CN113067024A - Alkaline electrolyte membrane and preparation and application thereof - Google Patents

Alkaline electrolyte membrane and preparation and application thereof Download PDF

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CN113067024A
CN113067024A CN201911275022.8A CN201911275022A CN113067024A CN 113067024 A CN113067024 A CN 113067024A CN 201911275022 A CN201911275022 A CN 201911275022A CN 113067024 A CN113067024 A CN 113067024A
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王素力
杨丛荣
孙公权
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses an alkaline electrolyte membrane and preparation and application thereof, wherein the alkaline electrolyte membrane synthesizes ionic liquid with stable chemical property and high conductivity through the structural design and optimization of ionic liquid, and then the stable state of the ionic liquid in the alkaline polymer electrolyte membrane is further improved through the anchoring effect of corresponding MOF materials, so that the ionic liquid-based alkaline electrolyte membrane with good chemical stability, higher conductivity, high temperature resistance and strong binding force is finally obtained. Such alkaline electrolyte membranes are composed of an organic polymer backbone, MOF material and ionic liquid. The invention solves the problem of performance reduction of the alkaline membrane in a high-temperature and low-humidity environment, and can be applied to an alkaline polymer electrolyte membrane fuel cell or a water electrolysis cell which takes the alkaline polymer membrane as a solid electrolyte.

Description

Alkaline electrolyte membrane and preparation and application thereof
Technical Field
The invention belongs to the field of alkaline electrolyte membranes; the invention also relates to a preparation method of the alkaline electrolyte membrane which has good chemical stability and higher conductivity and can be used at high temperature (90 ℃).
Background
The Alkaline Polymer Electrolyte Membrane Fuel Cells (APEMFCs) using alkaline polymer membranes as solid electrolyte have high cathode reaction kinetics rate, and can adopt non-noble metals asThe electrocatalyst can effectively avoid the dendrite short circuit problem caused by salt deposition. Since the first report in 2005, it has become one of the research hotspots in the field of fuel cells. As one of the key materials of alkaline fuel cells, alkaline polymer electrolyte membranes have been widely studied and developed. Through molecular structure design, a continuous and obvious micro-phase separation structure is constructed in APEMs, a channel beneficial to OH-transmission is established, and the conductivity of the membrane is greatly improved and even exceeds that of the current commercial Nafion membrane. On the basis, the electrode structure is continuously optimized, the test conditions are changed, and the performance of the alkaline fuel cell is also improved. But the operating temperature of the alkaline fuel cell is currently<At 80 ℃, the effect of CO2 in air on the cell is large under this condition. The conductivity of the alkaline membrane and the alkaline ionomer inside the electrode is reduced 2/3 once exposed to air, and even larger, which directly leads to the increase of ohmic polarization of the fuel cell and the great degradation of the cell performance. Studies have shown that the adsorption of CO2 is effectively reduced at elevated temperatures (Huang et al, Sci China Chem, 2016, 360->Decomposition occurs at 100 ℃, so increasing the temperature of the alkaline fuel cell to 100 ℃ or above is very beneficial to relieving CO2Impact on battery performance. However, when the operating temperature of the battery is increased, the partial pressure of water is increased, so that the conductivity of the currently common alkaline membrane with cationic functional groups is reduced, and the chemical stability of the alkaline membrane is rapidly reduced, so that the application value is lost.
Disclosure of Invention
Aiming at the problem of performance reduction of an alkaline membrane in a high-temperature and low-humidity environment, the invention aims to design and prepare an alkaline electrolyte with good chemical stability and higher conductivity, so that the alkaline electrolyte can be used at the temperature of more than 90 ℃ or even higher; the physicochemical and electrochemical properties of such alkaline electrolytes were characterized and tested. According to the invention, through the structural design and optimization of the ionic liquid, the ionic liquid with stable chemical property and high conductivity is synthesized, and then the stable state of the ionic liquid in the alkaline polymer electrolyte membrane is further improved through the anchoring effect of the corresponding MOF material, so that the ionic liquid-based alkaline electrolyte membrane with good chemical stability, high conductivity, high temperature resistance and strong binding force is finally obtained.
