Filler for modifying proton exchange membrane and preparation method thereof
By introducing various functional groups supported on carbon carriers into proton exchange membranes, the problem of insufficient water retention of proton exchange membranes under intermediate temperature conditions was solved, the proton conductivity was improved, and the mass production of composite membranes was realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-12
- Publication Date
- 2026-04-07
Smart Images
Figure CN121812653A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of nanomaterial preparation or catalyst precursor material preparation, in particular to a filler for proton exchange membrane modification and a preparation method thereof. BACKGROUND
[0002] Proton exchange membrane fuel cells have the characteristics of low temperature start, high energy conversion rate, clean and environmental protection, and are considered as one of the most promising power sources. The commonly used proton exchange membrane is perfluorosulfonic acid proton exchange membrane, and with the gradual increase of temperature, the proton exchange membrane will have obvious membrane dehydration phenomenon, which will cause the serious decline of proton conductivity, and the working temperature is limited to 60-80℃.
[0003] It is reported that the water absorption performance of the proton exchange membrane can be improved by adding water-absorbing fillers such as silicon dioxide and graphene oxide. However, the water retention performance cannot meet the working requirements of the proton exchange membrane at medium temperature by introducing a single water-absorbing functional group. SUMMARY
[0004] The present application aims to overcome the deficiencies in the prior art, and provides a filler for proton exchange membrane modification and a preparation method thereof. The filler for proton exchange membrane modification introduces multiple functional groups, utilizes the synergistic effect of different functional groups, realizes water locking of the material, improves the water retention performance of the material, has high stability, simple preparation process, controllable product quality, and can realize batch production.
[0005] To achieve the above-mentioned purposes, the present application adopts the following technical solutions:
[0006] On the one hand, the present application provides a filler for proton exchange membrane modification, which comprises a carbon carrier and multiple functional groups loaded on the carbon carrier.
[0007] The carbon carrier has a sheet structure.
[0008] The multiple functional groups include hydroxyl groups and amino groups, and the multiple functional groups are used as water absorption and proton conduction sites.
[0009] Further, the multiple functional groups further include sulfonic acid groups.
[0010] On the other hand, the present application provides a preparation method of the filler, which comprises:
[0011] Mixing glucose, ammonium salt and molten salt uniformly, and then performing grinding treatment to obtain a slurry;
[0012] Performing multiple suction filtration treatment on the slurry, and then drying to obtain the final filler.
[0013] Further, comprising:
[0014] Mixing the glucose, the ammonium salt and the molten salt uniformly, and then performing a grinding treatment to obtain a slurry;
[0015] Performing multiple times of suction filtration treatment on the slurry, and then drying to obtain a solid;
[0016] Adding the solid into a sulfuric acid solution under the condition of an oil bath at 40 DEG C, heating and stirring, and obtaining a mixed solution after cooling;
[0017] Performing multiple times of suction filtration treatment on the mixed solution, and then drying to obtain a final filler.
[0018] Further, the molten salt comprises one or more of sodium chloride and potassium chloride; the ammonium salt is ammonium chloride, ammonium sulfate or ammonium phosphate; and the mass ratio of the glucose, the ammonium salt and the molten salt is 1: (1-2): (20-60).
[0019] Further, the grinding treatment is performed by using a planetary ball mill, and the grinding speed is 500-800 rpm.
[0020] Further, the multiple times of suction filtration treatment on the slurry is performed, and then drying; wherein the drying time is 12-24 h.
[0021] Further, the concentration of the sulfuric acid solution is 0.5-2 mol / L, and the volume ratio of the solid to the sulfuric acid solution is 1: (10-20).
[0022] Further, the stirring mode is magnetic stirring, the stirring duration is 36-48 h, and the stirring speed is 20-30 rpm.
[0023] Further, the multiple times of suction filtration treatment on the mixed solution is performed, and then drying to obtain a final filler, wherein the drying time is 12-24 h.
[0024] Compared with the prior art, the present application has the following beneficial effects:
[0025] The filler for modifying a proton exchange membrane provided by the present application comprises a carbon carrier and multiple functional groups loaded on the carbon carrier; the multiple functional groups comprise hydroxyl groups and amino groups, and further comprise sulfonic acid group; by introducing multiple functional groups, the water locking of the material is realized by the synergistic effect of different functional groups, the water retention performance of the material is improved, and the stability of the filler is high.
