CN114621496A - Preparation and application of Daramic composite ion conduction membrane with bromine blocking and fixing functions - Google Patents

Preparation and application of Daramic composite ion conduction membrane with bromine blocking and fixing functions Download PDF

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CN114621496A
CN114621496A CN202011455860.6A CN202011455860A CN114621496A CN 114621496 A CN114621496 A CN 114621496A CN 202011455860 A CN202011455860 A CN 202011455860A CN 114621496 A CN114621496 A CN 114621496A
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daramic
membrane
bromine
prepared
flow battery
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CN114621496B (en
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李先锋
华朗
鲁文静
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on 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 halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on 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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on 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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
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    • 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
    • C08J2427/00—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 halogen; Derivatives of such polymers
    • C08J2427/02—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 halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—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 halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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

Abstract

The invention discloses a Daramic composite ion conduction membrane applied to a flow battery, and particularly designs an application of the membrane in a zinc-bromine flow battery. The film is prepared by coating a bromine-blocking and bromine-fixing functional layer on the surface of a commercialized Daramic film serving as a substrate. The invention has the advantages that: the porous composite ion-conducting membrane prepared by taking a commercial Daramic membrane as a substrate is applied to a flow battery for the first time. The Daramic membrane has high stability and low cost; the ion selectivity and the ion conductivity of the Daramic composite ion conduction membrane can be regulated and controlled by regulating the composition and the thickness of the bromine blocking and fixing functional layer; the prepared Daramic composite ion conduction membrane has the advantages of high mechanical strength, good chemical stability, high efficiency, low cost and the like; in addition, the preparation process of the Daramic composite ion conduction membrane is simple and controllable, and is suitable for large-scale production; therefore, the invention widens the selection range of the ion-conducting membrane material for the flow battery.

Description

Preparation and application of Daramic composite ion conduction membrane with bromine blocking and fixing functions
Technical Field
The invention provides a preparation method and application of a Daramic composite ion conduction membrane with a bromine blocking function, and particularly relates to application of the Daramic composite ion conduction membrane in the field of bromine-based flow batteries.
Background
In recent years, the use of renewable clean energy has been more and more loud, but the power generation of renewable energy such as wind energy, solar energy and the like is influenced by seasons, weather and regional conditions, and has obvious discontinuity and instability. The generated power fluctuation is large, and the adjustability is poor. And will likely have a large impact on the grid. Therefore, with the rapid rise of renewable energy sources such as wind energy and solar energy and smart grid industry, the energy storage technology becomes the focus of much attention. Large-scale energy storage technology is considered as strategic technology supporting the popularization of renewable energy, and is highly concerned by governments and business industries of various countries.
Energy storage techniques include two broad categories, physical and chemical. The physical energy storage comprises water pumping energy storage, compressed air energy storage, flywheel energy storage and the like. The chemical energy storage mainly comprises a lead-acid battery, a sodium-sulfur battery, a flow battery, a lithium ion battery and the like. However, various energy storage technologies have suitable application fields, and chemical energy storage technologies suitable for large-scale energy storage mainly comprise flow batteries, sodium-sulfur batteries, lead-acid batteries and lithium ion batteries. The advantages and the disadvantages of various energy storage technologies are comprehensively considered, and the energy storage technology of the flow battery is more widely concerned.
Among various flow battery energy storage technologies, the zinc-bromine flow battery energy storage technology has high energy density and low cost, and is very suitable for large-scale energy storage. At present, the energy storage technology of the zinc-bromine flow battery is in a demonstration stage, and the industrialization is expected to be successfully realized.
However, the strong diffusivity of bromine leads to severe self-discharge reactions, resulting in faster capacity fade and shorter service life, thereby hindering the commercial production of zinc-bromine flow batteries. The membrane is one of the key materials of zinc-bromine flow batteries and is also a barrier to prevent cross-mixing of bromine, and the properties of the membrane are important to inhibit bromine diffusion.
Therefore, the improvement of membrane selectivity is very important for reducing self-discharge reaction and further accelerating the practical application of the Zn-Br flow battery. The membrane is an important component of the battery and accounts for a relatively high proportion of the cost of the battery. Therefore, the development of an ion conductive membrane for a battery, which has low cost, high performance and good stability, is one of the important approaches for reducing the cost of the battery and improving the performance of the battery.