An alkaline electrolyte membrane consists of an organic polymer, an MOF material and an ionic liquid, wherein the organic polymer is used as a main material of the electrolyte membrane, the MOF material is uniformly dispersed in the main material, and the ionic liquid is coated in a pore structure of the MOF material;
the organic polymer is polystyrene, poly (styrene-ethylene-butylene) block copolymer, polystyrene derivative, poly (styrene-ethylene-butylene) block copolymer derivative, the polystyrene derivative comprises chlorinated alkyl polystyrene and brominated alkyl polystyrene, the poly (styrene-ethylene-butylene) block copolymer derivative comprises one or more than two of chlorinated alkyl poly (styrene-ethylene-butylene) block copolymer and brominated alkyl poly (styrene-ethylene-butylene) block copolymer, or polyvinyl alcohol crosslinked by glutaraldehyde, wherein the mass of the glutaraldehyde crosslinking agent is 0.5-15% of the mass of the polyvinyl alcohol. The organic cation of the ionic liquid is tetramethylammonium, trimethylethylammonium, triethylmethylammonium, tetraethylammonium, 1-methyl-3-methylimidazole, 1-methyl-3-ethylimidazole, 1-methyl-3-propylimidazole, 1-methyl-3-isopropylimidazole, 1-methyl-3-butylimidazole, 1-methyl-3-hexylimidazole, 1-methyl-3-octylimidazole, 1-methyl-3-ethanoldiimidazole, 1, 2-dimethyl-3-methylimidazole, 1, 2-dimethyl-3-ethylimidazole, 1, 2-dimethyl-3-propylimidazole, 1, 2-dimethyl-3-isopropylimidazole, 1, 2-dimethyl-3-butylimidazole, N-dimethylpyrrolidine, N-dimethyl-N-ethylpyrrolidine, N-dimethyl-N-propylpyrrolidine, N-dimethyl-N-butylpyrrolidine, N-dimethylpiperidine, N-methyl-N-ethylpiperidine, N-methyl-N-propylpiperidine and N-methyl-N-butylpiperidine (particularly, trimethylethylammonium, triethylmethylammonium, tetraethylammonium, N-dimethylpyrrolidine, N-dimethyl-N-ethylpyrrolidine, N-dimethyl-N-propylpyrrolidine, N-dimethyl-N-butylpyrrolidine, N-ethylpyrrolidine, N-dimethylpyrrolidine, N-ethylpyrrolidine, N-dimethylpyrrolidine, N-ethylpyrrolidine, N, N, N-dimethylpiperidine, N-methyl-N-ethylpiperidine, N-methyl-N-propylpiperidine, N-methyl-N-butylpiperidine); the ionic liquid is Br for anions-、Cl-、I-、BF4 -、BF6 -、FSI-、TFSI-One or more (especially BF)4 -、FSI-、TFSI-One or two or more kinds of them). MOF is one or more of MIL-101(Cr), MIL-53(Fe), MIL-53(Al), ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12 and UO-66, preferably one or more of MIL-101(Cr), MIL-53(Fe), ZIF-6, ZIF-8, ZIF-10, ZIF-11, ZIF-12 and UO-66. Wherein the organic polymer is the support of the alkaline electrolyte membrane, the function of the organic polymer is to provide the mechanical strength of the alkaline polymer electrolyte membrane, the function of the ionic liquid is to ensure the ionic conductivity of the alkaline polymer electrolyte, and the function of the MOF is to anchor the ionic liquid with the ionic conduction function and ensure OH-Ionic or hydrated OH-To be transmitted. The size of the channels formed in the MOF should be larger than OH-Ionic or hydrated OH-And not much larger than the size of the ionic liquid.
The preparation of the alkaline electrolyte membrane with good chemical stability and higher conductivity and capable of being used at high temperature (>90 ℃) comprises the following steps:
(1) preparation of ionic liquids
The preparation of different ionic liquids involves two main steps: preparation of halogenated ionic liquids and anion conversion of halogenated ionic liquids.
a. The preparation process of the halogenated ionic liquid comprises the following steps: mixing amine, imidazole, methyl pyrrolidine or methyl piperidine with halogenated hydrocarbon, reacting, and returning to room temperature; precipitating with a solvent A, fully washing and drying for later use; the halogenated hydrocarbon is one or more than two of C1-C6 straight chain or branched chain halogenated hydrocarbon or ethanol-based halogenated hydrocarbon;
the halogen in the halogenated hydrocarbon being Br-、Cl-、I-One or more than two of the above-mentioned compounds to obtain Br as anion-、Cl-、I-One or more kinds of amine halide, imidazole, methylpyrrolidine, or methylpiperidine;
b. the process of anion conversion of the halogenated ionic liquid is as follows: dissolving the prepared amine halide, imidazole, methyl pyrrolidine or methyl piperidine in a solvent B or not dissolving the amine halide, imidazole, methyl pyrrolidine or methyl piperidine in the solvent B, adding a solution of an inorganic salt in the solvent B, separating after reaction, fully washing with a solvent C, and drying to obtain ionic liquids with different anions;
the anion in the inorganic salt is BF4 -、BF6 -、FSI-、TFSI-One or more than two of the above; obtaining the anion as BF4 -、BF6 -、FSI-、TFSI-One or two or more ionic liquids;
(2) preparation of alkaline electrolyte membrane based on ionic liquid
Adding ionic liquid into MOF material, adding solvent D, adding a certain amount of organic polymer/D solution, pouring the solution on a glass plate, and volatilizing the solvent to obtain the ionic liquid-based alkaline electrolyte membrane.
