CN111106372A - Application of cation membrane with rigid chain segment in alkaline zinc-based flow battery - Google Patents
Application of cation membrane with rigid chain segment in alkaline zinc-based flow battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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Abstract
The invention relates to application of a cation exchange membrane with a rigid chain segment structure in an alkaline zinc-based flow battery, in particular to application of a sulfonated or carboxylated aromatic ion exchange membrane in the alkaline zinc-based flow battery. The benzene ring structure of the main chain rigid chain segment endows the membrane with good mechanical stability, and the side chain sulfonic acid group or carboxylic acid group endows the membrane with higher ionic conductivity; sulfonic or carboxylic acid cation exchange groups replace traditional quaternary ammonium anion exchange groups; in addition, sulfonic acid or carboxylic acid cation exchange groups have negative charges and have charge repulsion on active substances (negative electrode: Zn (OH)42-) in the alkaline zinc-based flow battery, so that the ion selectivity of the membrane on the active substances is greatly improved; the method can effectively inhibit the deposition of zinc dendrites along the membrane direction, and avoid the damage of the zinc dendrites to the membrane, thereby greatly prolonging the cycle life of the alkaline zinc-based flow battery.
Description
Technical Field
The invention relates to an application of a cation exchange membrane with a rigid chain segment structure in the field of flow batteries, in particular to an application of a sulfonated or carboxylated aromatic ion exchange membrane in the field of alkaline zinc-based flow batteries.
Background
Currently, a "distributed energy source + energy storage" system is in a rapid development stage, and revolutionary changes are brought to an energy system. The flow battery technology has the advantages of safety, reliability, high cost performance in the life cycle, environmental friendliness and the like, and is a mature electrochemical energy storage technology at present. The all-vanadium redox flow battery is one of the most developed and mature redox flow battery technologies at present, is also one of the energy storage technologies (100MW grade all-vanadium redox flow battery energy storage power stations) which are mainly supported by the country, and is in the industrial demonstration stage at present. However, the battery has the problems of low energy density and high cost, and the industrial application of the battery is limited. Therefore, the electrochemical energy storage battery with excellent development performance and low cost is very important for popularization and application of renewable energy sources.
The energy storage technology of the alkaline zinc-based flow battery has the characteristics of low cost, high safety, high open circuit voltage, environmental friendliness and the like, and is very suitable for application in the fields of distributed energy sources and household energy storage. The alkaline zinc-based flow battery adopts zinc with abundant resources as a battery negative active substance, has low cost, has negative potential of a zinc electrode pair in an alkaline environment, and can endow the battery with higher open-circuit voltage after being paired with other positive electrode pairs, for example, the open-circuit voltage of the alkaline zinc-nickel single flow battery can reach more than 1.7V, and the open-circuit voltage of the alkaline zinc-iron flow battery can reach more than 1.74V.
As a key material of the alkaline zinc-based flow battery, the physical and chemical properties and the cost of an ion exchange membrane directly influence the performance and the cost of a battery system. A commercial perfluorosulfonic acid ion exchange membrane (trade name:
) The production process is complex and expensive (about $ 600--2The coulomb efficiency of the battery is only 76%) under the condition of working current density, and the performance of the flow battery is seriously influenced. The traditional anion exchange membrane has been proved to have poor alkali resistance stability in an alkaline fuel cell, so that the traditional anion exchange membrane cannot meet the requirement of the traditional anion exchange membrane on an alkaline zinc baseThe need for long run times in flow batteries. In addition, the problem of dendritic crystal growth and zinc accumulation is accompanied in the charge-discharge cycle process of the alkaline zinc-based flow battery, and the continuously grown dendritic crystal is easy to damage the diaphragm. The formation of the negative dendrite puts higher requirements on the ion exchange membrane for the alkaline zinc-based flow battery. Therefore, research and development have alkali-resistant stability concurrently, mechanical strength is high, ion exchange membrane with low costs, utilize the ion exchange membrane of development simultaneously to solve battery charge-discharge in-process zinc dendrite and zinc accumulation problem, avoid dendrite to cause the destruction to the diaphragm, improve battery cycle life, have very important meaning to the practicality and the industrialization that realize alkaline zinc-based redox flow battery.