The Daramic membrane is a porous membrane compounded by polyethylene with ultrahigh molecular weight, amorphous silicon, mineral oil and the like. The commercial porous Daramic membrane is commonly used in the zinc-bromine flow battery due to the advantages of good chemical and mechanical stability, low cost and the like. However, the porous Daramic membrane has insufficient ion selectivity, and thus cannot effectively inhibit the diffusion of bromine. Therefore, the selectivity of the Daramic membrane is improved by coating the surface of the Daramic membrane with a coating with the functions of bromine blocking and bromine fixing. The coating has a porous structure and excellent ion conductivity, so that the composite ion-conducting membrane can have high conductivity while the selectivity is improved. The high stability of the Daramic membrane substrate enables the composite ion conduction membrane to have excellent stability in the flow battery, and the long-term stable operation of the battery can be ensured. In addition, the Daramic membrane is commercialized at present, the preparation process of the porous polymer coating is simple and easy to implement, and the membrane preparation process is simple and controllable and is suitable for large-scale production. The ion selectivity and ion conductivity of the Daramic composite ion-conducting film thickness can be adjusted by adjusting the types and proportions of components in the coating according to the requirements of the flow battery.
Disclosure of Invention
The invention provides a Daramic composite ion conduction membrane applied to a flow battery, which is prepared by coating a Daramic membrane substrate and a bromine blocking and fixing functional layer on one side surface of the substrate, and solves the problems that the ion selectivity of a porous Daramic membrane is not high and the diffusion of bromine cannot be effectively inhibited.
The technical scheme of the invention is as follows:
in one aspect, the invention provides a Daramic composite ion conduction membrane with bromine blocking and fixing functions, which comprises a Daramic membrane substrate and a bromine blocking and fixing functional layer compounded on one side surface of the Daramic membrane substrate; the bromine-blocking and bromine-fixing functional layer is composed of a bromine complexing agent and organic polymer resin; the bromine complexing agent is MEPBr (1-methyl-1-ethyl pyrrolidine bromide) or quaternary ammonium salt containing more than two N; the thickness of the functional layer is less than 300 μm.
The polymer material which plays a role of a binder in the functional layer is organic polymer resin Nafion, and the functional layer has good stability due to the interaction between the organic polymer resin Nafion and the molecules of a complexing agent, so that the complexing agent is prevented from being dissolved.
Preferably, the organic polymer resin is Nafion; the quaternary ammonium salt is one or a mixture of hexamethonium bromide and hexadimethrine bromide.
Preferably, the functional layer has a porous structure; the aperture of the functional layer is 1 nm-70 nm, and the porosity is 10% -50%; the thickness of the functional layer is 50-250 μm; the mass ratio of the bromine complexing agent to the organic polymer resin is 1-10: 1.
preferably, the thickness of the functional layer is between 80 and 200 μm; the mass ratio of the bromine complexing agent to the organic polymer resin is 2-8: 1.
in another aspect, the present invention provides a method for preparing the above ion-conducting membrane, wherein the Daramic composite ion-conducting membrane is prepared by the following steps:
(1) dissolving bromine complexing agent in organic solvent of organic polymer resin, and stirring at 10-40 deg.C for 1-24 hr to obtain a mixed solution; wherein the mass concentration of the organic polymer resin is 1-25% (preferably 3-15%);
(2) and (2) dripping the miscible liquid prepared in the step (1) on a Daramic film substrate, and scraping a layer of the blended solution on the Daramic film substrate by using a scraper, wherein the thickness of the coating is between 50 and 300 mu m (preferably 80 to 200 mu m).
(3) Placing the membrane obtained in the step (2) on a hot table, and preparing the Daramic composite ion conduction membrane with the functional layer coated on one side of the Daramic membrane substrate at the temperature of 45-55 ℃ for more than 3 hours (preferably 4-24 hours);
preferably, the organic solvent may be one or more of isopropyl alcohol, DMAC (N, N-dimethylacetamide), NMP (N-methylpyrrolidone), DMF (N, N-dimethylformamide).
The Daramic composite ion-conducting membrane is applied to flow batteries including, but not limited to, a zinc/bromine flow battery, a hydrogen/bromine flow battery, a lithium/bromine flow battery, a quinone/bromine flow battery, a magnesium/bromine flow battery, a sodium polysulfide/bromine flow battery, or a vanadium/bromine flow battery.
The beneficial results of the invention are as follows:
1. the originality is high, the composite ion conduction membrane which takes the Daramic membrane as a substrate and is coated with the bromine-blocking and bromine-fixing functional layer is prepared, and the composite ion conduction membrane is applied to the field of flow batteries for the first time;
2. the Daramic membrane substrate has high stability and low cost and can be purchased commercially. The thickness, the content and the type of the complexing agent of the bromine blocking and fixing functional layer are adjustable, so that the ion selectivity and the ion conductivity of the Daramic composite ion conduction membrane are adjustable.
3. The bromine-blocking solid bromine functional layer prepared by the invention has a porous structure, and the excellent ion conduction capability of the bromine-blocking solid bromine functional layer enables the composite ion conduction membrane to have high conductivity while improving the selectivity.
