CN107546398B - Ion-conducting membrane with microphase separation structure and preparation and application thereof - Google Patents
Ion-conducting membrane with microphase separation structure and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to an ion-conducting membrane with a microphase separation structure, which is prepared by dissolving one or more than two hydrophobic polymer resins and one or more than two hydrophilic polymer resins as raw materials in an organic solvent and volatilizing the solvent, wherein the hydrophilic phase is induced to aggregate in the volatilization process of the solvent, so that the microphase separation structure ion-conducting membrane with a hydrophobic area and a hydrophilic area is formed; wherein the mass ratio of the concentration of the hydrophobic polymer resin to the hydrophilic polymer resin is 0.5-5. The ion conduction membrane with the microphase separation structure has the advantages of simple process, environment-friendly process, controllable microphase structure and easy realization of batch production, and the assembled battery has good capacity retention rate and excellent battery performance.
Description
Technical Field
The present invention relates to an ion-conducting membrane for a flow battery.
Background
The flow battery is a new electrochemical energy storage technology, and compared with other energy storage technologies, the flow battery has the advantages of flexible system design, large storage capacity, free site selection, high energy conversion efficiency, deep discharge, safety, environmental protection, low maintenance cost and the like, and can be widely applied to the aspects of power generation and energy storage of renewable energy sources such as wind energy, solar energy and the like, emergency power supply systems, standby power stations, power systems and the like, and peak clipping and valley filling are realized. The full Vanadium Flow Battery (VFB) has the advantages of high safety, good stability, high efficiency, long service life (the service life is more than 15 years), low cost and the like, and thus is considered to have a good application prospect.
The battery diaphragm is an important component in the flow battery and plays a role in blocking electrolyte of the positive electrode and the negative electrode and providing a proton transmission channel. The proton conductivity, chemical stability, ion selectivity and the like of the membrane directly influence the electrochemical performance and service life of the battery; it is desirable that the membranes have low active material permeability (i.e., high selectivity) and low sheet resistance (i.e., high ionic conductivity), while also having good chemical stability and low cost. The membrane material used at home and abroad at present is mainly a Nafion membrane developed by DuPont in the United states, and the Nafion membrane has excellent performances in the aspects of electrochemical performance, service life and the like. The membrane consists of a hydrophobic fluorocarbon skeleton and a hydrophilic sulfonic acid side chain. When the perfluorosulfonic acid membrane is applied to a battery, due to the special structure, a microphase separation structure is generated between a hydrophobic framework and a hydrophilic group in the membrane, so that the perfluorosulfonic acid membrane has excellent proton conductivity. The micro-phase structure of the fixed structure causes the fixed structure to have the defects of poor ion selectivity and the like when being applied to batteries, particularly all-vanadium redox flow batteries; on the other hand, such membranes are expensive, which limits the industrial application of the membranes. Therefore, it is important to develop a battery separator having high selectivity, high stability and low cost. And the non-fluorine ion exchange membrane has insufficient chemical stability in the all-vanadium flow battery to meet the long-term use requirement due to the existence of the ion exchange group.
The copolymer can often form complex structures with different scales, and has wide application in the technical field of materials. The block or graft multicomponent polymer is composed of two or more segments with different properties. When the solubility parameters between the monomer segments differ significantly, resulting in incompatibility, there is a tendency for phase separation to occur; however, because the different monomer segments are connected by chemical bonds, the copolymers cannot undergo macroscopic phase separation, but only can form phase regions in the nanometer or micrometer scale range, the phase separation is called microphase separation, and the structure formed by the microphase separation is called microphase separation structure. Generally, the preparation process of the block copolymer forming the microphase separation structure is complex, a large amount of organic solvent is needed, and the ecological environment is not facilitated, so that the large-scale application of the block copolymer is limited to a certain extent.
Disclosure of Invention
The invention aims to prepare an ion-conducting membrane with a microphase separation structure, prepare ion-conducting membranes with different microphase structures by controlling preparation conditions, enable the ion-conducting membranes to have excellent ion selectivity and ion conductivity, and provide application of the ion-conducting membrane with the microphase separation structure in a flow battery, in particular application of the ion-conducting membrane in an all-vanadium flow battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an ion-conducting membrane with a microphase separation structure is prepared by dissolving one or more than two hydrophobic polymer resins and one or more than two hydrophilic polymer resins as raw materials in an organic solvent and volatilizing the solvent, wherein the hydrophilic phase is induced to aggregate in the volatilization process of the solvent, so that the microphase separation structure ion-conducting membrane with a hydrophobic area and a hydrophilic area is formed;
wherein the mass ratio of the hydrophobic polymer resin to the hydrophilic polymer resin is 0.5-5.
