和气氛中退火，使嵌段聚合物的孔道垂直贯通，制得盐差发电膜。
  2. 根据权利要求1所述的制备方法，其特征在于，所述功能性孔膜为具有功能性基团的多孔氧化铝或多孔聚对苯二甲酸乙二醇酯，所述功能性集团为羟基、羧基、氨基和磺酸基中的一种或几种。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述功能孔膜的孔径为20～300 nm，孔数为10 8～10 9 个/cm 2。
  4. 根据权利要求1所述的制备方法，其特征在于，所述牺牲层的材料为醋酸纤维素或聚苯乙烯磺酸钠。
  5. 根据权利要求1所述的制备方法，其特征在于，所述嵌段聚合物为聚（苯乙烯-四乙烯基吡啶），聚（苯乙烯-丙烯酸），聚（苯乙烯-甲基丙烯酸N,N-二甲基氨基乙酯），聚（苯乙烯- N-异丙基丙烯酰胺）和聚（苯乙烯-氧化乙烯）中的一种或几种。
  6. 根据权利要求1或5所述的制备方法，其特征在于，步骤2）所述溶剂为二氧六环、二氯甲烷、三氯甲烷、甲苯、苯、四氢呋喃或二甲基甲酰胺；或者，所述溶剂为混合溶剂，所述混合溶剂为四氢呋喃与二氯甲烷的混合溶剂，乙醇与甲苯混合溶剂，或者，二氧六环与二甲基甲酰胺混合溶剂。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤3）所述成膜的方法为悬涂法或浸渍提拉法。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤4）所述选择性溶剂为丙酮或水。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤5）所述退火温度为20～30℃，时间为0.5～24 h。
  10. 一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜，其特征在于，所述盐差发电膜由权利要求1-10任一所述的制备方法制得。
PCT/CN2018/085929 2017-05-24 2018-05-08 一种嵌段共聚物膜与功能性孔膜杂化的盐差发电膜的制备方法 WO2018214723A1 (zh)

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