The preparation of the ionic liquid-based alkaline electrolyte membrane comprises the following steps:
the volume ratio of the mass of the amine, the imidazole, the methylpyrrolidine or the methylpiperidine to the halogenated hydrocarbon in the preparation process of the halogenated ionic liquid in the step (1) a is 1:1-1:30g/mL (ensuring that the amount of the substance of the halogenated hydrocarbon is excessive compared with the amount of the substance of the amine, the imidazole, the methylpyrrolidine or the methylpiperidine);
in the preparation process of the halogenated ionic liquid in the step (1) a, the reaction temperature is between room temperature and 100 ℃; the reaction time is 10min-24 h;
in the preparation process of the halogenated ionic liquid in the step (1), the solvent A is one or more than two of acetone, ethyl acetate, cyclopentane, n-hexane, n-pentane, diethyl ether, acetonitrile and tetrahydrofuran, preferably one or more than two of acetone, ethyl acetate, diethyl ether and tetrahydrofuran;
in the preparation process of the halogenated ionic liquid in the step (1), the drying condition is forced air drying or vacuum drying; the drying temperature is room temperature-200 ℃; the drying time is 0.5-36 h;
halogenating the Ionic liquid anion in step (1) bIn the ion conversion process, the solvent B is one or more than two of water, acetonitrile, acetone and tetrahydrofuran which are mixed in proportion; the inorganic salt is LiBF4、NaBF4、KBF4、LiBF6、NaBF6、KBF6、MgBF6One or more than two of LiFSI, NaFSI, KFSI, LiTFSI, NaTFSI and KTFSI or Ag2O and HBF4Or HBF6The aqueous solution mixture of (Ag2O to HBF4 or HBF6 molar ratio is 1:2, and the concentration of the aqueous solution of HBF4 or HBF6 is 25-68 wt%);
the solvent C is one or more than two of acetone, ethyl acetate, cyclopentane, n-hexane, n-pentane, diethyl ether, acetonitrile, tetrahydrofuran and water;
in the step (1) B, the volume ratio of the mass of the halogenated ionic liquid to the solvent B in the anionic conversion process of the halogenated ionic liquid is 1:0-1:15 g/mL; the volume ratio of the mass of the inorganic salt to the solvent B is 1:10-1:100g/mL (preferably 1:15-1:30 g/mL); the mass ratio of the halogenated ionic liquid to the inorganic salt is 1:1-1:250 (preferably 1:2-1:150, particularly 1:5-1: 50);
in the step (1) B, in the process of converting the halogenated ionic liquid anions, the treatment condition is that the mixture is subjected to condensation reflux stirring at room temperature to 80 ℃, and is repeatedly treated for more than 2 times, and along with the increase of the treatment times, the mass fraction of inorganic salt in the solvent B is increased, otherwise, the ion replacement is incomplete, a target product cannot be obtained, the conductivity of the ionic liquid is reduced, or the stability of the ionic liquid under the high-temperature alkaline condition is damaged; the treatment time is >24 h; the separation method comprises filtration or/and suction filtration or/and liquid separation;
in the step (1) b, the drying condition in the process of converting the halogenated ionic liquid anions is rotary evaporation at 40-180 ℃, air blast or drying at 40-150 ℃ under vacuum; the drying time is 0.5-48 h;
preparing an ionic liquid-based alkaline electrolyte membrane, wherein the solvent D is deionized water, tetrahydrofuran, xylene, toluene, dichloromethane, chloroform, 1,2, 2-tetrachloroethane, carbon tetrachloride, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; wherein tetrahydrofuran, xylene, toluene, dichloromethane, chloroform, 1,2, 2-tetrachloroethane and carbon tetrachloride can be mixed, and one or more than two can be used as solvent; n, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone can also be mixed, and one or more than two can be used as a solvent;
the mass ratio of the ionic liquid to the MOF material is 50:1-2:1, preferably 30:1-5:1 based on the preparation of the ionic liquid alkaline electrolyte membrane; the volume ratio of the mass of the MOF material to the solvent D is 1:100-1:1g/mL, and the uniform dispersion of the MOF and the good dispersibility of the MOF in the organic polymer material can be realized in the concentration range;
the mass ratio of the mass of the MOF material to the organic polymer framework prepared on the basis of the ionic liquid alkaline electrolyte membrane in the step (2) is 1:1-1:20, preferably 1:3-1: 10;
step (2) based on the preparation of the ionic liquid alkaline electrolyte membrane, the time point of adding the solvent D after mixing the ionic liquid and the MOF material is that the ionic liquid and the MOF material are semi-transparent slurry after uniform slurry, the ionic liquid can be ensured to be fully placed in the pore structure of the MOF material only by mixing for more than 1 hour, if the solvent D is added before the ionic liquid and the MOF material are mixed or the ionic liquid is not fully placed in the pore structure of the MOF material after the ionic liquid and the MOF material are mixed, the solvent D is added, the ionic liquid can not be finally placed in the pore structure of the MOF material, and the ionic conductivity of the prepared alkaline electrolyte membrane is low or the ionic liquid is easy to lose;
the volume ratio of the mass of the organic polymer in the solution of the organic polymer/solvent D prepared based on the ionic liquid alkaline electrolyte membrane to the solvent D is 1:50-1:5g/mL, preferably 1:40-1:8g/mL, and the low concentration range can ensure that the organic polymer and the MOF material have good compatibility, otherwise, the prepared alkaline electrolyte membrane has obvious defects and non-uniform properties;
the method for adding the solution of the polymer organic framework/solvent D into the slurry of the ionic liquid and the MOF material based on the preparation of the ionic liquid alkaline electrolyte membrane in the step (2) is one or two of cell crushing and high-power mechanical stirring, so that no particle sedimentation is ensured, and the alkaline electrolyte membrane is ensured to have good uniformity finally;
the volatile casting film is prepared based on the ionic liquid alkaline electrolyte film in the step (2) by adopting a step-type heating mode, wherein the temperature of the first stage is room temperature to 50 ℃, the temperature of the second stage is 50 to 100 ℃, and the temperature of the third stage is 120-. The adoption of the step-type heating mode can avoid the phenomena that the surface of the film is uneven and the thickness of the film is uneven due to the fact that the solvent is volatilized too fast at the low temperature in the first stage, and the operation of the high-temperature area in the second stage and the third stage can ensure that the solvent is fully removed from the film, so that the difference of the performance of the film due to the existence of the solvent is avoided.