Disclosure of Invention
The invention aims to provide a cation exchange membrane with a rigid chain segment structure for an alkaline zinc-based flow battery, the membrane is composed of a benzene ring with a rigid chain segment in a main chain and a structure with a sulfonic acid group or a carboxylic acid group in a side chain, the alkaline zinc-based flow battery has excellent alkali resistance stability, excellent ion selectivity and ion conductivity, and the sulfonic acid group or the carboxylic acid group with negative charges in the side chain can remarkably inhibit the damage of dendritic crystals to the ion exchange membrane, thereby remarkably improving the charge and discharge performance and the cycle life of the alkaline zinc-based flow battery and meeting the strict requirements of the high-performance alkaline zinc-based flow battery on the ion exchange membrane.
The cation exchange membrane with the rigid chain segment structure is applied to the alkaline zinc-based flow battery, the structural formula of the cation exchange membrane with the rigid chain segment structure is shown as follows,
R1is-SO3 -or-COO-Any one of
R2Is a group which can react with R1The same may be-H
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
（R4is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(y is 0. ltoreq. y.ltoreq.3)
Any one of
The structural units with ion exchange groups and the structural units without ion exchange groups are arranged in disorder or order, m and n represent the degree of polymerization, and the range of m + n is 8-10000; the sulfonation or carboxylation degree of the sulfonation cation exchange membrane with the rigid chain segment structure is 0.4-1.8, preferably 0.5-0.95;
the preparation method of the sulfonated cation exchange membrane with the rigid chain segment structure can be prepared by directly sulfonating resin with the rigid chain segment structure by concentrated sulfuric acid (98 wt%) or fuming sulfuric acid; or by polymerizing a monomer having a hard segment structure containing a sulfonic acid group with a monomer having a hard segment structure containing no sulfonic acid group;
the preparation method of the carboxylic acid cation exchange membrane with the rigid chain segment structure can be obtained only by polymerizing the monomer with the rigid chain segment structure containing carboxylic acid groups and the monomer with the rigid chain segment structure not containing carboxylic acid groups;
wherein, the structural formula of the resin with the rigid chain segment structure is as follows:
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3(0. ltoreq. b. ltoreq.3)
Any one of
The preparation method of the cation exchange membrane with the rigid chain segment structure comprises the following specific synthetic reactions when the monomer with the rigid chain segment structure containing carboxylic acid groups (sulfonic acid groups) and the monomer with the rigid chain segment structure not containing carboxylic acid groups (sulfonic acid groups) are polymerized:
when R1 is-SO 3-, the preparation process of the cation exchange membrane material is that the resin with the rigid chain segment structure is directly sulfonated by 98 wt% concentrated sulfuric acid or fuming sulfuric acid; wherein, the structural formula of the resin with the rigid chain segment structure is as follows:
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3(0. ltoreq. b. ltoreq.3)
Any one of the above.
When R1 is-SO 3-, the cation exchange membrane material can be obtained by polymerizing a monomer with a rigid chain segment structure and containing a sulfonic acid group with a monomer with a rigid chain segment structure and containing no sulfonic acid group; the structural formula of the monomer with the rigid chain segment structure containing the sulfonic acid group and the monomer with the rigid chain segment structure containing no sulfonic acid group is as follows:
R1is-SO3 -
R2Is a group which can react with R1The same may be-H
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3(0. ltoreq. b. ltoreq.3)
Any one of the above.
When R1 is-COO-, the cation exchange membrane material is prepared by polymerizing a monomer with a rigid chain segment structure containing carboxylic acid groups and a monomer with a rigid chain segment structure not containing carboxylic acid groups; the polymerization reaction of the monomer having a rigid segment structure containing a carboxylic acid group and the monomer having a rigid segment structure containing no carboxylic acid group is as follows:
R1is-COO-
R2Is a group which can react with R1The same may be-H
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3(0. ltoreq. b. ltoreq.3)
Any one of the above.