[0026] The preparation method of the filler for modifying a proton exchange membrane provided by the present application has a simple preparation process, controllable product quality, and can realize batch production. BRIEF DESCRIPTION OF DRAWINGS
[0027] Figure 1TEM images of the filler provided for the embodiment of the present application, wherein Figure 1 (a) TEM images of the filler provided for the embodiment 1, Figure 1 (b) TEM images of the filler provided for the embodiment 2;
[0028] Figure 2 FT-IR images of the filler provided for the embodiment 2 of the present application;
[0029] Figure 3 XPS full spectrum images of the filler provided for the embodiment of the present application, wherein Figure 3 (a) XPS full spectrum images of the filler provided for the embodiment 1, Figure 3 (b) XPS full spectrum images of the filler provided for the embodiment 2;
[0030] Figure 4 Schematic diagram of the water uptake of the composite proton exchange membrane added with the filler provided for the embodiment of the present application at 40℃, 60℃ and 80℃;
[0031] Figure 5 Schematic diagram of the water uptake of the different composite proton exchange membranes added with the filler provided for the embodiment of the present application at 40℃, 60℃ and 80℃;
[0032] Figure 6 Schematic diagram of the proton conductivity of the composite proton exchange membrane added with the filler provided for the embodiment of the present application under different conditions, wherein, Figure 6 (a) the proton conductivity diagram under different temperatures, Figure 6 (b) the proton conductivity diagram under different humidities. DETAILED DESCRIPTION
[0033] The present application will be further described below in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the present application, and cannot be used to limit the protection scope of the present application.
[0034] Embodiment 1
[0035] The present embodiment provides a filler for proton exchange membrane modification and a preparation method thereof.
[0036] The filler for proton exchange membrane modification provided by the present embodiment comprises a carbon carrier and a plurality of functional groups loaded on the carbon carrier, the carbon carrier has a sheet structure, and the plurality of functional groups comprises hydroxyl groups and amino groups, and the plurality of functional groups are used as water absorption and proton conduction sites.
[0037] The preparation method comprises the following steps:
[0038] (1) 1 g of glucose, 1.2 g of ammonium chloride and 44 g of sodium chloride are mixed and placed in a planetary ball mill pot;
[0039] (2) Put the planetary ball mill jar into the planetary ball mill and grind for 5h at a grinding speed of 600rpm;
[0040] (3) After the grinding is completed, draw filtration for 4 times, and dry for 24h to obtain the filler provided in the embodiment.
[0041] Embodiment 2
[0042] The embodiment provides a filler for modification of a proton exchange membrane and a preparation method thereof.
[0043] The filler for modification of a proton exchange membrane provided in the embodiment comprises a carbon carrier and a plurality of functional groups loaded on the carbon carrier, the carbon carrier has a sheet structure, the plurality of functional groups comprises hydroxyl groups, amino groups and sulfonic acid group, and the plurality of functional groups are used as water absorption and proton conduction sites.
[0044] The preparation method comprises the following steps:
[0045] (1) Mix 1g of glucose, 1.2g of ammonium chloride and 44g of sodium chloride, and place them in a planetary ball mill jar;
[0046] (2) Put the planetary ball mill jar into the planetary ball mill and grind for 5h at a grinding speed of 600rpm;
[0047] (3) After the grinding is completed, draw filtration for 4 times, and dry for 24h to obtain a solid.
[0048] (4) Under the condition of an oil bath at 40℃, add 100ml of 0.5mol / L dilute sulfuric acid solution to the solid, heat and magnetically stir for 48h at a stirring speed of 20rpm;
[0049] (5) After cooling, draw filtration for 4 times, and dry for 24h to obtain the filler provided in the embodiment.
[0050] Figure 1 The TEM image of the filler provided in the embodiment of the application is shown in the following figure, Figure 1 (a) is a TEM image of the filler provided in embodiment 1, Figure 1 (b) is a TEM image of the filler provided in embodiment 2, and Figure 1 It can be known that the fillers provided in embodiment 1 and embodiment 2 both have a sheet structure.
[0051] Figure 2 The Fourier transform infrared spectrum of the filler provided in the embodiment 2 of the application is shown in the following figure, Figure 2 It can be known that the filler provided in embodiment 2 has peaks at 1705 and 1635 wavelengths, respectively, corresponding to the stretching vibration peaks of C=O and N-H, the obviously wide peak at about 3430 is the peak of N-H and -OH, and the peaks at 1105 and 1210 prove the introduction of sulfonic acid groups.
[0052] Figure 3 XPS full spectrum of the filler provided by the embodiment of the present application, wherein Figure 3 (a) XPS full spectrum of the filler provided by Example 1, Figure 3 (b) XPS full spectrum of the filler provided by Example 2, in the XPS full spectrum of the two fillers, the characteristic peaks of the newly introduced group elements appear, from which Figure 3 (a) it can be known that the filler provided by Example 1 successfully introduces amino groups, from which Figure 3 (b) it can be known that the filler provided by Example 2 successfully introduces amino groups and sulfonic acid groups.