The hydrophobic polymer resin is polyether sulfone, polysulfones, polyether ketones, polytetrafluoroethylene, polyvinylidene fluoride or polystyrene; the hydrophilic polymer resin is sulfonated polysulfone, sulfonated polyimide, sulfonated polyether ketone, sulfonated polybenzimidazole, polyvinylpyrrolidone or polyethylene glycol.
Wherein, the phase separation structure is a layered structure, a co-continuous structure, a spherical structure or a columnar structure.
The ion-conducting membrane with the microphase separation structure is prepared by adopting the following steps:
(1) dissolving hydrophobic polymer resin and hydrophilic polymer resin in an organic solvent, and fully stirring for 20-60 hours at the temperature of 20-100 ℃ to prepare a uniformly blended solution; wherein the mass ratio of the hydrophobic polymer resin to the hydrophilic polymer resin is 0.5-5; the mass concentration of the hydrophobic polymer resin and the hydrophilic polymer resin in the organic solvent is 10-50%.
(2) Pouring the blending solution prepared in the step (1) on a non-woven fabric substrate or directly on a glass plate, volatilizing the solvent for 0-60 seconds, and evaporating the solvent at the temperature of 40-200 ℃ to dryness to form a film; solvent volatilization induces the hydrophilic phase to gather to obtain a membrane with a microphase separation structure; the thickness of the film is 20 to 500 μm.
The organic solvent is one or more of dimethyl sulfoxide (DMSO), N '-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF) and Tetrahydrofuran (THF).
The ion-conducting membrane with the microphase separation structure is used in a flow battery.
The flow battery comprises an all-vanadium flow battery, a zinc/cerium flow battery, a vanadium/bromine flow battery or an iron/chromium flow battery.
Advantageous results of the invention
1. The blending method is that hydrophobic high molecular polymer and hydrophilic high molecular polymer are blended and dissolved in organic solvent to obtain homogeneous casting liquid, and the casting liquid is coated homogeneously onto non-woven fabric or clean glass plate and then solvent is evaporated to form film. In the solvent volatilization process, the solvent induces the hydrophilic polymer resin to aggregate, so that the mixture is subjected to microphase separation. The prepared ion-conducting membrane with the micro-phase separation structure is applied to a flow battery, and the ion-conducting membranes with different micro-phase structures are prepared by controlling preparation conditions, so that the ion-conducting membranes have excellent ion selectivity and ion conductivity, and the application of the ion-conducting membrane with the micro-phase separation structure in the flow battery, in particular the application of the ion-conducting membrane in an all-vanadium flow battery, is provided.
2. The ionic conduction membrane with the microphase separation structure prepared by the invention has adjustable microphase structure and is easy to realize mass production.
3. The ion-conducting membrane with the micro-phase separation structure is prepared by the blending method, only the aqueous solution of the ion exchange resin and the cleaning solvent are needed, and the preparation process is clean and environment-friendly.
4. The method can realize the controllability of the battery efficiency and the capacity of the flow battery, particularly the all-vanadium flow battery.
Drawings
FIG. 1 SEM image of surface and cross-section of microphase ion-conducting membrane prepared in example 1
(a: surface SEM picture of film facing air side; b: enlarged surface view of white dotted line in figure a; c: surface SEM picture of film facing glass plate side; d: cross-sectional SEM picture of prepared film).