The cation exchange membrane with the rigid chain segment structure is prepared by adopting the following steps:
(1) dissolving one or more than one cation exchange resin with a rigid chain segment structure in one or more than one organic solvent of dimethyl sulfoxide (DMSO), N '-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF) and the like, and fully stirring for 5-100 hours at the temperature of 5-80 ℃ to prepare a blending solution; wherein the concentration of the cation exchange resin is 1-60 wt%;
(2) pouring the blending solution prepared in the step (1) on a non-woven fabric substrate or directly on a glass plate or a stainless steel plate, volatilizing the solvent for 0-120 s, and then evaporating the solvent to dryness at the temperature of 20-200 ℃ to form a film.
(3) The prepared cation exchange membrane with the rigid chain segment structure can be firstly applied to the alkaline zinc-based flow battery, and can be firstly added with water or 0.0001mol L-1-8molL-1Soaking in the alkali solution for 0.1-48 h; can also be directly used for the alkaline zinc-based flow battery;
the alkaline zinc-based flow battery comprises an alkaline zinc-nickel single flow battery, an alkaline zinc-iron single flow battery, an alkaline zinc-air flow battery, an alkaline zinc-manganese flow battery and an alkaline zinc-silver single flow battery.
Advantageous results of the invention
1. The cation exchange membrane with the rigid chain segment structure can be prepared into cation ion exchange resin with controllable sulfonation degree or carboxylation degree by controlling sulfonation or carboxylation conditions, and is easy to realize mass production;
2. the cation exchange membrane with the rigid chain segment structure is applied to the alkaline zinc-based flow battery, and the sulfonic acid or carboxylic acid group with negative charge can repel negative active substances (Zn (OH) through electrostatic repulsion4 2-) The ion selectivity of the battery is greatly improved through the diaphragm;
3. the cation exchange membrane with the rigid chain segment structure prepared by the invention can conduct K in an alkaline system through an ion exchange transfer mechanism+Or Na+Isocationic, while OH can also be transferred by swelling of the membrane-Ion, greatly improving the ion transmission of the membraneConductivity, thereby increasing the voltage efficiency of the cell;
4. based on negatively charged sulphonic or carboxylic acid groups on Zn (OH)4 2-Rejection of (3), Zn (OH) during charging of the cell4 2-The zinc dendrite can not be deposited along the direction of the diaphragm, so that the damage of the zinc dendrite to the diaphragm is effectively inhibited, and the cycle stability of the battery is greatly improved;
5. negatively charged sulfonic or carboxylic acid groups force Zn (OH)4 2-In the charging process, the zinc/carbon felt composite electrode is mainly deposited along the direction of the carbon felt electrode, the deposited metal zinc and the carbon felt electrode form a metal zinc/carbon felt composite electrode, and the metal zinc and the carbon felt electrode form a good contact network, so that the metal zinc can be completely utilized in the discharging process of the battery, the problem of accumulation of zinc at the negative electrode can be effectively solved, and the service life of the battery is greatly prolonged;
6. the cation exchange membrane has excellent durable stability in alkaline solution, so the invention widens the variety and the application range of membrane materials in alkaline environment;
7. the invention can realize the controllability of the performance of the alkaline zinc-based flow battery.
Drawings
FIG. 1 shows the flow of alkaline zinc-iron solution assembled by perfluorinated sulfonic acid ion exchange membranes with different thicknesses at 80mA cm-2Performance testing under the condition of working current density;
FIG. 2 shows the structural formula of sulfonated polyether ether ketone resin;
FIG. 3 is a test of permeation of sulfonated polyether ether ketone cation exchange membranes with different degrees of sulfonation to hydroxide ions;
FIG. 4 shows that the alkali zinc-iron liquid flow assembled by sulfonated polyether ether ketone cation exchange membranes with different sulfonation degrees is 80mAcm-2Performance testing under the condition of working current density;
fig. 5 represents electrochemical performance of alkaline zinc-iron flow battery assembled with SK2 film. (a) Testing the rate performance; (b) open Circuit Voltage (OCV) testing of the battery at different states of charge (SOC); (c) testing a polarization curve; (d) cycle performance test
FIG. 6 SK2 film was placed at 5mol L-1NaO (r) ofTreating in H solution at 60 deg.c for 22 days, and assembling the alkaline zinc-iron flow cell in 80mA cm-2Testing the cycling stability under the working current density condition;
fig. 7 shows cell performance of alkaline zinc-iron flow cells assembled with SK membranes in different modes of operation. (a) Alkaline zinc-iron flow battery assembled by SK film at 20mA cm-2Charging for 8h and 160mA cm under the condition of working current density-2The discharge charge-discharge curve under the working current density condition of (1); (b) alkaline zinc-iron flow battery assembled by SK film at 20mA cm-2Charging for 8h and 80mA cm under the condition of working current density-2The discharge charge-discharge curve under the working current density condition of (1); (c) alkaline zinc-iron flow battery assembled by SK film at 20mA cm-2Charging for 8h under the working current density condition of (1), and battery performance during discharging under different current densities; (d) discharge capacity and discharge energy maps corresponding to the map c;
FIG. 8 alkaline zinc-iron flow battery assembled by SK film at 40mA cm-2Charging for 4h at 80mA cm under the condition of working current density-2Part of charge-discharge curve chart of (a) when discharging under the working current density condition of (a); (b) a battery performance map;
FIG. 9 Synthesis of carboxylated polyetheretherketone;
FIG. 10 shows the structural formula of sulfonated polyether ether ketone containing side chain.
