CN109411795B - Preparation method of polybenzimidazole polymer electrolyte membrane used in flow battery - Google Patents
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Abstract
The invention belongs to the technical field of new materials and membranes, and provides a preparation method of a polybenzimidazole polymer electrolyte membrane used in a flow battery. The preparation method comprises the following steps: (1) respectively dissolving Polybenzimidazole (PBI), 2, 3-epoxypropyltrimethylammonium chloride (Epoxy) and (5-bromopentyl) -trimethylammonium (EPTA) in a polar organic solvent, and performing ultrasonic treatment to obtain a uniform solution; (2) preparing a composite membrane material by adopting a solution casting method; (3) washing with a large amount of deionized water to obtain a polymer electrolyte membrane; (4) completely soaking the polymer electrolyte membrane in a sulfuric acid solution for doping, and measuring the surface resistance; (5) the polymer electrolyte membrane is used for an all-vanadium redox flow battery, and the vanadium ion transmittance and the mass change are measured. According to the invention, the grafting content of Epoxy and EPTA in the PBI membrane is regulated, the control of different quaternary ammonium salt contents in the PBI is realized, the acid doping content and the conductivity of the membrane are increased, and the grafted membrane material has lower vanadium ion transmittance.
Description
Technical Field
The invention belongs to the technical field of new materials and membranes, and relates to a preparation method of a polybenzimidazole polymer electrolyte membrane used in a flow battery.
Background
The all-vanadium redox flow battery (called vanadium battery for short, VRB) has the advantages of high energy efficiency, long cycle life, simple design, large-scale energy storage and the like, and is increasingly paid more attention by people. Therefore, as one of the core components of VRBs, ideal Ion Exchange Membranes (IEMs) must meet the requirements of high conductivity, strong chemical stability, low vanadium ion permeability, low cost, etc.
The polymer electrolyte membrane widely used in VRB today is a perfluoro type sulfonic acid membrane (e.g., Nafion membrane). The structure of the membrane material consists of hydrophilic sulfonic acid groups and hydrophobic polytetrafluoroethylene chains, and the hydrophilic and hydrophobic structures enable the membrane material to have higher conductivity and oxidation resistance. However, when the membrane is hydrated, micro-phase separation between hydrophilic groups and hydrophobic chains can form water channels, so that the transmittance of vanadium ions is increased, self-discharge of the vanadium battery is caused, and the service life of the battery is further influenced. In addition, the production process of the perfluorosulfonic acid membrane material is complex, and the cost is very high, so that the large-scale application and development of the perfluorosulfonic acid membrane material are restricted.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a method for preparing a polybenzimidazole polymer electrolyte membrane used in a flow battery, namely a side-chain branched Polybenzimidazole (PBI) membrane, which has the advantages of simple preparation method, low IEM cost, good vanadium resistance, high oxidation resistance, etc. According to the invention, PBI is taken as a matrix material, two compounds, namely 3-epoxypropyltrimethylammonium chloride (Epoxy) and (5-bromopentyl) -trimethylammonium (EPTA), are respectively grafted to a PBI framework through a nucleophilic substitution reaction, and the membrane material with low surface resistance, high vanadium resistance, strong oxidation resistance and excellent mechanical property is prepared. The prepared polymer electrolyte membrane is a transparent, uniform and compact membrane material. The chemical structures of the PBI, the Epoxy and the EPTA are as follows:
a method of making a polybenzimidazole polymer electrolyte membrane for use in a flow battery comprising the steps of:
(1) respectively dissolving PBI, Epoxy and EPTA in a polar organic solvent at normal temperature, and ultrasonically dissolving to respectively obtain transparent PBI, Epoxy and EPTA solutions with the mass fraction of 1-3%;
(2) mixing the PBI and the Epoxy in the step (1) according to a molar ratio of Epoxy/PBI of 0.5-2.0, mixing the PBI and the EPTA according to a molar ratio of EPTA/PBI of 1.0-4.0, and carrying out ultrasonic treatment for 30-60 min to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 60-100 ℃ in the membrane forming process, and the membrane forming time is 12-48 hours;
(4) and (4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain the polymer electrolyte membrane.
Completely soaking the polymer electrolyte membrane in 3-5 mol/L H2S04Acid doping is carried out in the solution, and the surface resistance is measured;
completely soaking the polymer electrolyte membrane in vanadyl sulfate and sulfuric acid (1-3 mol/L VOSO)4+3～5mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
Further, the polar organic solvent in the step (1) is one of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
The invention has the beneficial effects that:
(a) the prepared polymer electrolyte is based on a PBI polymer, and has good chemical stability and thermal stability;
(b) different Epoxy and EPTA compounds are grafted on the PBI framework, so that the free volume and the sulfuric acid action site of the membrane material are increased, the sulfuric acid doping capacity of the PBI membrane is enhanced, and the sheet resistance of the membrane material is reduced;
(c) the preparation method is simple, processes such as chloromethylation quaternization and the like in the traditional ion exchange membrane preparation process are not needed, the use of carcinogenic reagents in the chloromethyl process is avoided, and the phenomena of membrane structure damage and uneven ammonification caused in the quaternization process are prevented;
(d) the acid doping, vanadium permeability and mechanical strength of the prepared ion exchange membrane can be simply regulated and controlled through different grafting degrees.
