CN112803051A - Preparation method of novel lignosulfonic acid/Nafion composite proton exchange membrane - Google Patents
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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Abstract
The invention provides a preparation method of a novel lignosulfonic acid/Nafion composite proton exchange membrane. The method comprises the following steps: the first step is as follows: adding sodium lignosulfonate powder into deionized water to be fully dissolved, adjusting the pH of the solution by using a hydrochloric acid solution until precipitation appears in the solution, centrifugally washing, and freeze-drying to obtain lignosulfonic acid; the second step is that: adding lignosulfonic acid and polyvinyl alcohol into a Nafion solution, forming a uniform solution after magnetic stirring and ultrasonic dispersion, coating the obtained solution on the surface of a glassware, and drying in vacuum at 80-120 ℃ for 12-24 hours to obtain the composite proton exchange membrane material. The preparation conditions of the lignosulfonic acid composite proton exchange membrane are mild, the cost of the prepared proton exchange membrane is greatly reduced, the proton conductivity is high, and the thermal stability and the mechanical property are excellent.
Description
Technical Field
The invention relates to a preparation method of a novel lignosulfonic acid/Nafion composite proton exchange membrane, and belongs to the field of fuel cell proton exchange membranes.
Background
With the continuous advance of human industrialization, environmental pollution and energy crisis become important factors that restrict the continued development of human beings. Therefore, the development and utilization of clean and renewable new energy sources have been regarded as important in various countries of the world. A Fuel Cell (Fuel Cell) is an energy conversion device that converts chemical energy stored in a Fuel into electrical energy and uses the electrical energy. The fuel cell has no combustion process in the operation process, the conversion process is green and environment-friendly, the energy density is high, the noise is low, and the fuel cell is an effective way for solving the current energy crisis and slowing down the greenhouse effect.
A Proton Exchange Membrane (PEM) is one of the key components in a Proton Exchange Membrane Fuel Cell (PEMFC), and unlike the membrane of a general energy storage cell, the PEM plays a role of transporting protons in addition to functions of isolating the cathode and anode and preventing fuel permeation. Excellent proton exchange membranes need to have excellent proton conductivity, good gas barrier capability, good chemical and thermal stability, good mechanical properties and dimensional stability, and the like. The performance of the proton exchange membrane directly affects the efficiency of the fuel cell. To date, the most successfully and widely used proton exchange membrane is the perfluorosulfonic acid (Nafion) proton exchange membrane of dupont, which has the advantages of good chemical stability, high mechanical strength, high proton conductivity at a proper temperature, and the like. But the defects are that the Nafion membrane has complex production process and high price, and the poor performance at high temperature (more than 80 ℃) and the environmental pollution after the waste become key problems for limiting the wide application of the fuel cell.
Chinese patent publication No. CN106188433A discloses a preparation method of a sulfonated polyarylethersulfone polymer composite membrane containing graft modified sodium lignosulfonate. Firstly, styrene, acrylate and a peroxysulfuric acid initiator are used for carrying out graft modification on sodium lignosulfonate, so that the sodium lignosulfonate can be well and uniformly mixed with a polymer, and has the characteristics of low cost and good thermal stability.
Chinese patent publication No. CN102477162A discloses a method for preparing a proton exchange membrane, which has high proton conductivity and good high temperature resistance, but also has the disadvantages of high cost, few material sources, complex process and environmental pollution.
According to the above, the existing proton exchange membrane has the defects of high cost, complex preparation conditions, poor performance at high temperature and environmental pollution, so that the development of a membrane material with low price, simple preparation process and good comprehensive performance becomes urgent.
Disclosure of Invention
The invention provides a preparation method of a novel lignosulfonic acid/Nafion proton exchange membrane material aiming at the defects of high cost, poor performance at high temperature, environmental pollution and the like of the existing proton exchange membrane, and simultaneously adopts polyvinyl alcohol (PVA) as a reinforcing agent to solve the problem of mechanical property reduction caused by doping Nafion into lignosulfonic acid; the method comprises the steps of fully dissolving sodium lignosulfonate in deionized water, and adjusting the pH value of the solution by using hydrochloric acid, namely under an acidic condition, combining sodium ions and chloride ions in the solution into sodium chloride to be dissolved in water due to electrostatic interaction, and combining sulfonate ions with hydrogen ions to form sulfonic acid to be separated out in the solution; the atomic absorption spectrum is used for detecting the sodium content of the obtained lignosulfonic acid, and the result shows that the sodium content is only 0.32%, while the sodium content in the original sodium lignosulfonate is 11.9%. The preparation process is simple, the reaction conditions are mild, and the prepared proton exchange membrane has high stability, mechanical property and proton conductivity under the condition of reducing the cost.