4. The Daramic composite ion conduction membrane has high mechanical strength, low cost, high efficiency and good stability;
5. the film preparation process is simple and controllable, and is suitable for large-scale production;
6. the ionic conductivity and ionic selectivity of the bromine-blocking and bromine-fixing functional layer of the Daramic composite ionic conduction membrane can be adjusted according to the requirements of the flow battery;
7. the invention widens the selection range of the ion conduction membrane of the flow battery.
Drawings
FIG. 1 is a graph of the cycling stability of a Daramic composite ion-conducting membrane.
Detailed Description
The Daramic composite ion conduction membrane prepared by the method can be applied to the fields of bromine-based flow batteries, zinc-based flow batteries and the like. The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
Dissolving MEPBr (1-methyl, 1-ethyl pyrrolidine bromide) in a solution with Nafion as a solute and isopropanol as a solvent, and fully stirring for 2 hours at 25 ℃ to prepare a uniform membrane casting solution; wherein the mass fraction of Nafion is 5%, and the mass ratio of MEPBr to Nafion is 2: 1; then, the prepared casting solution is uniformly dripped on a Daramic membrane substrate, a layer of blending solution is blade-coated on the surface of one side of the Daramic membrane substrate by using a scraper, and the Daramic membrane substrate is dried for more than 4 hours at the temperature of 50 ℃ to prepare the Daramic composite ion conduction membrane which coats the bromine-blocking and bromine-fixing functional layer on one side of the Daramic membrane substrate (the thickness is 200 mu m, the porosity is 60 percent, the pore diameter distribution range is 0.1-100nm, and the Daramic membranes used in the following examples and comparative examples adopt the parameters), wherein the thickness of the coating is 100 mu m.
The performance of the prepared Daramic composite ion conduction membrane is tested and compared with the performance of a Daramic membrane substrate, and the zinc-bromine flow battery is taken as an example in the invention. The area resistance of the prepared Daramic composite ion-conducting membrane is shown in Table 1 and is similar to that of a Daramic membrane substrate, which indicates that the prepared Daramic composite ion-conducting membrane has the ion conductivity similar to that of the Daramic membrane substrate; bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The transmittance is shown in table 1 and is obviously lower than the bromine ion transmittance of the Daramic membrane substrate, which indicates that the prepared Daramic composite ion conduction membrane has better ion selectivity than the Daramic membrane substrate. Therefore, the coating of the bromine-blocking and bromine-fixing functional layer on one side of the Daramic membrane substrate can greatly improve the ion selectivity of the Daramic membrane substrate and can keep the ion conductivity similar to that of the Daramic membrane substrate.
The prepared Daramic composite ion conduction membrane is used for assembling the zinc-bromine 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 36cm2The current density is 40mA cm-2The electrolyte comprises the following components: 2mol/L zinc bromide, 3mol/L potassium chloride and 0.8mol/L N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; electricity is adopted in the discharging processAnd in a voltage cut-off mode, the cut-off voltage is 0.8V. The coulomb efficiency of the prepared zinc-bromine flow battery assembled by the Daramic composite ion conduction membrane is 95.00 percent and is obviously higher than the coulomb efficiency (89.41 percent) of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the voltage efficiency was 86.36%, similar to that of a Daramic membrane substrate assembled zinc-bromine flow cell (86.73%); the energy efficiency is 82.04%, which is significantly higher than that of the zinc-bromine flow battery assembled on the Daramic membrane substrate (77.54%) (table 2), and it is demonstrated that the Daramic composite ion conductive membrane prepared in this example has better performance than that of the zinc-bromine flow battery assembled on the Daramic membrane substrate. The capacity retention rate of the prepared zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane is 98% within 100 cycles, which is obviously higher than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate (78%, Table 2). And the prepared zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane can continuously and stably run for more than 300 cycles, the performance is not obviously attenuated, and excellent stability is shown (figure 1).
Example 2
The preparation of the polymer solution and the preparation of the Daramic composite ion conductive membrane were carried out according to the method described in example 1, but the difference between the procedure and the conditions of example 1 was that the mass ratio of MEPBr to Nafion was 4: 1 (table 1).
The prepared Daramic composite ion conduction membrane is subjected to performance test and is compared with the performance of the Daramic composite ion conduction membrane prepared in example 1 and the performance of the Daramic membrane substrate, and the zinc-bromine flow battery is taken as an example in the invention. The sheet resistance of the prepared Daramic composite ion-conducting membrane is shown in table 1, which is lower than the sheet resistance of the Daramic composite ion-conducting membrane and the Daramic membrane substrate prepared in example 1, indicating that the increase in mass concentration of MEPBr reduces the impedance of the prepared Daramic composite ion-conducting membrane and increases the ion conductivity (table 5). This is because the higher the MEPBr concentration and the lower the polymer concentration, the larger the pore size and the higher the porosity of the prepared bromine-blocking solid bromine coating, the lower the resistance to ion transport, and the lower the impedance of the membrane. Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The transmittance is shown in Table 1 and is lower than that of the Dara prepared in example 1The bromine ion permeability of the mic composite ion conducting membrane and the Daramic membrane substrate shows that the prepared Daramic composite ion conducting membrane has ion selectivity superior to that of the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in example 1.