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
Comparative examples of the present invention are perfluorosulfonic acid ion exchange membranes having flexible segments of different thicknesses. Adopting perfluorinated sulfonic acid ion exchange membranes (Nafion 115, Nafion 212 and Nafion 211) with different thicknesses to assemble the alkaline zinc-iron flow battery, wherein 60mL of 0.6mol L of positive electrolyte is adopted-1K of4Fe(CN)6+5mol L-1The negative electrode electrolyte adopts 60mL0.3mol L-1Zn(OH)4 2-+5mol L-1NaOH at 80mA cm-2Under the condition of working current density of (2), subjecting it to electrochemical treatmentThe chemical performance test results are shown in FIG. 1. It can be seen that the perfluorosulfonic acid ion exchange membrane has excellent ion selectivity in the alkaline zinc-iron flow battery, the coulombic efficiency of which is close to 100%, while the energy efficiency of the battery is lower, close to 80%. This is mainly because the interaction between the perfluororesin backbone of the perfluorosulfonic acid ion-exchange membrane and the side chain sulfonic acid group is strong, resulting in the side chain sulfonic acid group and the cation (K) in the solution+Or Na+) Bonding energy between them is weak, K+Or Na+The perfluorinated sulfonic acid ion exchange membrane has lower ionic conductivity in an alkaline system due to higher resistance of the membrane in permeation through an ion exchange transfer mechanism, so that the voltage efficiency of the battery is lower.
Example 1
The sulfonated polyether ether ketone resin with different sulfonation degrees (SK 1, SK2 and SK3 for short, the structural formula is shown in figure 2, and the sulfonation degrees are 0.70, 0.81 and 0.91 respectively) is prepared by adopting concentrated sulfuric acid to directly sulfonate polyether ether ketone and controlling the sulfonation reaction time. DMAC (dimethylacetamide) is used as a solvent, the resin is prepared into a film, and a hydroxide ion permeation test is carried out on the film, so that the swelling effect of the film is increased and the hydroxide ion permeation rate is increased along with the increase of the sulfonation degree as can be seen from figure 3. And assembling the prepared sulfonated polyether ether ketone with different sulfonation degrees into an alkaline zinc-iron flow battery, and testing, wherein the testing conditions are consistent with those of the alkaline zinc-iron flow battery assembled by perfluorinated sulfonic acid ion exchange membranes with different thicknesses. The test results are shown in fig. 4. As can be seen from FIG. 4, the alkaline zinc-iron flow battery assembled by sulfonated polyether ether ketone with different sulfonation degrees is 80mA cm-2The coulombic efficiency of the battery is close to 100% under the condition of working current density, and the voltage efficiency and the energy efficiency are close to or even exceed 90%, which shows that the cation exchange membrane with the rigid chain segment structure has excellent battery performance in the alkaline zinc-iron flow battery. In order to further prove the application prospect of the cation exchange membrane with the rigid chain segment structure in the alkaline zinc-iron flow battery, an SK2 membrane is selected and the other electrochemical properties of the cation exchange membrane in the alkaline zinc-iron flow battery are characterized (electrolyte composition: positive electrode: 0.8mol L)-1Na4Fe(CN)6+3mol L-1KOH; negative electrode: 0.4mol L-1Zn(OH)4 2-+3mol L-1NaOH)。