The preparation of the ionic liquid-based alkaline electrolyte membrane has the following advantages:
(1) the invention combines the screening effect of the MOF material and the high ionic conductivity of the ionic liquid, can effectively improve the chemical stability of the ionic liquid, increase the conductivity of the ionic liquid and improve the binding capacity of the ionic liquid in the pore canal of the MOF material by screening the MOF material which is stable under alkaline conditions and has proper pores, designing the molecular structure of the ionic liquid and optimizing the binding conditions of the MOF material and the ionic liquid, thereby improving the OH-Conductivity, chemical stability and other properties under the ion high-temperature anhydrous condition;
(2) chemical degradation of the ionic liquid and leakage of the ionic liquid can be effectively avoided, so that the ionic liquid-based alkaline polymer electrolyte membrane with better performance is obtained;
(3) the prepared ion-based alkaline electrolyte membrane has higher ionic conductivity under the high-temperature anhydrous condition;
(4) the prepared alkaline electrolyte membrane based on the ionic liquid has better chemical stability in a high-temperature alkaline environment.
Drawings
FIG. 1 is a schematic structural diagram of an ionic liquid-based alkaline polymer electrolyte prepared.
Fig. 2 is a nuclear magnetic hydrogen spectrum of the ionic liquid prepared in the example.
Fig. 3 is a graph of the conductivity versus temperature of the ionic liquid based alkaline electrolyte membrane of the example.
Detailed Description
Examples
Preparation of hexyl SEBS bromide
2g of SEBS is dissolved in 60mL of chloroform, 6mL of 6-bromohexanoyl chloride and 1.0g of anhydrous aluminum chloride are dropwise added at the speed of 0.5mL/min under the condition of an ice-water bath (0 ℃), after 15min, 3mL of 6-bromohexanoyl chloride and 0.8g of anhydrous aluminum chloride are added under the same adding condition, the mixture is reacted for 1h under the condition of the ice-water bath (<10 ℃), the temperature is raised to 60 ℃ again, and the mixture is magnetically stirred and reacted for 24h while maintaining the temperature. And after the reaction solution is returned to the room temperature, precipitating a solid in ethanol, dissolving the solid in tetrahydrofuran and then precipitating the solid in ethanol, repeating the process for three times, fully washing the solid with ethanol, and then drying the solid in vacuum at the room temperature for 12 hours to obtain the solid named BrKC6 SEBS.
Dissolving 2g of BrKC6SEBS in 80mL of chloroform, sequentially adding 8g of triethylsilane and 8mL of trifluoroacetic acid at room temperature, heating to 80 ℃ for reaction for 48 hours to obtain a brownish red transparent solution, recovering to room temperature, dissolving with ethanol to separate out a solid, dissolving with tetrahydrofuran, then separating out with ethanol, repeating the process for three times, fully washing with ethanol, and drying the solid under natural conditions to obtain light yellow solid powder which is named as BrC6 SEBS.
0.5g of BrC6SEBS prepared above is dissolved in 2mL of chloroform, then 8mL of tetrachloroethane is added, and the mixture is stirred at room temperature to obtain an orange yellow transparent solution for standby.
Preparation of ionic liquids
26.4g N-methylpyrrolidine and 40mL methyl iodide are respectively added into a 100mL single-neck round-bottom flask and react for 6h at room temperature to obtain 1-methyl-3-ethylpyrrolidine iodide. Dissolving 100g of LiTFSI in 1L of deionized water, adding the prepared 1-methyl-3-ethyl pyrrolidine iodide into a LiTFSI/water solution, fully stirring for 36h at room temperature, separating, treating with 50g of LiTFSI/1L of water solution once, treating with 50g of LiTFSI/1L of water solution overnight (about 12h), separating, drying in a vacuum drying oven at 120 ℃ for 48h, and naming as PyrTFSI.