The Daramic composite ion conduction membrane prepared by the embodiment is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mAcm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in this example is 96.40%, which is slightly higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in example 1, but is obviously higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the voltage efficiency is 86.98%, which is slightly higher than the voltage efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared in example 1 and the voltage efficiency of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the energy efficiency is 83.85%, which is slightly higher than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared in example 1, and is obviously higher than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate. It is demonstrated that the performance of the Daramic composite ionic conduction membrane prepared in this example in the zinc-bromine flow battery is significantly better than that of the Daramic membrane substrate in the zinc-bromine flow battery, and the performance of the Daramic composite ionic conduction membrane prepared in example 1 in the zinc-bromine flow battery is slightly superior. The capacity retention rate of the prepared zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane is 98% within 100 cycles, which is equal to the capacity retention rate of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in example 1, but is significantly higher than the capacity retention rate of the zinc-bromine flow battery assembled by the Daramic membrane substrate (78%, table 2). And 300 prepared zinc-bromine flow batteries assembled by the Daramic composite ion conducting membrane can continuously and stably runThe performance is not obviously attenuated after the circulation, and the excellent stability is shown.
Example 3
A Daramic composite ion conductive membrane was prepared by preparing a polymer solution as described in example 1 above, under the same process and conditions as in example 1, except that the bromine-blocking and bromine-fixing functional layer had a thickness of 200 μm (Table 1).
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in example 1, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion-conducting membrane is shown in table 1 and is higher than that of the Daramic composite ion-conducting membrane prepared in example 1 and the Daramic membrane substrate, which indicates that the improvement of the thickness of the bromine-blocking and bromine-fixing functional layer increases the impedance of the prepared Daramic composite ion-conducting membrane, because the larger the thickness of the prepared coating, the higher the resistance to ion transmission (table 5). However, the area resistance of the prepared Daramic composite ion conductive membrane is not much different from the area resistances of the Daramic composite ion conductive membrane and the Daramic membrane substrate prepared in example 1, which indicates that the prepared Daramic composite ion conductive membrane can also have ion conductivity similar to that of the Daramic composite ion conductive membrane and the Daramic membrane substrate prepared in example 1; bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The permeability is shown in table 1 and is lower than the bromide ion permeability of the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in example 1, indicating that the prepared Daramic composite ion conducting membrane has ion selectivity superior to that of the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in example 1.
The Daramic composite ion conduction membrane prepared by the embodiment is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off moduleThe cut-off voltage was 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in this example is 95.96%, which is slightly higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in example 1, but is obviously higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the voltage efficiency is 86.06%, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in example 1; the energy efficiency is 82.58%, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared in example 1, but is obviously higher than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate. It is demonstrated that the performance of the Daramic composite ion conductive membrane prepared in this example in a zinc-bromine flow battery is significantly better than that of the Daramic membrane substrate in a zinc-bromine flow battery, but is inferior to that of the Daramic composite ion conductive membrane prepared in example 1 in a zinc-bromine flow battery. The capacity retention rate of the prepared zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane is 98% within 100 cycles, which is equal to the capacity retention rate of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in example 1, but is significantly higher than the capacity retention rate of the zinc-bromine flow battery assembled by the Daramic membrane substrate (78%, table 2). And the prepared zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane can continuously and stably run for more than 300 cycles, the performance is not obviously attenuated, and the zinc-bromine flow battery shows excellent stability.
Example 4
The preparation of the polymer solution and the preparation of the Daramic composite ion conductive membrane were carried out according to the method described in example 1, but the difference between the procedure and the conditions of example 1 was that the mass ratio of MEPBr to Nafion was 4: 1, the thickness of the bromine-blocking and bromine-fixing functional layer was 200. mu.m (Table 1).