As can be seen from FIG. 5a, the alkaline zinc-iron flow battery assembled with the SK2 film has excellent rate performance even at 200mA cm-2Under the condition of high working current density, the energy efficiency of the battery can still be kept above 80%; fig. 5b shows the Open Circuit Voltage (OCV) of the alkaline zinc-iron flow battery assembled by using SK2 film under different states of charge (SOC), and the higher OCV of the battery indicates the smaller internal resistance of the battery under the same SOC, and it can be seen that the OCV of the battery has a gradually increasing trend along with the increase of the SOC. Fig. 5c is a polarization curve test of alkaline zinc-iron flow batteries assembled with SK2 films at different states of charge (SOC) cells. From the voltage curve, the concentration polarization and the activation polarization of the battery can be basically ignored, and the battery is mainly controlled by ohmic polarization; as can be seen from the power density curve, even at 20% SOC, the peak power density of the battery can still reach 800mW cm-2The flow rate is far higher than that of the water-based new system flow battery reported at present. FIG. 5d shows an alkaline zinc-iron flow cell assembled with SK2 membrane at 200mA cm-2The cycle performance test under the operating current density condition of (1) shows that even at 200mA cm-2Under the condition of high working current density, the battery can still continuously and stably run for more than 200 cycles, the energy efficiency of the battery is always kept above 80%, and excellent cycle stability is shown. In the circulation process, the charge-discharge curve of the battery is kept stable, the discharge capacity and the discharge energy are not obviously attenuated, and the prepared cation exchange membrane with the rigid chain segment structure is further proved to have excellent performance in the alkaline zinc-iron flow battery, and is expected to realize large-scale application in the alkaline zinc-iron flow battery.
In order to confirm the alkali resistance stability of the prepared cation exchange membrane with the rigid chain segment structure, the SK2 membrane is placed at 5mol L-1The electrochemical performance of the solution was characterized after 22 days of treatment at 60 ℃. The test results are shown in fig. 6. As can be seen from the figure, the SK2 film was measured at 5mol L-1After the NaOH solution is treated for 22 days at 60 ℃, the alkaline zinc-iron flow battery assembled by the NaOH solution can still keep excellent circulation stability, which shows that the cation exchange membrane with the rigid chain segment structure has excellent alkali-resistant stability.
For conventional flow batteries, such as all-vanadium flow batteries, the capacity of the battery depends on the volume of electrolyte used. While for zinc-based flow batteries, the surface capacity of the battery depends on the electrodes used to assemble the battery. The application of zinc-based batteries is often limited to zinc cathodes. Generally, higher surface capacity leads to more severe problems with zinc dendrites and zinc accumulation, which in turn leads to reduced cell performance. For the cation exchange membrane with the rigid chain segment structure, the zinc acid radical ions are prevented from depositing along the direction of the membrane side and only can deposit along the opposite direction of the membrane, namely along the direction of the inner part of the electrode in the charging process of the battery due to the repulsion action of negative charges in the membrane on zinc acid radicals in an alkaline environment. While the porous carbon felt electrode can accommodate more metallic zinc. Therefore, alkaline zinc-iron flow battery assembled with SK film, even at 20mA cm-2The charging curve of the battery is still kept smooth when the battery is charged for 8 hours under the working current density condition (figure 7), the voltage does not rise sharply at the end of charging, and the surface capacity of the battery reaches 160mAh cm-2The battery can be 160mA cm-2The battery is continuously and stably discharged for 1 hour under the condition of working current density, the coulomb efficiency of the battery is kept above 99%, and the voltage efficiency is kept above 83%; at 80mA cm-2The battery is continuously and stably discharged for 2 hours under the condition of working current density, the coulomb efficiency of the battery is close to 100 percent, and the voltage efficiency is always kept at about 90 percent.