Preparation of alkaline polymer electrolyte membrane based on ionic liquid
Weighing 0.05g of ZIF-8 material, adding 0.5g of PyrTFSI prepared above into the ZIF-8 material, magnetically stirring for 30min, adding 2mL of 1,1,2, 2-tetrachloroethane into the mixture after the two materials present uniform semitransparent slurry and stirring for 30min, adopting high-power mechanical stirring, adding the BrC6 SEBS/tetrachloroethane solution prepared above into the mixture in a dropwise adding mode, fully stirring for 30min to obtain a semitransparent yellow solution, pouring the semitransparent yellow solution onto a flat glass plate, drying for 2h at room temperature, drying for 3h at 70 ℃, and drying for 4h at 130 ℃ to obtain a yellow transparent uniform film.
The structure and purity of the ionic liquid are characterized by Bruker ACIII 400, and the resonant frequency is 400.13 MHz. During the experiment, a small amount of sample to be tested is dissolved in heavy water, and the sample is obtained on a nuclear magnetic resonance apparatus1H NMR spectrum with Tetramethylsilane (TMS) as internal standard. FIG. 1 is a drawing showing 1-methyl-3-ethylpyrrolidine bromide1H NMR. FIG. 1 shows that the present invention successfully synthesizes ionic liquid with high purity.
And testing the ohmic impedance of the prepared long alkyl chain alkaline polymer electrolyte membrane based on the ionic liquid and taking the SEBS as the main chain by adopting an alternating current impedance method, and then calculating the conductivity value according to a calculation formula of the conductivity. Wherein the calculation formula of the conductivity is as follows:
Figure BDA0002315335080000071
where σ is the conductivity (S/cm) of the film, L is the distance (cm) between the SensorI and SensorII electrodes, W is the width (cm) of the film, T is the thickness (cm) of the film, and R is the impedance (Ω) of the measured film.
The alkaline polymer electrolyte membranes were cut to 0.5 x 4cm before testing2The method comprises the following steps of fixing the rectangular membrane in the middle of a polytetrafluoroethylene mould, putting metal wires (silver wires or platinum wires) into a groove of the mould to lead out three electrodes, putting the mould into deionized water, balancing at a set temperature for at least 30min, and measuring the impedance of the membrane by adopting alternating current impedance. Laboratory apparatusIs a Solartron AC1260 impedance analyzer and a 1287 electrochemical workstation with a scanning frequency range of 1-106Hz. The conductivity of the membrane is the average of the results of the impedance calculations measured a number of times.
Fig. 2 is a graph showing the change of conductivity with temperature of the long alkyl chain basic polymer electrolyte membrane prepared in the example. In FIG. 2, the abscissa is temperature (. degree. C.) and the ordinate is conductivity (mS cm)-1) (ii) a As can be seen from the results in FIG. 2, the conductivity at 100 ℃ was close to 6mS cm-1。
Comparative example 1
The ionic liquid prepared in the embodiment is mixed with BrC6SEBS tetrachloroethane solution with the same concentration in the embodiment, and then the mixture is volatilized to form a membrane, so that the ionic liquid in the prepared alkaline electrolyte membrane without the MOF material is easily lost from the polymer, and the conductivity is reduced.
Comparative example 2
The conductivity of the traditional positively charged alkaline membrane is almost zero at 100 ℃ and no humidity. And cannot be used as an electrolyte under high temperature conditions.
Comparative example 3
When selected for addition to the alkaline polymer electrolyte membrane using MOF materials such as ZIF-1 having small pore sizes, not only will the MOF materials have limited capacity for ionic liquids, resulting in limited conductivity of the membrane under high temperature anhydrous conditions, but also the blocking of hydrated OH-Ion transport, alkaline polymer electrolyte membrane is not able to conduct OH-Ions, which makes the prepared membrane unusable under high temperature anhydrous conditions.