The prepared Daramic composite ion conduction membrane is subjected to performance test and is compared with the performance of the Daramic composite ion conduction membrane prepared in example 1 and the performance of the Daramic membrane substrate, and the zinc-bromine flow battery is taken as an example in the invention. The sheet resistance of the prepared Daramic composite ion-conducting membrane is shown in Table 1, which is similar to that prepared in example 1The surface resistance of the prepared Daramic composite ion-conducting membrane is similar to that of the Daramic composite ion-conducting membrane and is slightly higher than that of the Daramic membrane substrate, because the improvement of the MEPBr mass concentration balances the improvement of the thickness of the functional layer, and the ion transmission resistance of the prepared Daramic composite ion-conducting membrane is kept stable (Table 5). Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The transmission rates are shown in table 1 and are lower than the bromine ion transmission rates of the Daramic composite ion conductive membrane and the Daramic membrane substrate prepared in example 1, which indicates that the prepared Daramic composite ion conductive membrane has ion selectivity superior to that of the Daramic composite ion conductive membrane and the Daramic membrane substrate prepared in example 1
The Daramic composite ion conduction membrane prepared by the embodiment is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2The current density is 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in the embodiment is 97.60%, which is higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ionic conduction membrane prepared in the embodiment 1, and is obviously higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the voltage efficiency is 86.78%, which is higher than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in the example 1; the energy efficiency is 84.70%, which is higher than that of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared in example 1, and is obviously higher than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate. The performance of the Daramic composite ion conduction membrane prepared in the embodiment in the zinc-bromine flow battery is obviously superior to that of the Daramic membrane substrate in the zinc-bromine flow battery. The capacity retention rate of the prepared Daramic composite ion-conducting membrane assembled zinc-bromine flow battery is 98 percent within 100 cycles, and the capacity retention rate of the prepared Daramic composite ion-conducting membrane assembled zinc-bromine flow battery in example 1 isThe rate is equal and is obviously higher than the capacity retention rate of the zinc-bromine flow battery assembled by the Daramic membrane substrate (78%, Table 2). And the prepared zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane can continuously and stably run for more than 300 cycles, the performance is not obviously attenuated, and the zinc-bromine flow battery shows excellent stability.
Example 5
The preparation of the polymer solution and the preparation of the Daramic composite ion conductive membrane were carried out according to the method described in example 1, but the difference between the procedure and the conditions of example 1 was that the mass ratio of MEPBr to Nafion was 12: 1 (table 1).
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion conductive membrane is shown in table 1 and is lower than that of the Daramic composite ion conductive membranes and the Daramic membrane substrates prepared in examples 1 to 4, which indicates that the Daramic composite ion conductive membrane prepared in the comparative example has high ion conductivity because the mass concentration of MEPBr is high and the binder ratio is small, which results in large aperture of the prepared functional layer, high porosity and reduced resistance to ion transmission (table 1). Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The permeability, as shown in table 1, is higher than that of the Daramic composite ion conductive membranes prepared in examples 1-4, but lower than that of the Daramic membrane substrates, indicating that the prepared Daramic composite ion conductive membranes have ion selectivity inferior to that of the Daramic composite ion conductive membranes prepared in examples 1-4, but superior to that of the Daramic membrane substrates
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. Da prepared in this comparative exampleThe coulombic efficiency of the zinc-bromine flow battery assembled by the ramic composite ion conducting membrane is 93.8 percent, which is lower than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared in examples 1-4; the voltage efficiency is 86.90 percent, which is higher than that of the Daramic composite ion conduction membrane prepared in the examples 1-4 and lower than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the energy efficiency was 81.51%, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in examples 1-4. Illustrating that the performance of the Daramic composite ion conductive membranes prepared in this comparative example in zinc-bromine flow batteries was inferior to the performance of the Daramic composite ion conductive membranes and Daramic membrane substrates prepared in examples 1-4 in zinc-bromine flow batteries (table 5).
Example 6
The preparation of the polymeric solution to prepare the Daramic composite ion conductive membrane was carried out according to the method described in example 1, and the process and conditions were the same as those of example 1, except that the mass ratio of MEPBr to Nafion was 12: 1, the thickness of the coating was 200 μm (Table 1).
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion conductive membrane is shown in table 1 and is significantly higher than the sheet resistance of the Daramic composite ion conductive membranes and the Daramic membrane substrates prepared in examples 1 to 4, which indicates that the Daramic composite ion conductive membrane prepared in the comparative example has low ion conductivity (table 6); bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The permeability is shown in table 1 and is significantly lower than the bromine ion permeability of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4, indicating that the prepared Daramic composite ion conducting membranes have ion selectivity superior to that of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4.
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the comparative example is 97.00 percent, which is higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the examples 1-4 and the Daramic membrane substrate; the voltage efficiency is 86.10%, which is similar to the voltage efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conduction membrane and the Daramic membrane substrate prepared in the examples 1-4; the energy efficiency was 83.52%, lower than examples 2 and 4, but higher than that of the zinc-bromine flow cell assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in examples 1 and 3. Illustrating that the performance of the Daramic composite ion conductive membrane prepared in this example in a zinc-bromine flow battery is slightly inferior to that of the Daramic composite ion conductive membranes prepared in examples 2 and 4, but superior to that of the Daramic membrane substrates prepared in examples 1 and 3 and example 5 (table 5).