[0053] Figure 4 The swelling rate of the composite proton exchange membrane added with the filler provided by the embodiment of the present application at 40℃, 60℃ and 80℃ is shown in the schematic diagram, Figure 5 The water absorption rate of the composite proton exchange membrane added with the filler provided by the embodiment of the present application at 40℃, 60℃ and 80℃ is shown in the schematic diagram. Among them, NR212 is a commercial Nafion212 membrane, the unmodified self-made membrane is named PFSA-0, and the composite membrane is named NSGO / PFSA-X (X is 1-2.5, representing the mass percentage). Figure 4 and Figure 5 It can be known that the composite proton exchange membrane added with the filler provided by Example 2 has been significantly improved in water absorption performance and anti-swelling performance. With the increase of the filler, the water absorption performance of the composite membrane presents a trend of first increasing and then decreasing, while the swelling rate presents an opposite trend. This is due to the additional introduction of water absorption functional groups by the filler. In addition, the electrostatic interaction between amino groups and sulfonic acid groups and the hydrogen bond between multiple oxygen-containing functional groups limit the movement of polymer chains, thereby enhancing the anti-swelling performance of the composite membrane. However, when the mass ratio of the filler is 2.5wt%, the performance decreases due to the enhanced agglomeration of the filler in the membrane, forming more defects.
[0054] Figure 6 The proton conductivity of the composite proton exchange membrane added with the filler provided by the embodiment of the present application is shown in the schematic diagram, wherein, Figure 6 (a) is the proton conductivity diagram at different temperatures, Figure 6(b) is the proton conductivity graph under different humidity. Among them, Nafion 212 represents the commercial Nafion 212 membrane, PFSA-0 represents the self-made proton exchange membrane without adding fillers, NGO-PFSA represents the composite proton exchange membrane added with the fillers provided in Example 1, and NSGO-PFSA represents the composite proton exchange membrane added with the fillers provided in Example 2. It can be seen from the graph that the composite proton exchange membranes prepared by using the fillers of Example 1 and Example 2 are both improved in proton conductivity, and the fillers prepared in Example 2 are better for improving the proton conductivity of the proton exchange membrane, and have higher proton conductivity under the change of temperature and humidity. This is due to the fact that the fillers of Example 2 are further introduced with sulfonic acid groups on the basis of Example 1, so that there are more proton conduction sites and it is more conducive to forming a proton transfer channel, thereby further improving the performance.
[0055] The embodiments of the present application are described above in combination with the drawings, but the present application is not limited to the above specific embodiments, and the above specific embodiments are only illustrative but not restrictive. Those skilled in the art can make many forms under the inspiration of the present application without departing from the purpose of the present application and the scope protected by the claims, and these all belong to the protection of the present application.
Claims
1. A packing material for modifying proton exchange membranes, characterized in that: It includes a carbon support and various functional groups supported on the carbon support; The carbon support has a sheet-like structure; The various functional groups include hydroxyl groups and amino groups, which serve as sites for water absorption and proton conduction.
2. The packing material according to claim 1, characterized in that: The various functional groups also include sulfonic acid groups.
3. A method for preparing the filler as described in claim 1, characterized in that, include: Glucose, ammonium salt, and molten salt are mixed evenly and then ground to obtain a slurry. The slurry is subjected to multiple filtration processes and then dried to obtain the final filler.
4. A method for preparing the filler as described in claim 2, characterized in that, include: Glucose, ammonium salt, and molten salt are mixed evenly and then ground to obtain a slurry. The slurry was filtered multiple times and then dried to obtain a solid. The solid was added to a sulfuric acid solution in an oil bath at 40°C, heated and stirred, and then cooled to obtain a mixed solution. The mixed solution was subjected to multiple filtration processes and then dried to obtain the final packing material.
5. The preparation method according to claim 3 or 4, characterized in that: The molten salt includes one or more of sodium chloride and potassium chloride; the ammonium salt is ammonium chloride, ammonium sulfate, or ammonium phosphate; the mass ratio of glucose, ammonium salt, and molten salt is 1:(1-2):(20-60).
6. The preparation method according to claim 3 or 4, characterized in that: The grinding process is performed using a planetary ball mill at a grinding speed of 500-800 rpm.
7. The preparation method according to claim 3 or 4, characterized in that: The slurry is subjected to multiple filtration processes and then dried; the drying time is 12-24 hours.
8. The preparation method according to claim 4, characterized in that: The concentration of the sulfuric acid solution is 0.5-2 mol / L, and the volume ratio of the solid to the sulfuric acid solution is 1:(10-20).
9. The preparation method according to claim 4, characterized in that: The stirring method is magnetic stirring, the stirring duration is 36-48 hours, and the stirring speed is 20-30 rpm.
10. The preparation method according to claim 4, characterized in that: The mixed solution is subjected to multiple filtration processes and then dried to obtain the final packing material, wherein the drying time is 12-24 hours.