Claims (16)

1. An alkaline electrolyte membrane, characterized in that: the electrolyte membrane consists of an organic polymer, an MOF material and ionic liquid, wherein the organic polymer is used as a main material of the electrolyte membrane, the MOF material is uniformly dispersed in the main material, and the ionic liquid is coated in a pore structure of the MOF material;
the organic polymer is one or more than two of polystyrene, poly (styrene-ethylene-butylene) block copolymer, polyvinyl alcohol, polystyrene derivative and poly (styrene-ethylene-butylene) block copolymer derivative, wherein the polystyrene derivative comprises chlorinated alkyl polystyrene and brominated alkyl polystyrene, and the poly (styrene-ethylene-butylene) block copolymer derivative comprises chlorinated alkyl poly (styrene-ethylene-butylene) block copolymer and brominated alkyl poly (styrene-ethylene-butylene) block copolymer; or the organic polymer is polyvinyl alcohol crosslinked by glutaraldehyde, wherein the mass of the glutaraldehyde crosslinking agent is 0.5-15% of that of the polyvinyl alcohol;
the organic cation of the ionic liquid is tetramethylammonium, trimethylethylammonium, triethylmethylammonium, tetraethylammonium, 1-methyl-3-methylimidazole, 1-methyl-3-ethylimidazole, 1-methyl-3-propylimidazole, 1-methyl-3-isopropylimidazole, 1-methyl-3-butylimidazole, 1-methyl-3-hexylimidazole, 1-methyl-3-octylimidazole, 1-methyl-3-ethanoldiimidazole, 1, 2-dimethyl-3-methylimidazole, 1, 2-dimethyl-3-ethylimidazole, 1, 2-dimethyl-3-propylimidazole, 1, 2-dimethyl-3-isopropylimidazole, triethylmethylammonium, tetraethylammonium, or a mixture thereof, 1, 2-dimethyl-3-butylimidazole, N-dimethylpyrrolidine, N-dimethyl-N-ethylpyrrolidine, N-dimethyl-N-propylpyrrolidine, N-dimethyl-N-butylpyrrolidine, N-dimethylpiperidine, N-methyl-N-ethylpiperidine, N-methyl-N-propylpiperidine and N-methyl-N-butylpiperidine (particularly, trimethylethylammonium, triethylmethylammonium, tetraethylammonium, N-dimethylpyrrolidine, N-dimethyl-N-ethylpyrrolidine, N-dimethyl-N-propylpyrrolidine, N-dimethyl-N-butylpyrrolidine, N-ethylpyrrolidine, N-dimethylpyrrolidine, N-ethylpyrrolidine, N-dimethylpyrrolidine, N-ethylpyrrolidine, N, One or more of N, N-dimethylpiperidine, N-methyl-N-ethylpiperidine, N-methyl-N-propylpiperidine and N-methyl-N-butylpiperidine);
the counter anion of the ionic liquid is Br-、Cl-、I-、BF4 -、BF6 -、FSI-、TFSI-One or more (especially BF)4 -、FSI-、TFSI-One or two or more of the above);
the MOF material is one or more of MIL-101(Cr), MIL-53(Fe), MIL-53(Al), ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12 and UO-66, preferably one or more of MIL-101(Cr), MIL-53(Fe), ZIF-6, ZIF-8, ZIF-10, ZIF-11, ZIF-12 and UO-66.
2. The electrolyte membrane according to claim 1, wherein: the mass ratio of the ionic liquid to the MOF material is 50:1-2:1, preferably 30:1-5: 1; the mass ratio of the MOF material to the organic polymer is 1:1 to 1:20, preferably 1:3 to 1: 10.
3. A method for preparing an ionic liquid based alkaline electrolyte membrane according to claim 1 or 2, characterized in that:
adding ionic liquid into the MOF material, then adding a solvent D solution of an organic polymer, pouring the solution onto a glass plate, and volatilizing the solvent to obtain an ionic liquid-based alkaline electrolyte membrane;
the organic cation of the ionic liquid is tetramethylammonium, trimethylethylammonium, triethylmethylammonium, tetraethylammonium, 1-methyl-3-methylimidazole, 1-methyl-3-ethylimidazole, 1-methyl-3-propylimidazole, 1-methyl-3-isopropylimidazole, 1-methyl-3-butylimidazole, 1-methyl-3-hexylimidazole, 1-methyl-3-octylimidazole, 1-methyl-3-ethanoldiimidazole, 1, 2-dimethyl-3-methylimidazole, 1, 2-dimethyl-3-ethylimidazole, 1, 2-dimethyl-3-propylimidazole, 1, 2-dimethyl-3-isopropylimidazole, triethylmethylammonium, tetraethylammonium, or a mixture thereof, 1, 2-dimethyl-3-butylimidazole, N-dimethylpyrrolidine, N-dimethyl-N-ethylpyrrolidine, N-dimethyl-N-propylpyrrolidine, N-dimethyl-N-butylpyrrolidine, N-dimethylpiperidine, N-methyl-N-ethylpiperidine, N-methyl-N-propylpiperidine and N-methyl-N-butylpiperidine (particularly, trimethylethylammonium, triethylmethylammonium, tetraethylammonium, N-dimethylpyrrolidine, N-dimethyl-N-ethylpyrrolidine, N-dimethyl-N-propylpyrrolidine, N-dimethyl-N-butylpyrrolidine, N-ethylpyrrolidine, N-dimethylpyrrolidine, N-ethylpyrrolidine, N-dimethylpyrrolidine, N-ethylpyrrolidine, N, One or more of N, N-dimethylpiperidine, N-methyl-N-ethylpiperidine, N-methyl-N-propylpiperidine and N-methyl-N-butylpiperidine);
pair of the ionic liquidsThe anion is Br-、Cl-、I-、BF4 -、BF6 -、FSI-、TFSI-One or more (especially BF)4 -、FSI-、TFSI-One or two or more of the above);
the organic polymer is one or more than two of polystyrene, poly (styrene-ethylene-butylene) block copolymer, polyvinyl alcohol, polystyrene derivative and poly (styrene-ethylene-butylene) block copolymer derivative, wherein the polystyrene derivative comprises chlorinated alkyl polystyrene and brominated alkyl polystyrene, and the poly (styrene-ethylene-butylene) block copolymer derivative comprises chlorinated alkyl poly (styrene-ethylene-butylene) block copolymer and brominated alkyl poly (styrene-ethylene-butylene) block copolymer; or the organic polymer is polyvinyl alcohol crosslinked by glutaraldehyde, wherein the mass of the glutaraldehyde crosslinking agent is 0.5-15% of that of the polyvinyl alcohol;
the MOF material is one or more of MIL-101(Cr), MIL-53(Fe), MIL-53(Al), ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12 and UO-66, preferably one or more of MIL-101(Cr), MIL-53(Fe), ZIF-6, ZIF-8, ZIF-10, ZIF-11, ZIF-12 and UO-66;
the solvent D is deionized water, tetrahydrofuran, xylene, toluene, dichloromethane, chloroform, 1,2, 2-tetrachloroethane, carbon tetrachloride, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; wherein tetrahydrofuran, xylene, toluene, dichloromethane, chloroform, 1,2, 2-tetrachloroethane and carbon tetrachloride can be mixed, and one or more than two can be used as solvent; one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone are used as a solvent.