Drawings
Fig. 1 is a graph showing mechanical properties of the polymer electrolyte membrane obtained in the embodiment. The abscissa of the graph represents the different composite membrane materials, and the ordinate represents the Tensile Strength Tensil Strength (MPa).
Detailed Description
The present invention is further illustrated by the following examples.
Example 1, a method of preparing a PBI composite membrane comprising the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 15g of N, N-dimethylacetamide solution at normal temperature, and performing ultrasonic treatment to obtain a polymer solution with the mass fraction of 1%;
(2) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 60 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(3) washing the composite membrane material obtained in the step (2) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(4) completely soaking the polymer electrolyte membrane in the step (3) in 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(5) completely soaking the polymer electrolyte membrane in the step (3) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 2.95 multiplied by 10-7cm2Min, surface resistance 0.68 omega/cm21.7M VOSO at room temperature4And 3M H2SO4After the solution is soaked for 57 days, the mass loss is 1.4 percent, the mechanical strength is 116.4MPa, and the comprehensive performance is good.
Example 2, a method of preparing a 0.5Epoxy/PBI composite membrane comprises the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 7.5g of N, N-dimethylacetamide solution at normal temperature, and carrying out ultrasonic treatment to obtain a polymer solution with the mass fraction of 2%;
(2) adding an Epoxy solution into the PBI solution according to the proportional relation that the molar ratio of Epoxy/PBI is 0.5, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 24 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(5) completely soaking the polymer electrolyte membrane in the step (4) in a 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(6) completely impregnating the polymer electrolyte membrane of the step (4)Soaking in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 8.59 multiplied by 10-8cm2Min, surface resistance 0.53 omega/cm21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 53 days, the mass loss is 2.2 percent, the mechanical strength is 61.2MPa, and the comprehensive performance is good.
Example 3, a method of preparing a 1.0Epoxy/PBI composite membrane comprises the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 5g of N, N-dimethylacetamide solution at normal temperature, and performing ultrasonic treatment to obtain a polymer solution with the mass fraction of 3%;
(2) adding an Epoxy solution into the PBI solution according to the proportional relation that the molar ratio of Epoxy/PBI is 1.0, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 36 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(5) completely soaking the polymer electrolyte membrane in the step (4) in a 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(6) completely soaking the polymer electrolyte membrane in the step (4) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 5.11 × 10-7cm2Min, surface resistance 0.19 omega/cm21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 54 days, the mass loss is 1.1 percent, the mechanical strength is 84MPa, and the comprehensive performance is good.
Example 4, a method of preparing a 1.5Epoxy/PBI composite membrane comprises the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 15g of N, N-dimethylacetamide solution at normal temperature, and performing ultrasonic treatment to obtain a polymer solution with the mass fraction of 1%;
(2) adding an Epoxy solution into the PBI solution according to the proportional relation that the molar ratio of Epoxy/PBI is 1.5, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(5) completely soaking the polymer electrolyte membrane in the step (4) in a 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(6) completely soaking the polymer electrolyte membrane in the step (4) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 2.55 x 10-6cm2Min, surface resistance 0.39 omega/cm21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 45 days, the mass loss is 8.4 percent, the mechanical strength is 86MPa, and the comprehensive performance is good.
Example 5, a method of preparing a 2.0Epoxy/PBI composite membrane comprises the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 15g of N, N-dimethylacetamide solution at normal temperature, and performing ultrasonic treatment to obtain a polymer solution with the mass fraction of 1%;
(2) adding an Epoxy solution into the PBI solution according to the proportional relation that the molar ratio of Epoxy/PBI is 2.0, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(5) completely soaking the polymer electrolyte membrane in the step (4) in a 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(6) completely soaking the polymer electrolyte membrane in the step (4) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 4.4 x 10-7cm2Area resistance of 0.41 omega/cm/min21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 32 days, the mass loss is 33.0 percent, the mechanical strength is 64MPa, and the comprehensive performance is good.
Example 6, a method of preparing a 1.0EPTA/PBI composite membrane comprises the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 15g of N, N-dimethylacetamide solution at normal temperature, and performing ultrasonic treatment to obtain a polymer solution with the mass fraction of 1%;
(2) adding an EPTA solution into the PBI solution according to the proportion relationship that the molar ratio of EPTA/PBI is 1.0, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 12 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(5) completely soaking the polymer electrolyte membrane in the step (4) in a 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(6) completely soaking the polymer electrolyte membrane in the step (4) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The permeability and mass change of vanadium ions were measured in the aqueous solution of (1).
The resulting polymer electrolyteThe film has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the film is 2.78 multiplied by 10-6cm2Min, surface resistance 0.32 omega/cm21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 48 days, the mass loss is 2.8 percent, the mechanical strength is 48.9MPa, and the comprehensive performance is good.