Comparative example 1
A Daramic composite ion-conducting membrane was prepared by preparing a polymer solution as described in example 1 above, but under the same conditions and procedures as in example 1 except that the coating thickness was 300. mu.m (Table 1).
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in the examples 1-4, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion conductive membrane is shown in table 1 and is significantly higher than that of the Daramic composite ion conductive membranes and the Daramic membrane substrates prepared in examples 1 to 4, which indicates that the Daramic composite ion conductive membrane prepared in the comparative example has low ion conductivity because the prepared bromine-blocking solid-bromine functional layer has too large coating thickness and too large resistance to ion transmission (table 5). Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The transmittance is shown in Table 1 and is significantly lower than that of example 1-4 bromine ion permeability of the prepared Daramic composite ion conducting membranes and Daramic membrane substrates, indicating that the prepared Daramic composite ion conducting membranes have superior ion selectivity to the Daramic composite ion conducting membranes and Daramic membrane substrates prepared in examples 1-4.
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the comparative example cannot operate because the impedance is too large, which shows that the Daramic composite ion conducting membrane prepared by the comparative example has too low ion conductivity to be applied to the zinc-bromine flow battery (table 5).
Comparative example 2
The preparation of the polymeric solution for preparing the Daramic composite ion conductive membrane was carried out according to the method described in example 1, and the process and conditions were the same as those of example 1, except that the mass ratio of MEPBr to Nafion was 4: 1, the thickness of the coating was 300 μm (Table 1).
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion conductive membrane is shown in table 1 and is much higher than that of the Daramic composite ion conductive membranes and the Daramic membrane substrate prepared in examples 1 to 4, which indicates that the Daramic composite ion conductive membrane prepared in the comparative example has low ion conductivity because the excessively thick bromine-blocking and bromine-fixing functional layer causes the ion transmission resistance of the prepared Daramic composite ion conductive membrane to be excessively high (table 5). Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The transmission rates are shown in Table 1 and are significantly lower than the bromide ions of the Daramic composite ion-conducting membranes and the Daramic membrane substrates prepared in examples 1-4The permeability shows that the prepared Daramic composite ion-conducting membrane has better ion selectivity than the Daramic composite ion-conducting membrane and the Daramic membrane substrate prepared in the examples 1 to 4
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the comparative example cannot operate because the impedance is too large, which shows that the Daramic composite ion conducting membrane prepared by the comparative example has too low ion conductivity to be applied to the zinc-bromine flow battery (table 5).
Comparative example 3
The preparation of the polymer solution and the preparation of the Daramic composite ion conductive membrane were carried out according to the method described in example 1, but the difference between the procedure and the conditions of example 1 was that the mass ratio of MEPBr to Nafion was 6: 1, the thickness of the coating was 300 μm (Table 1).
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion-conducting membrane is shown in table 1 and is much higher than that of the Daramic composite ion-conducting membranes and the Daramic membrane substrates prepared in examples 1 to 4, which indicates that the Daramic composite ion-conducting membrane prepared in the comparative example has low ion conductivity (table 5). Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The permeability is shown in table 1 and is significantly lower than the bromine ion permeability of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4, indicating that the prepared Daramic composite ion conducting membranes have ion selectivity superior to that of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4.
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the comparative example cannot operate because the impedance is too large, which shows that the Daramic composite ion conducting membrane prepared by the comparative example has too low ion conductivity to be applied to the zinc-bromine flow battery (table 5).
Example 7
The preparation of a polymer solution and the preparation of a Daramic composite ion conductive membrane were carried out as described in example 1 above, except that hexamethonium bromide was used as the complexing agent, under the same conditions and procedures as in example 1.
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion-conducting membrane is shown in table 3, which is higher than that of the Daramic composite ion-conducting membrane prepared in example 1. Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The permeability is shown in table 3, which is slightly lower than the bromine ion permeability of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4, indicating that the prepared Daramic composite ion conducting membranes have superior ion selectivity to the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4.
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). Charging processA constant-capacitance charging mode is adopted, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared in the comparative example is 95.32 percent, which is higher than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared in the example 1 and the Daramic membrane substrate, but lower than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared in the examples 2 to 4; the voltage efficiency is 85.42%, which is higher than that of the Daramic composite ion conduction membrane prepared in examples 1-4 and lower than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the energy efficiency was 81.42%, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in examples 1-4. It is shown that the performance of the Daramic composite ion conductive membranes prepared in this comparative example in zinc-bromine flow batteries is inferior to that of the Daramic composite ion conductive membranes and the Daramic membrane substrates prepared in examples 1-4 in zinc-bromine flow batteries (table 5).