4. The method for producing an electrolyte membrane according to claim 3, wherein:
preparing an ionic liquid alkaline electrolyte membrane, wherein the mass ratio of the ionic liquid to the MOF material is 50:1-2: 1; the volume ratio of the mass of the MOF material to the solvent D is 1:100-1:1 g/mL;
the mass ratio of the mass of the MOF material to the mass of the organic polymer is 1:1 to 1:20 based on the preparation of the ionic liquid alkaline electrolyte membrane.
5. The method for producing an electrolyte membrane according to claim 3, wherein:
the ionic liquid and the MOF material are mixed and then added to the solvent D at a time point when the two are a homogeneous slurry, and the semi-transparent slurry is usually mixed for 1 hour or more.
6. The method for producing an electrolyte membrane according to claim 3, wherein:
preparation of the Ionic liquid based alkaline electrolyte Membrane the ratio of the mass of organic polymer in the organic polymer/solvent D solution to the volume of solvent D is 1:50 to 1:5g/mL, preferably 1:40 to 1:8 g/mL.
7. The method for producing an electrolyte membrane according to claim 3, wherein:
preparation based on the ionic liquid alkaline electrolyte membrane, the polymer organic framework/solvent D solution is added into the slurry of the ionic liquid and the MOF material in one or two modes of crushing by a cell crusher or high-power mechanical stirring, and no particle sedimentation is ensured.
8. The method for producing an electrolyte membrane according to claim 3, wherein:
the preparation of the volatile casting film based on the ionic liquid alkaline electrolyte film is carried out in a step-type heating mode, wherein the temperature of the first stage is room temperature to 50 ℃, the temperature of the second stage is 50 ℃ to 100 ℃, and the temperature of the third stage is 120 ℃ to 150 ℃, wherein the casting time of the first stage is 0.5 h to 4h, the casting time of the second stage is 2h to 8h, and the casting time of the third stage is 2h to 6 h.
9. The method for producing an electrolyte membrane according to claim 3, wherein: the preparation of the ionic liquid comprises the preparation of halogenated ionic liquid and anion conversion of the halogenated ionic liquid;
a. the preparation process of the halogenated ionic liquid comprises the following steps: one or more than two of amine, imidazole, methyl pyrrolidine or methyl piperidine is mixed with halogenated hydrocarbon for reaction, and the temperature is returned to room temperature; precipitating with a solvent A, fully washing and drying;
the halogenated hydrocarbon is one or more than two of C1-C6 straight chain or branched chain halogenated hydrocarbon or ethanol-based halogenated hydrocarbon; the halogen in the halogenated hydrocarbon is Br-、Cl-、I-One or more than two of the above-mentioned compounds to obtain Br as anion-、Cl-、I-One or more of halogenated amine, imidazole, methylpyrrolidine, and methylpiperidine;
b. the process of anion conversion of the halogenated ionic liquid is as follows: adding the prepared amine halide, imidazole, methyl pyrrolidine or methyl piperidine into a solution of an inorganic salt solvent B, separating after reaction, fully washing with a solvent C, and drying to obtain ionic liquids with different anions;
the anion in the inorganic salt is BF4 -、BF6 -、FSI-、TFSI-One or more than two of the above; obtaining the anion as BF4 -、BF6 -、FSI-、TFSI-One or two or more ionic liquids.
10. The method for producing an electrolyte membrane according to claim 9, wherein:
the volume ratio of the mass of the amine, the imidazole, the methyl pyrrolidine or the methyl piperidine to the volume of the halogenated hydrocarbon in the preparation process of the halogenated ionic liquid is 1:1-1:30 g/mL.
11. The method for producing an electrolyte membrane according to claim 9, wherein:
the reaction temperature in the preparation process of the halogenated ionic liquid in the step a is room temperature to 100 ℃; the reaction time is 10min-24 h.