Example 7, a method of preparing a 2.0EPTA/PBI composite membrane comprising the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 7.5g of N, N-dimethylacetamide solution at normal temperature, and carrying out ultrasonic treatment to obtain a polymer solution with the mass fraction of 2%;
(2) adding an EPTA solution into the PBI solution according to the proportion relationship that the molar ratio of EPTA/PBI is 2.0, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 70 ℃ in the membrane forming process, and the membrane forming time is 24 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(6) completely soaking the polymer electrolyte membrane in the step (4) in 3mol/L sulfuric acid aqueous solution for acid doping, and measuring the surface resistance;
(6) completely soaking the polymer electrolyte membrane in the step (4) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 3.50 multiplied by 10-6cm2Min, surface resistance 0.43 omega/cm21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 28 days, the mass loss is 12.4 percent, the mechanical strength is 33.5MPa, and the comprehensive performance is good.
Example 8, a method of preparing a 4.0EPTA/PBI composite membrane comprising the steps of:
(1) weighing 0.15g of PBI (Poly-p-phenylene benzobisoxazole) and dissolving the PBI in 5g of N, N-dimethylacetamide solution at normal temperature, and performing ultrasonic treatment to obtain a polymer solution with the mass fraction of 3%;
(2) adding an EPTA solution into the PBI solution according to the proportion relationship that the molar ratio of EPTA/PBI is 4.0, and carrying out ultrasonic treatment to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 80 ℃ in the membrane forming process, and the membrane forming time is 48 hours;
(4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain a polymer electrolyte membrane;
(5) completely soaking the polymer electrolyte membrane in the step (4) in a 3mol/L sulfuric acid solution for acid doping, and measuring the surface resistance;
(6) completely soaking the polymer electrolyte membrane in the step (4) in vanadyl sulfate and sulfuric acid (1.7mol/L VOSO)4+3mol/L H2SO4) The vanadium ion permeability and mass change were measured in the solution of (1).
The obtained polymer electrolyte membrane has good vanadium resistance and chemical stability, and the vanadium ion transmittance of the membrane is 1.63 multiplied by 10-6cm2Min, surface resistance 0.66 omega/cm21.7M VOSO at room temperature4And 3M H2SO4The solution is soaked for 34 days, the mass loss is 7.6 percent, the mechanical strength is 22.4MPa, and the comprehensive performance is good.
Table 1 shows the surface resistance, vanadium ion permeability, ion selectivity, and the like of the polymer electrolyte membrane obtained in the embodiment.
The test results of the above examples show that the prepared polybenzimidazole-based polymer electrolyte membrane has good vanadium resistance and chemical stability, and good mechanical strength, and can be used as an electrolyte membrane material of a flow battery device.
Claims (2)
1. The preparation method of the polybenzimidazole polymer electrolyte membrane used in the all-vanadium redox flow battery is characterized by comprising the following steps of:
(1) respectively dissolving PBI, Epoxy and EPTA in a polar organic solvent at normal temperature, and ultrasonically dissolving to respectively obtain transparent PBI, Epoxy and EPTA solutions with the mass fraction of 1-3%; the chemical structure of the PBI, Epoxy and EPTA is as follows:
(2) mixing the PBI and the Epoxy in the step (1) according to a molar ratio Epoxy/PBI of 0.5-2.0 or mixing the PBI and the EPTA according to a molar ratio EPTA/PBI of 1.0-4.0, and performing ultrasonic treatment for 30-60 min to obtain a transparent and uniform casting film solution;
(3) preparing a composite membrane material by adopting a solution casting method, wherein the solvent is volatilized at the temperature of 60-100 ℃ in the membrane forming process, and the membrane forming time is 12-48 hours;
(4) and (4) washing the composite membrane material obtained in the step (3) by using a large amount of deionized water to obtain the polymer electrolyte membrane.
2. The method of claim 1, wherein the polar organic solvent in step (1) is one of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone.
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| CN110048148A (en) * | 2019-04-24 | 2019-07-23 | 东北大学 | Polybenzimidazole polymer porous electrolyte membrane preparation method for flow battery |
| CN110112448B (en) * | 2019-05-21 | 2021-01-19 | 大连理工大学 | Comb-structured high-conductivity polybenzimidazole anion exchange membrane and preparation method thereof |
| CN112011051B (en) * | 2019-05-28 | 2022-05-17 | 大连理工大学 | Heterocyclic ammonium ion polybenzimidazole and anion exchange membrane as well as preparation method and application thereof |
| CN113451625B (en) * | 2021-06-28 | 2022-08-05 | 东北大学 | Preparation method and application of polymer membrane containing nitrogen heterocycle |
| CN113929943B (en) * | 2021-08-27 | 2022-09-16 | 湖南大学 | Polybenzimidazole membrane and preparation method and application thereof |
| CN114213688B (en) * | 2021-12-06 | 2022-10-14 | 河北科技大学 | Polybenzimidazole type amphoteric ion exchange membrane material and preparation method and application thereof |
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