The technical scheme of the invention is as follows:
(1) preparing lignosulfonic acid:
adding sodium lignosulfonate powder into deionized water at normal temperature, and fully stirring and dissolving to obtain a sodium lignosulfonate aqueous solution; slowly dripping 10% hydrochloric acid solution into the above solution until pH is 2, allowing insoluble substance to precipitate in the solution, stirring for 2 hr, centrifuging at 2500rpm, washing, and freeze drying to obtain lignosulfonic acid;
(2) preparation of lignosulfonic acid/Nafion composite proton exchange membrane
Firstly, evaporating a solvent from a proper amount of 20% Nafion dispersion liquid at 60 ℃ to obtain Nafion solid resin, weighing, then dissolving in a quantitative organic solvent at 60 ℃ to ensure that the concentration of Nafion in the organic solvent is 0.045g/ml, and magnetically stirring for 12 hours to obtain a uniform membrane casting solution. Adding lignosulfonic acid and 10 wt% of PVA solution into the solution, wherein the mass of lignosulfonic acid is 5-20% of that of Nafion solid resin, the mass of PVA is 10% of that of Nafion, and magnetically stirring for 12 hours. And coating the obtained solution on the surface of a glassware, and drying for 12-24 hours at 80-120 ℃ to obtain the composite proton exchange membrane.
In the preparation method of the lignosulfonic acid, the pH of the solution is 1.0-2.5.
In the preparation method of the novel lignosulfonic acid composite proton exchange membrane, the coating method is a tape casting method or a solution casting method.
In the preparation method of the novel lignosulfonic acid composite proton exchange membrane, the organic solvent is one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP).
The invention has the substantive characteristics that:
the lignosulfonate is used as a natural renewable resource, the precursor lignin of the lignosulfonate is widely present in plant roots and stems, is a natural high polymer with the content inferior to that of cellulose and chitin in the nature, and has the advantages of wide source, low price and the like. The lignosulfonate contains more sulfonic groups and has strong binding capacity with water, and the lignosulfonate has the potential of being prepared into a high-performance proton exchange membrane. However, according to research, the solubility of the lignosulfonate in an organic solvent is poor, and the solubility of the lignosulfonate in water is strong, so that in order to solve the problem, the lignosulfonate is converted into the lignosulfonate in a simple mode, the solubility of the lignosulfonate in the organic solvent is enhanced, and the lignosulfonate and a polymer have good compatibility. PVA is an economical and effective hydrophilic polymer, contains a large number of hydroxyl groups, and has excellent physical properties due to strong intermolecular and intramolecular hydrogen bond interactions. Meanwhile, the hydroxyl group of PVA can be used as a hydrogen donor to form a hydrogen bond with the sulfonic group of Nafion, so that the mechanical property of the proton exchange membrane is remarkably improved.
The invention has the beneficial effects that:
1. the lignosulfonic acid proton exchange membrane disclosed by the invention is low in cost, simple in modification process and free from complicated chemical experiments, easily solves the problem of poor solubility of lignosulfonate in an organic solvent, solves the problems of complicated modification of lignosulfonate in the publication No. CN106188433A and the like, and lays a solid foundation for large-scale preparation of composite membranes.
PVA is a water-soluble polymer material, and has the characteristics of good film forming property, low price, biodegradability and the like. In addition, documents report that the hydroxyl group of PVA can form a hydrogen bond network with a sulfonic group in a Nafion matrix, so that the mechanical property of the proton exchange membrane is obviously improved, and the PVA has certain self-healing property and the durability of the proton exchange membrane is improved.
3. The proton exchange membrane prepared by the invention has good thermal stability; TG analyzer shows that the membrane can still keep stable at 300 ℃, infrared spectrum shows that the introduction of lignosulfonic acid does not affect Nafion structure, and the proton exchange membrane has high capacity and excellent mechanical property.
4. The composite proton exchange membrane prepared by the invention is formed into a membrane by evaporating a solvent, and the surface of the membrane is observed by an SEM (scanning Electron microscope), so that the prepared proton exchange membrane has compact and stable surface, can meet the application on a fuel cell, and is suitable for commercial production.
Drawings
FIG. 1 is a graph comparing solubility in N, N-dimethylacetamide before and after lignosulfonate modification.
FIG. 2 is a SEM scanning electron microscope comparison image of the lignosulfonic acid composite membrane and a Nafion membrane.
FIG. 3 is a thermogravimetric analysis (TGA) characterization of the lignosulfonic acid composite membrane and Nafion membrane.
FIG. 4 is a mechanical property curve diagram of the lignosulfonic acid composite membrane and the Nafion membrane.