The sheet resistance of the ion-conducting membrane with microphase separation structure and the Nafion115 membrane prepared under different conditions in fig. 2 were obtained by a two-electrode ac impedance test (Solartron Electrochemical System), in the following specific test manner: the membrane is first placed in 0.5mol L-1Fully soaking in sulfuric acid aqueous solution for 24 hours; the membrane was then filled with 0.5mol L-1In the test pool of dilute sulfuric acid, graphite plates with fixed inter-polar distance are used as electrodes, and an alternating current impedance instrument is used for scanning in the range of 1kHZ-1MHZ, and the measured resistance is r1(ii) a Finally, willThe film is removed and the resistance of the blank is again measured as r using an AC impedance2. The effective area S of the membrane is 1cm2The calculation formula of the surface resistance is as follows: r ═ r (r)1-r2)xS。
FIG. 3 vanadium permeability of ion conducting membranes with microphase separation structures and Nafion115 membranes prepared under different conditions;
the solution composition of the left side infiltration tank of the vanadium infiltration testing device is 80mL and 3mol L-1VOSO4+3mol L-1H2SO4The composition of the solution in the right side infiltration tank is 80mL and 3mol L-1MgSO4+3mol L-1H2SO4Wherein MgSO is used4To balance the ionic strength of the solutions on both sides to reduce water migration due to osmotic pressure, the effective area of the membrane is 9cm2. To avoid concentration polarization at the liquid/membrane interface, the solutions were continuously stirred on both sides during the test. Every 24h, 3mL of sample solution was removed from the right side permeate cell while the same volume of vanadium solution was replenished. VO in sample solution2+The concentration of (b) is determined by an ultraviolet-visible spectrophotometer.
FIG. 4 shows that the ion-conducting membrane and the Nafion115 membrane with microphase separation structure prepared under different conditions are at 80mA cm-2Cell performance under the conditions of (1).
FIG. 5 polyethersulfone ion-conducting membrane with microphase separation structure at 80mA cm-2And 120mA cm-2The cycling stability under the conditions of (1).
FIG. 6 shows polyethersulfone ion-conducting membrane with microphase separation structure and Nafion115 membrane at 80mA cm-2Capacity stability under conditions.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example
14.9184g of Polyethersulfone (PES) was dissolved in 45.0593g of DMAC and stirred for 48 hours to form a polymer solution, which was spread on a glass plate, which was then heated on a 50 ℃ hot plate for 48 hours and cooled at room temperature, and the glass plate was placed in a water bath to obtain a homogeneous polyethersulfone membrane.
The prepared polyether sulfone membrane and a commercial Nafion115 membrane are utilized to assemble the all-vanadium redox flow battery, wherein a catalytic layer is an activated carbon felt, a bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. Because the polyether sulfone membrane has no phase separation structure, the ion transmission resistance is large, and the assembled flow battery cannot be charged and discharged normally; the coulombic efficiency of the all-vanadium redox flow battery assembled by the commercial Nafion115 membrane is 93.38%, the voltage efficiency is 88.30%, and the energy efficiency is 82.45%.
Example 1
1.6087g of polyether sulfone, 0.4028g of sulfonated polyether ether ketone and 1.0029g of polyethylene glycol are dissolved in 8.0655g of DMAC, the mixture is stirred for 24 hours, the formed polymer solution is paved on a glass plate, then the glass plate is transferred to a 50 ℃ hot table to be heated for 48 hours, the hydrophilic phase sulfonated polyether ether ketone, the polyethylene glycol and the hydrophobic phase polyether sulfone are induced to be subjected to phase separation in the solvent volatilization process, a polyether sulfone membrane with a microphase separation structure (shown in figure 1) is obtained, the glass plate is placed in a water tank after being cooled at room temperature, and the membrane thickness is 22 mu m. The prepared ion-conducting membrane with the microphase separation structure is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. The coulombic efficiency of the assembled flow battery was 91.09%, the voltage efficiency was 90.08%, and the energy efficiency was 82.05% (fig. 3).
Example 2
7.4592g of polyether sulfone and 7.5062g of polyvinylpyrrolidone (PVP) are dissolved in 45.1121g of DMAC, the mixture is stirred for 48 hours, the formed polymer solution is paved on a glass plate, then the glass plate is transferred to a 50 ℃ hot table to be heated for 48 hours, the PVP phase separation is induced in the solvent volatilization process, a polyether sulfone membrane (PES) with a microphase separation structure is obtained, the glass plate is placed in a water tank after being cooled at room temperature, and the membrane thickness is 55 mu m. By means of prepared microphase separated junctionsThe ion-conducting membrane assembled all-vanadium redox flow battery comprises a catalyst layer made of activated carbon felt, a bipolar plate made of graphite, and an effective membrane area of 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. The coulombic efficiency of the assembled flow battery is 99.09%, the voltage efficiency is 89.55%, the energy efficiency is 88.74% (fig. 4), and the battery has no obvious performance attenuation after more than 8000 cycles and shows excellent stability (fig. 5). The single cell assembled with the polyethersulfone ion-conducting membrane having a microphase-separated structure had excellent capacity retention compared to the Nafion115 membrane (fig. 6).