12. The method for producing an electrolyte membrane according to claim 9, wherein:
in the preparation process of the halogenated ionic liquid in the step a, the solvent A is one or more than two of acetone, ethyl acetate, cyclopentane, n-hexane, n-pentane, diethyl ether, acetonitrile and tetrahydrofuran, and preferably one or more than two of acetone, ethyl acetate, diethyl ether and tetrahydrofuran;
in the preparation process of the halogenated ionic liquid in the step a, the drying condition is forced air drying or vacuum drying; the drying temperature is room temperature-200 ℃; the drying time is 0.5-36 h.
13. The method for producing an electrolyte membrane according to claim 9, wherein:
b, in the process of converting the halogenated ionic liquid anions, the solvent B is one or more than two of water, acetonitrile, acetone and tetrahydrofuran which are mixed in proportion;
the inorganic salt is LiBF4、NaBF4、KBF4、LiBF6、NaBF6、KBF6、MgBF6One or more than two of LiFSI, NaFSI, KFSI, LiTFSI, NaTFSI and KTFSI or Ag2O and HBF4Or HBF6The aqueous solution mixture of Ag2O and HBF4Or HBF6Is 1:2, and the concentration of the aqueous solution of HBF4 or HBF6 is 25-68 wt%;
in the B, the volume ratio of the mass of the halogenated ionic liquid to the solvent B in the anion conversion process of the halogenated ionic liquid is 1:0-1:15 g/mL; the volume ratio of the mass of the inorganic salt to the solvent B is 1:10-1:100g/mL (preferably 1:15-1:30 g/mL); the mass ratio of the halogenated ionic liquid to the inorganic salt is 1:1 to 1:250 (preferably 1:2 to 1:150, particularly 1:5 to 1: 50).
14. The method for producing an electrolyte membrane according to claim 9, wherein:
in the process of converting the halogenated ionic liquid anions in the step B, the treatment condition is that the mixture is condensed, refluxed and stirred at the temperature of between room temperature and 80 ℃, and is repeatedly treated for more than 2 times, and the mass fraction of the inorganic salt in the solvent B is improved along with the increase of the treatment times; the treatment time is >24 h.
15. The method for producing an electrolyte membrane according to claim 9, wherein:
b, the separation method is filtration or/and suction filtration or/and liquid separation;
b, the solvent C is one or more than two of acetone, ethyl acetate, cyclopentane, n-hexane, n-pentane, diethyl ether, acetonitrile, tetrahydrofuran and water;
in the process of converting the halogenated ionic liquid anions in the step b, the drying condition is rotary evaporation at 40-180 ℃, air blast or drying at 40-150 ℃ under vacuum; the drying time is 0.5-48 h.
16. Use of the electrolyte membrane according to claim 1 or 2 in an alkaline polymer electrolyte membrane fuel cell or a water electrolysis cell in which an alkaline polymer membrane is used as a solid electrolyte.
CN201911275022.8A 2019-12-12 2019-12-12 Alkaline electrolyte membrane and preparation and application thereof Pending CN113067024A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563601A (en) * 2021-08-18 2021-10-29 苏州大学 Cation-deficient ZIF porous material and preparation method and application thereof
CN115806676A (en) * 2021-09-16 2023-03-17 中国科学院化学研究所 Method for rapidly synthesizing metal organic framework compound at normal temperature by using imidazole free radical assistance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461790A (en) * 2016-12-13 2018-08-28 中国科学院大连化学物理研究所 A kind of long side chain SEBS bases alkaline polymer electrolyte membrane and its preparation and application
CN108878970A (en) * 2018-06-29 2018-11-23 华中科技大学 A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof
CN109935874A (en) * 2017-12-19 2019-06-25 中国科学院大连化学物理研究所 A kind of crosslinking high temperature electrolyte membrane and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461790A (en) * 2016-12-13 2018-08-28 中国科学院大连化学物理研究所 A kind of long side chain SEBS bases alkaline polymer electrolyte membrane and its preparation and application
CN109935874A (en) * 2017-12-19 2019-06-25 中国科学院大连化学物理研究所 A kind of crosslinking high temperature electrolyte membrane and preparation method thereof
CN108878970A (en) * 2018-06-29 2018-11-23 华中科技大学 A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TINGTING ZHANG, ET AL.: "《Development of anion conducting zeolitic imidazolate framework bottle around ship incorporated with ionic liquids》", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563601A (en) * 2021-08-18 2021-10-29 苏州大学 Cation-deficient ZIF porous material and preparation method and application thereof
CN113563601B (en) * 2021-08-18 2022-06-14 苏州大学 Cation-deficient ZIF porous material and preparation method and application thereof
CN115806676A (en) * 2021-09-16 2023-03-17 中国科学院化学研究所 Method for rapidly synthesizing metal organic framework compound at normal temperature by using imidazole free radical assistance
CN115806676B (en) * 2021-09-16 2023-09-15 中国科学院化学研究所 Method for rapidly synthesizing metal organic framework compound at normal temperature by utilizing imidazole free radicals

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