Detailed Description
The following examples are given to illustrate but not limit the invention, the scope of which is defined by the claims.
Example 1:
(1) at normal temperature, 10g of sodium lignosulfonate powder is dissolved in 40mL of deionized water, and the mixture is fully stirred until no obvious solid matter exists in the solution;
(2) slowly dripping a 10% hydrochloric acid solution prepared in advance into the sodium lignosulphonate solution in the step 1) until the pH value is 2.0, continuously stirring for 2 hours until the lignosulphonic acid is fully separated out, centrifuging, washing, and freeze-drying for 24 hours to obtain solid lignosulphonate powder;
(3) taking 1.5mL of 20% Nafion dispersion liquid into a clean small beaker, drying at 60 ℃ for 12h to evaporate a solvent to obtain 370mg of solid Nafion resin, adding 8mL of N, N-dimethylacetamide solution, dissolving uniformly in a water bath environment at 60 ℃ in a sealed state, adding 18.5mg of lignosulfonic acid and 370mg of 10% PVA solution, and continuously stirring for 12 h;
(4) and (4) pouring the uniform membrane casting solution obtained in the step (3) into a clean culture dish, horizontally placing the culture dish into a vacuum drying oven, drying for 12 hours at the temperature of 80 ℃, and drying for 6 hours at the temperature of 120 ℃ to obtain the proton exchange membrane with the doping amount of the lignosulfonic acid of 5%.
Example 2:
(1) at normal temperature, 15g of sodium lignosulfonate powder is dissolved in 50mL of deionized water and fully stirred until no obvious solid matter exists in the solution;
(2) slowly dripping a 10% hydrochloric acid solution prepared in advance into the sodium lignosulphonate solution in the step 1) until the pH value is 2.0, continuously stirring for 2 hours until the lignosulphonic acid is fully separated out, centrifuging, washing, and freeze-drying for 24 hours to obtain solid lignosulphonate powder;
(3) taking 1.5mL of 20% Nafion dispersion liquid into a clean small beaker, drying at 60 ℃ for 12h to evaporate a solvent to obtain 370mg of solid Nafion resin, adding 8mL of N, N-dimethylacetamide solution, dissolving uniformly in a water bath environment at 60 ℃ in a sealed state, adding 55.5mg of lignosulfonic acid and 370mg of 10% PVA solution, and continuously stirring for 12 h;
(4) and (4) pouring the uniform membrane casting solution obtained in the step (3) into a clean culture dish, horizontally placing the culture dish into a vacuum drying oven, drying for 12 hours at the temperature of 80 ℃, and drying for 6 hours at the temperature of 120 ℃ to obtain the proton exchange membrane with the doping amount of the lignosulfonic acid of 10%.
Example 3:
(1) at normal temperature, 15g of sodium lignosulfonate powder is dissolved in 50mL of deionized water and fully stirred until no obvious solid matter exists in the solution;
(2) slowly dripping a 10% hydrochloric acid solution prepared in advance into the sodium lignosulphonate solution in the step 1) until the pH value is 2.0, continuously stirring for 2 hours until the lignosulphonic acid is fully separated out, centrifuging, washing, and freeze-drying for 24 hours to obtain solid lignosulphonate powder;
(3) taking 1.5mL of 20% Nafion dispersion liquid into a clean small beaker, drying at 60 ℃ for 12h to evaporate a solvent to obtain 370mg of solid Nafion resin, adding 8mL of N, N-dimethylacetamide solution, dissolving uniformly in a water bath environment at 60 ℃ in a sealed state, adding 37mg of lignosulfonic acid and 370mg of 10% PVA solution, and continuously stirring for 12 h;
(4) and (4) pouring the uniform membrane casting solution obtained in the step (3) into a clean culture dish, horizontally placing the culture dish in a vacuum drying oven, drying for 12 hours at the temperature of 80 ℃, and drying for 6 hours at the temperature of 120 ℃ to obtain the proton exchange membrane with the doping amount of the lignosulfonic acid of 15%.