Example 3
3.0396g of Polysulfone (PSF), 3.1204g of polyether sulfone (PES) and 6.003g of polyvinyl alcohol 6000(PEG-6000) are dissolved in 42.6982g of DMAC, the mixture is stirred for 48 hours to form a polymer solution, the polymer solution is laid on a glass plate, then the glass plate is transferred to a 50 ℃ hot table to be heated for 48 hours, PEG-6000 is induced to carry out phase separation in the solvent volatilization process to obtain a polysulfone/polyether sulfone membrane (PSF for short) with a microphase separation structure, and the glass plate is placed in a water tank after being cooled at room temperature, wherein the membrane thickness is 52 mu m. The prepared ion-conducting membrane with the microphase separation structure is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. The coulombic efficiency of the assembled flow battery was 98.87%, the voltage efficiency was 91.14%, and the energy efficiency was 90.11% (fig. 4).
Example 4
6.3019g of Polysulfone (PSF) and 4.8015g of polyvinylpyrrolidone (PVP) are dissolved in 48.0144g of DMAC, stirred for 48 hours to form a polymer solution, the polymer solution is paved on a glass plate, then the glass plate is transferred to a 50 ℃ hot bench to be heated for 48 hours, phase separation of the PVP is induced in the solvent volatilization process to obtain a polysulfone membrane with a microphase separation structure, and the glass plate is placed in a water tank after being cooled at room temperature, wherein the thickness of the membrane is 42 mu m. Utilizing prepared ion-conducting membrane with microphase separation structureAssembling the all-vanadium redox flow battery, wherein the catalyst layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. The coulombic efficiency of the assembled flow battery was 99.36%, the voltage efficiency was 88.66%, and the energy efficiency was 88.10% (fig. 4).
Example 5
7.2048g of polyvinylidene fluoride (PVDF) and 4.8015g of polyvinylpyrrolidone (PVP) are dissolved in 45.3598g of DMAC, stirring is carried out for 48 hours, the formed polymer solution is paved on a glass plate, then the glass plate is transferred to a 50 ℃ hot table to be heated for 48 hours, PVP phase separation is induced in the solvent volatilization process, a polyvinylidene fluoride film (PVDF for short) with a microphase separation structure is obtained, the glass plate is placed in a water tank after being cooled at room temperature, and the film thickness is 45 microns. The prepared ion-conducting membrane with the microphase separation structure is used for assembling the all-vanadium redox flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 48cm2Current density of 80mA.cm-2The concentration of vanadium ions in the electrolyte is 1.50mol L-1，H2SO4The concentration is 3mol L-1. The coulombic efficiency of the assembled flow battery is 97.62%, the voltage efficiency is 89.39%, and the energy efficiency is 87.26%.
The topographical map prepared in fig. 1 with microphase-separated structures can be seen that the surfaces of the membrane facing the air side (fig. 1a and b) are more distinct, mainly because water vapor in air can further induce the separation of the hydrophilic and hydrophobic phases within the membrane, thereby forming membranes with structures of different degrees of microphase separation.
As can be seen from the surface resistance test of fig. 2, the surface resistance of the ion conducting membrane with the microphase separation structure is lower than that of the Nafion115 membrane, so that the membrane should have higher ion conductivity in the flow battery, especially in the all-vanadium flow battery, and a single cell assembled by the membrane is expected to obtain higher voltage efficiency.
As can be seen from the vanadium permeation test in fig. 3, the vanadium ion permeation rate of the ion conducting membrane with the microphase separation structure is much lower than that of the Nafion115 membrane, so that the membrane should have higher ion selectivity in the flow battery, especially in the all-vanadium flow battery, and a single cell assembled by the membrane is expected to obtain higher coulombic efficiency.
As can be seen from the cell performance of FIG. 4, the cell assembled with the ion-conducting membrane having a microphase separation structure was 80mA cm in comparison with the Nafion115 membrane due to the specific microphase separation structure within the membrane-2Has excellent battery performance under the conditions of (1).