Further increasing the charging current density of the battery to 40mA cm-2(FIG. 8), the battery was charged continuously and stably for 4 hours, and the voltage curve at the end of charging was smooth at 80mA cm-2The battery is continuously and stably discharged for 2 hours under the working current density condition, the coulomb efficiency of the battery is close to 100 percent, the voltage efficiency is kept about 86 percent, and the excellent battery performance is shown.
Example 2
Adopts concentrated sulfuric acid to directly sulfonate polyether-ether-ketone, and adopts the control of sulfonation reactionPreparing sulfonated polyether ether ketone resin (SK 4, structural formula shown in figure 2, and degree of sulfonation of 0.34) with different degrees of sulfonation in response to time, dissolving the resin in NMP to obtain a casting solution with a solid content of 20 wt.% by taking NMP as a solvent, preparing a membrane, and characterizing the electrochemical performance of the membrane in an alkaline zinc-iron flow battery at 80mA cm-2The coulombic efficiency of the cell was close to 100% under the operating current density conditions of (1), but the voltage efficiency of the cell was only 61% due to the low sulfonation degree of the membrane.
Example 3
Adopting a monomer method to synthesize carboxylated polyether ether ketone (figure 9, the carboxylation degree is 0.85), taking DMAC as a solvent, dissolving the resin in the DMAC to obtain a casting solution with the solid content of 20 wt.%, preparing a film, and characterizing the electrochemical performance of the film in the alkaline zinc-iron flow battery, wherein the electrochemical performance is 80mA cm-2Under the condition of working current density, the coulombic efficiency of the battery is close to 100 percent, the voltage efficiency is 87 percent, the battery continuously and stably runs for more than 300 cycles, the performance is not obviously attenuated, and the excellent battery performance is shown.
Example 4
The carboxylated polyether-ether-ketone is synthesized by a monomer method (figure 9, the carboxylation degree is 0.32), and the electrochemical performance of the prepared film in the alkaline zinc-iron flow battery is characterized at 80mA cm-2The coulombic efficiency of the battery is close to 100% under the condition of working current density, and the voltage efficiency of the battery is only 57% due to the small number of carboxylic acid groups in the film and the large film group.
Example 5
Dissolving polyether-ether-ketone containing side chains with a certain mass (10g) in concentrated sulfuric acid with a certain volume (100mL) by adopting a direct sulfonation method, sulfonating for a certain time (11h, the sulfonation degree is 0.91) at a certain temperature (70 ℃) (figure 10), and characterizing the electrochemical performance of the prepared film in an alkaline zinc-iron flow battery at 160mAcm-2Under the condition of working current density, the coulombic efficiency of the battery is close to 100 percent, the voltage efficiency is about 81 percent, the battery continuously and stably runs for 230 cycles without obvious attenuation of performance, and the excellent battery performance is shown. By sulfonation with conventional catalystsIn contrast, the sulfonated polyether ether ketone (SK) with side chains has poorer hydrophilicity than that of the traditional SK membrane due to the existence of the side chain benzotrifluoride, because the sulfonated polyether ether ketone with side chains is used at 160mA cm-2Under the condition of working current density, the voltage efficiency of the battery is only about 81 percent, which is lower than the battery performance (at 160mA cm) of the battery assembled by the traditional sulfonated polyether ether ketone membrane under the same condition-2The voltage efficiency of the cell is about 85%) at the operating current density of (d).
Example 6
Dissolving polyether-ether-ketone containing side chains with a certain mass (10g) in concentrated sulfuric acid with a certain volume (100mL) by adopting a direct sulfonation method, sulfonating for a certain time (5h, the sulfonation degree is 0.62) at a certain temperature (70 ℃) (figure 10), and characterizing the electrochemical performance of the prepared film in an alkaline zinc-iron flow battery after the film is prepared, wherein the electrochemical performance is 80mA cm/cm-2The coulombic efficiency of the cell is close to 100% and the voltage efficiency is only 74% under the operating current density condition of (1).
Example 7
The SK2 film is applied to an alkaline zinc air single flow battery, and NiCo is adopted2O4The alkaline zinc-air single flow battery assembled by using/G as oxygen reduction and oxygen evolution (ORR, OER) catalyst is 10mA cm-2Can continuously and stably operate for more than 60 hours under the condition of working current density, and the performance is kept stable.