Example 4:
(1) at normal temperature, 20g of sodium lignosulfonate powder is dissolved in 100mL of deionized water and fully stirred until no obvious solid matter exists in the solution;
(2) slowly dripping a 10% hydrochloric acid solution prepared in advance into the sodium lignosulphonate solution in the step 1) until the pH value is 2.0, continuously stirring for 2 hours until the lignosulphonic acid is fully separated out, centrifuging, washing, and freeze-drying for 24 hours to obtain solid lignosulphonate powder;
(3) taking 1.5mL of 20% Nafion dispersion liquid into a clean small beaker, drying at 60 ℃ for 12h to evaporate a solvent to obtain 370mg of solid Nafion resin, adding 8mL of N, N-dimethylacetamide solution, dissolving uniformly in a water bath environment at 60 ℃ in a sealed state, adding 74mg of lignosulfonic acid and 370mg of 10% PVA solution, and continuously stirring for 12 h;
(4) and (4) pouring the uniform membrane casting solution obtained in the step (3) into a clean culture dish, horizontally placing the culture dish into a vacuum drying oven, drying for 12 hours at the temperature of 80 ℃, and drying for 6 hours at the temperature of 120 ℃ to obtain the proton exchange membrane with the doping amount of the lignosulfonic acid of 20%.
The following table is a comparison of the performance of the composite membrane of the present invention with a commercial Nafion 112 proton exchange membrane
By comparison under the same test conditions, the proton conductivity of the composite membrane is 80mS/cm and the maximum tensile stress is 13.6MPa when the doping amount of the modified lignosulfonic acid is 10 wt% in example 2; after the PVA is added, the proton conductivity of the composite membrane is 82mS/cm, the maximum tensile stress is 23.4MPa, and the introduction of the PVA can greatly enhance the mechanical property of the proton exchange membrane, has very obvious effect and is improved by 50 percent compared with the commercial Nafion 112; in conclusion, the proton exchange membrane of the invention can be used at a temperature of more than 100 ℃, has simple preparation method, higher proton conductivity and cost far lower than that of a commercial Nafion 112 membrane, and has wide application market.
The invention is not the best known technology.
Claims (5)
1. A preparation method of a novel lignosulfonic acid/Nafion composite proton exchange membrane is characterized in that the lignosulfonic acid/Nafion composite proton exchange membrane is formed by compounding lignosulfonic acid, perfluorosulfonic acid (Nafion) and polyvinyl alcohol (PVA); the addition of lignosulfonic acid can reduce the usage amount of Nafion to reduce cost; the PVA is used as a reinforcing agent, so that the mechanical property of the proton exchange membrane can be remarkably enhanced; the two are added into Nafion to prepare a novel lignosulfonic acid/Nafion composite proton exchange membrane, which comprises the following steps:
(1) adding sodium lignosulfonate powder into deionized water, and fully stirring and dissolving to obtain a sodium lignosulfonate aqueous solution;
(2) dropwise adding a proper amount of 10% hydrochloric acid solution into the sodium lignosulfonate aqueous solution in the step (1), adjusting the pH of the solution to be acidic, continuously stirring until lignosulfonic acid is fully separated out, centrifuging, washing, and freeze-drying for 24 hours to obtain lignosulfonic acid solid powder;
(3) taking a proper amount of Nafion dispersion liquid, evaporating the solvent at a proper temperature to obtain Nafion solid resin, weighing, and dissolving in an organic solvent at a certain temperature to obtain a uniform polymer solution;
(4) and (3) adding the lignosulfonic acid obtained in the step (2) and a proper amount of 10% polyvinyl alcohol (PVA) solution into the polymer solution obtained in the step (3), fully stirring and carrying out ultrasonic treatment to obtain a uniform membrane casting solution, then coating the obtained solution on the surface of a glassware, and drying at 80-120 ℃ for 12-24 h to obtain the lignosulfonic acid/Nafion composite proton exchange membrane.
2. The preparation method of the novel lignosulfonic acid/Nafion composite proton exchange membrane according to claim 1, characterized in that the mass of lignosulfonic acid is 5-20% of the mass of Nafion, and the solid content of polyvinyl alcohol solution is 5-15% of the mass of Nafion solid.
3. The method for preparing a novel lignosulfonic acid/Nafion composite proton exchange membrane according to claim 1, wherein in step (2), the coating method is a casting method or a solution casting method.
4. The preparation method of the novel lignosulfonic acid/Nafion composite proton exchange membrane according to claim 1, wherein the pH of the solution in step (2) is 1.0-2.5.
5. The method for preparing a novel lignosulfonic acid/Nafion composite proton exchange membrane according to claim 1, characterized in that the organic solvent in step (2) is one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
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| CN115763921A (en) * | 2022-10-24 | 2023-03-07 | 广州大学 | Proton exchange membrane with self-healing capability and preparation method thereof |
| CN116253817A (en) * | 2023-03-13 | 2023-06-13 | 浙江聚合储能科技有限公司 | Fluorine ion exchange membrane and preparation method thereof |
| CN117183041A (en) * | 2023-07-11 | 2023-12-08 | 南京林业大学 | Gelatin-lignin sulfonic acid wood composite acoustic diaphragm and preparation method and application thereof |
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