Example 8
The polymer solution was prepared according to the method described in example 7 above to prepare a Daramic composite ion conductive membrane, the procedure and conditions were the same as those in example 1, except that hexamethonium bromide was used as the complexing agent, and the mass ratio of hexamethonium bromide to Nafion was 4: 1.
the performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion-conducting membranes is shown in table 3, which is higher than that of the Daramic composite ion-conducting membranes prepared in examples 1-4. Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The permeability is shown in table 3, which is lower than the bromide ion permeability of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4, indicating that the prepared Daramic composite ion conducting membranes have superior ion selectivity to the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4.
Prepared by using this comparative exampleThe Daramic composite ion conduction membrane assembled zinc-bromine flow battery is characterized in that the catalytic layer is an activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L zinc bromide, 3mol/L potassium chloride and 0.8mol/L N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared in the comparative example is 94.7 percent, which is lower than the coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared in the examples 1 to 4; the voltage efficiency was 85.78%, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in examples 1-4; the energy efficiency was 81.46%, lower than that of the Daramic composite ion conducting membranes prepared in examples 1-4 but higher than that of the Daramic membrane substrate assembled zinc-bromine flow cell. Illustrating that the performance of the Daramic composite ion conductive membranes prepared in this comparative example in zinc-bromine flow batteries was inferior to that of the Daramic composite ion conductive membranes prepared in examples 1-4 in zinc-bromine flow batteries (table 5).
Example 9
The preparation of a polymer solution and the preparation of a Daramic composite ion-conducting membrane were carried out as described in example 1 above, except that hexamethylenediammonium bromide was used as the complexing agent.
The performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion conductive membranes is shown in table 3, which is higher than that of the Daramic composite ion conductive membranes prepared in examples 1-4. Bromine ion (Br) of the prepared Daramic composite ion-conducting membrane-) The transmittances, as shown in table 3, were slightly lower than the bromine ion transmittances of the Daramic composite ion conductive membranes and the Daramic membrane substrates prepared in examples 1-4, indicating that the prepared Daramic composite ion conductive membranes had better performance than the Daramic composite ion conductive membranes prepared in examples 1-4Ion selectivity of composite ion conducting membranes and Daramic membrane substrates.
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L zinc bromide, 3mol/L potassium chloride and 0.8mol/L N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared by the comparative example is 94.35 percent, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion-conducting membrane prepared by the examples 1-4 but higher than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the voltage efficiency is 84.72 percent and is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conduction membrane prepared in examples 1-4 and the Daramic membrane substrate; the energy efficiency was 79.93%, lower than that of the Daramic composite ion conducting membranes prepared in examples 1-4 but higher than that of the Daramic membrane substrate assembled zinc-bromine flow cell. It is shown that the performance of the Daramic composite ion conductive membranes prepared in this comparative example in zinc-bromine flow batteries is inferior to that of the Daramic composite ion conductive membranes prepared in examples 1-4, but superior to that of the Daramic membrane substrate in zinc-bromine flow batteries (table 5).
Example 10
The polymer solution was prepared according to the method described in example 1 above to prepare a Daramic composite ion conductive membrane, the process and conditions were the same as those of example 1, except that hexamethylenediammonium bromide was used as the complexing agent, the mass ratio of hexamethylenediammonium bromide to MEPBr to Nafion was 4: 1.
the performance of the prepared Daramic composite ion conducting membrane is tested and compared with the performance of the Daramic composite ion conducting membrane prepared in the examples 1-4 and the performance of the Daramic membrane substrate, and the invention takes a zinc-bromine flow battery as an example. The sheet resistance of the prepared Daramic composite ion-conducting membranes is shown in table 3, which is higher than that of the Daramic composite ion-conducting membranes prepared in examples 1-4. Bromine of the prepared Daramic composite ion-conducting membraneIon (Br)-) The permeability is shown in table 3, which is lower than the bromide ion permeability of the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4, indicating that the prepared Daramic composite ion conducting membranes have superior ion selectivity to the Daramic composite ion conducting membranes and the Daramic membrane substrates prepared in examples 1-4.