Example 8
The SK2 film is applied to an alkaline zinc-iron single flow battery, the negative electrode is fixed in the electrode, the positive electrode adopts a flow mode, and the assembled alkaline zinc-iron single flow battery is 20mA cm-2The battery can continuously and stably run for more than 80 cycles (charging time: 1h) under the condition of working current density, the coulombic efficiency of the battery is kept above 96%, the voltage efficiency is kept above 87%, and the performance is kept stable.
Claims (7)
1. Use of a cationic membrane having a rigid segment in an alkaline zinc-based flow battery, characterized in that: the structural formula of the cation exchange membrane material with the rigid chain segment structure is one or more than two of the following formulas,
R1is-SO3 -or-COO-Any one of
R2Is a group which can react with R1The same may be-H
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3Any one of (0. ltoreq. b. ltoreq.3)
Wherein the structural units with ion exchange groups (the parenthesis units corresponding to the subscript n) and the structural units without ion exchange groups (the parenthesis units corresponding to the subscript m) are arranged alternately or in blocks, m and n represent the degree of polymerization, and m + n is in the range of 8-10000.
2. Use according to claim 1, characterized in that: the degree of sulfonation or carboxylation is 0.4 to 1.8, preferably 0.5 to 0.95.
3. Use according to claim 1, characterized in that: when R1 is-SO 3-, the preparation process of the cation exchange membrane material is that the resin with the rigid chain segment structure is directly sulfonated by 98 wt% concentrated sulfuric acid or fuming sulfuric acid; wherein, the structural formula of the resin with the rigid chain segment structure is as follows:
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3Any one of (0. ltoreq. b. ltoreq.3).
4. Use according to claim 1, characterized in that: when R1 is-SO 3-, the cation exchange membrane material can be obtained by polymerizing a monomer with a rigid chain segment structure and containing a sulfonic acid group with a monomer with a rigid chain segment structure and containing no sulfonic acid group; the structural formula of the monomer with the rigid chain segment structure containing the sulfonic acid group and the monomer with the rigid chain segment structure containing no sulfonic acid group is as follows:
R1is-SO3 -
R2Is a group which can react with R1The same may be-H
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3Any one of (0. ltoreq. b. ltoreq.3).
5. Use according to claim 1, characterized in that: when R1 is-COO-, the cation exchange membrane material is prepared by polymerizing a monomer with a rigid chain segment structure containing carboxylic acid groups and a monomer with a rigid chain segment structure not containing carboxylic acid groups; the polymerization reaction of the monomer having a rigid segment structure containing a carboxylic acid group and the monomer having a rigid segment structure containing no carboxylic acid group is as follows:
R1is-COO-
R2Is a group which can react with R1The same may be-H
R3is-H or-F or- (CH)2)xCH3(0. ltoreq. x. ltoreq.4) or- (CF)2)yCF3(0. ltoreq. y. ltoreq.3) or
(R4is-H or-F or- (CH)2)aCH3(0. ltoreq. a. ltoreq.4) or- (CF)2)bCF3Any one of (0. ltoreq. b. ltoreq.3).
6. Use according to any one of claims 1 to 5, characterized in that: the cation exchange membrane with the rigid chain segment structure is prepared by adopting the following steps:
(1) dissolving one or more than two cation exchange resin materials with a rigid chain segment structure in one or more than one of organic solvents such as dimethyl sulfoxide (DMSO), N '-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF) and the like, and fully stirring for 5-100 hours at the temperature of 5-80 ℃ to prepare a blending solution; wherein the concentration of the cation exchange resin is 1-60 wt%;
(2) pouring the blending solution prepared in the step (1) on a non-woven fabric substrate or directly on a glass plate or a stainless steel plate, volatilizing the solvent for 0-120 s, and then evaporating the solvent to dryness at the temperature of 20-200 ℃ to form a film.
7. Use according to claim 1, characterized in that: the alkaline zinc-based flow battery is an alkaline zinc-nickel single flow battery, an alkaline zinc-iron single flow battery, an alkaline zinc-air flow battery, an alkaline zinc-manganese flow battery or an alkaline zinc-silver single flow battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114497643A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Flow battery and application thereof |
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