As can be seen from the battery cycle stability test of fig. 5, the polyethersulfone ion-conducting membrane with the microphase separation structure has excellent stability in the all-vanadium flow battery.
As can be seen in the cell performance of FIG. 6, at 80mA cm compared to the Nafion115 membrane-2Under the conditions of (1), a single cell assembled by the polyethersulfone ion-conducting membrane with the micro-phase separation structure has excellent capacity retention rate.
Claims (5)
1. Use of an ion-conducting membrane having a microphase separation structure, characterized in that: one or more than two hydrophobic polymer resins and one or more than two hydrophilic polymer resins are taken as raw materials, the ionic conduction membrane is prepared by dissolving the raw materials in an organic solvent and then volatilizing the solvent, and a hydrophilic phase is induced to aggregate in the volatilization process of the solvent, so that the ionic conduction membrane with a microphase separation structure with a hydrophobic area and a hydrophilic area is formed;
wherein the mass ratio of the hydrophobic polymer resin to the hydrophilic polymer resin is 0.5-5; the ion-conducting membrane with the microphase separation structure is used in a flow battery;
the ion-conducting membrane with the microphase separation structure is prepared by adopting the following steps:
(1) dissolving hydrophobic polymer resin and hydrophilic polymer resin in an organic solvent, and fully stirring for 20-60 hours at the temperature of 20-100 ℃ to prepare a uniformly blended solution; wherein the mass ratio of the hydrophobic polymer resin to the hydrophilic polymer resin is 0.5-5;
(2) pouring the blending solution prepared in the step (1) on a non-woven fabric substrate or directly on a glass plate, volatilizing the solvent for 0-60 seconds, and evaporating the solvent at the temperature of 40-200 ℃ to dryness to form a film; solvent volatilization induces the hydrophilic phase to gather to obtain a membrane with a microphase separation structure; the thickness of the film is 20 to 500 μm.
2. Use according to claim 1, characterized in that: the hydrophobic polymer resin is one or more than two of polyether sulfone, polysulfones, polyether ketones, polytetrafluoroethylene, polyvinylidene fluoride or polystyrene; the hydrophilic polymer resin is one or more of sulfonated polysulfone, sulfonated polyimide, sulfonated polyether ketone, sulfonated polybenzimidazole, polyvinylpyrrolidone and polyethylene glycol.
3. Use according to claim 1, characterized in that: wherein, the microphase separation structure is one or more than two of a lamellar structure, a co-continuous structure, a spherical structure or a columnar structure.
4. Use according to claim 1, characterized in that: the organic solvent is one or more of dimethyl sulfoxide (DMSO), N '-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF) and Tetrahydrofuran (THF), the mass concentration of the hydrophobic polymer resin in the organic solvent is 10-50%, and the mass concentration of the hydrophilic polymer resin in the organic solvent is 10-50%.
5. Use according to claim 1, characterized in that: the flow battery is an all-vanadium flow battery, a zinc/cerium flow battery, a vanadium/bromine flow battery or an iron/chromium flow battery.
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| CN111082117B (en) * | 2018-10-18 | 2021-06-01 | 中国科学院大连化学物理研究所 | Molecular sieve composite membrane and preparation method and application thereof |
| CN111106360B (en) * | 2018-10-25 | 2021-05-28 | 中国科学院大连化学物理研究所 | Ion conduction membrane with graphene-like structure, preparation and application |
| CN111224123B (en) * | 2018-11-26 | 2021-07-20 | 中国科学院大连化学物理研究所 | Preparation method of composite ion-conducting membrane, composite membrane and application thereof |
| CN112898620B (en) * | 2019-12-04 | 2022-04-01 | 中国科学院大连化学物理研究所 | Cross-linked fluorine-containing ethylene polymer ion-conducting membrane and preparation method and application thereof |
| CN112940306B (en) * | 2019-12-10 | 2022-04-15 | 中国科学院大连化学物理研究所 | Porous ion conduction membrane for flow battery and preparation and application thereof |
| CN113764693A (en) * | 2020-06-03 | 2021-12-07 | 中国科学院大连化学物理研究所 | Non-ionic ion conducting membrane and preparation and application thereof |
| CN114618312B (en) * | 2020-12-14 | 2023-07-25 | 上海交通大学 | Dual porous ion selective permeable membrane and preparation method thereof |
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