The Daramic composite ion conduction membrane prepared by the comparative example is used for assembling the zinc-bromine flow battery, wherein the catalytic layer is activated carbon felt, the bipolar plate is a graphite plate, and the effective area of the membrane is 36cm2Current density of 40mA cm-2The electrolyte comprises the following components: 2mol/L of zinc bromide, 3mol/L of potassium chloride and 0.8mol/L of N, N-methylethylpyrrolidine bromide (complexing agent). A constant-capacitance charging mode is adopted in the charging process, and the charging time is 1 h; the discharge process adopts a voltage cut-off mode, and the cut-off voltage is 0.8V. The coulombic efficiency of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the comparative example is 94.00 percent, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane prepared by the example 1 but higher than that of the zinc-bromine flow battery assembled by the Daramic membrane substrate; the voltage efficiency was 85.04%, which is lower than that of the zinc-bromine flow battery assembled by the Daramic composite ion conducting membrane and the Daramic membrane substrate prepared in examples 1-4; the energy efficiency was 79.94%, which is lower than the Daramic composite ion conducting membranes prepared in examples 1-4 but higher than the energy efficiency of the Daramic membrane substrate assembled zinc-bromine flow cell. Illustrating that the performance of the Daramic composite ion conductive membranes prepared in this comparative example in zinc-bromine flow batteries was inferior to that of the Daramic composite ion conductive membranes prepared in examples 1-4 but superior to that of the Daramic membrane substrate in zinc-bromine flow batteries (table 5).
TABLE 1 comparison of the performance of Daramic composite ion conducting membranes and Daramic base membranes when a bromine-blocking and bromine-fixing functional layer was coated on one side of the Daramic membrane substrate
Figure BDA0002828758640000151
Table 2 comparison of performance of Daramic composite ion conducting membrane and Daramic membrane substrate assembled zinc-bromine flow cell
Figure BDA0002828758640000152
Figure BDA0002828758640000161
TABLE 3 comparison of the Performance of Daramic composite ion-conducting membranes with different complexing agents
Figure BDA0002828758640000162
Table 4 comparison of performance of zinc-bromine flow batteries assembled with Daramic composite ion conducting membranes using different complexing agents
Figure BDA0002828758640000163
Figure BDA0002828758640000171
TABLE 5 summary of the conclusions of the examples and comparative examples
Figure BDA0002828758640000172

Claims (10)

1. A Daramic composite ion conduction membrane with the functions of bromine blocking and fixing is characterized in that: the composite ion conduction membrane comprises a Daramic membrane substrate and a bromine blocking and fixing functional layer compounded on the surface of one side of the Daramic membrane substrate; the bromine-blocking and bromine-fixing functional layer is composed of a bromine complexing agent and organic polymer resin;
the bromine complexing agent is MEPBr or quaternary ammonium salt containing two or more N;
the thickness of the functional layer is less than 300 μm.
2. An ion-conducting membrane according to claim 1, wherein:
the organic polymer resin is Nafion; the quaternary ammonium salt is one or a mixture of hexamethonium bromide and hexadimethrine bromide.
3. An ion-conducting membrane according to claim 1, wherein:
the functional layer has a porous structure; the aperture of the functional layer is 1 nm-70 nm, and the porosity is 10% -50%;
the thickness of the functional layer is 50-250 μm;
the mass ratio of the bromine complexing agent to the organic polymer resin is 1-10: 1.
4. an ion-conducting membrane according to claim 3, wherein:
the thickness of the functional layer is 80-200 μm;
the mass ratio of the bromine complexing agent to the organic polymer resin is 2-8: 1.
5. a process for preparing an ion-conducting membrane according to any one of claims 1 to 4, wherein:
the Daramic composite ion-conducting membrane is prepared by the following steps:
(1) dissolving the bromine complexing agent and the organic polymer resin in an organic solvent, and stirring for 1-24 hours at the temperature of 10-40 ℃ to prepare a blending solution;
(2) dripping the blending solution prepared in the step (1) on a Daramic membrane substrate, and blade-coating a layer of blending solution on one side surface of the Daramic membrane substrate;
or spraying the blended solution prepared in the step (1) on one side surface of a Daramic membrane substrate;
(3) and (3) drying the membrane obtained in the step (2) at the temperature of 45-55 ℃ for more than 3h to obtain the Daramic composite ion conduction membrane.
6. A process for preparing an ion-conducting membrane according to claim 5, wherein:
the organic solvent is one or more than two of isopropanol, DMAC, NMP and DMF.
7. A process for preparing an ion-conducting membrane according to claim 7, wherein:
in the step (1), the mass concentration of the organic polymer resin is 1-25%;
in the step (3), the drying time is 4-24 h.
8. A process for preparing an ion-conducting membrane according to claim 7, wherein:
the mass concentration of the organic polymer resin is 3-15%.
9. Use of an ion-conducting membrane according to any one of claims 1 to 3 in a bromine-based flow battery.
10. Use of an ion-conducting membrane according to claim 9, wherein:
the bromine-based flow battery comprises a zinc/bromine flow battery, a hydrogen/bromine flow battery, a lithium/bromine flow battery, a quinone/bromine flow battery, a magnesium/bromine flow battery, a sodium polysulfide/bromine flow battery, or a vanadium/bromine flow battery.
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