CN114874475B - Self-humidifying proton exchange membrane based on hollow polydopamine and preparation method and application thereof - Google Patents
Self-humidifying proton exchange membrane based on hollow polydopamine and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a self-humidifying proton exchange membrane based on hollow polydopamine, and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, a polydopamine coating layer is generated on the surface of the silicon dioxide particles to form polydopamine-coated silicon dioxide particle SiO 2 @ PDA, then to SiO using HF solution 2 Eroding silicon dioxide particles in the @ PDA to obtain a hollow polydopamine microsphere structure Hol-PDA; depositing nano Pt particles on the surface of the Hol-PDA to prepare Hol-PDA-Pt; and finally, mixing the Hol-PDA-Pt dispersion liquid with a resin solution, casting the mixture on the surface of glass, and performing drying and curing treatment to obtain the self-humidifying proton exchange membrane based on the hollow polydopamine. The self-humidifying proton exchange membrane prepared by the invention can ensure that the membrane has better proton conductivity under the condition of low humidity or no water.
Description
Technical Field
The invention relates to the technical field of proton exchange membranes, in particular to a self-humidifying proton exchange membrane based on hollow polydopamine, and a preparation method and application thereof.
Background
As a secondary energy source which has wide source, cleanness, no carbon, flexibility, high efficiency and rich application scene, the hydrogen energy is regarded as the ultimate energy source of the 21 st century and is an important component of the future world energy system. The Proton Exchange Membrane Fuel Cell (PEMFC) is an important link of a hydrogen energy industrial chain, is an environment-friendly and efficient power generation mode, and particularly has attractive prospect in the aspect of zero-emission traffic power application.
The design and preparation of proton exchange membranes with high proton conductivity are key to the commercial application of PEMFCs, and the most widely used membrane is polyperfluorosulfonic acid resin membrane, such as Nafion membrane manufactured by dupont.
However, such membranes need to maintain a certain humidity during proton conduction to ensure faster proton transfer from the anode to the cathode, and the reduced humidity or lack of water can cause a significant degradation in fuel cell performance. Therefore, a humidification system is generally required to be added to the PEMFC to maintain good wettability of the proton exchange membrane by humidifying the gas at the inlet of the fuel cell stack, but the introduction of the humidification system not only increases the complexity and volume of the system, but also greatly increases the preparation cost of the PEMFC. In addition, the failure of the humidifier may cause dehydration or flooding of the membrane, which also causes a drastic drop in the overall performance of the PEMFC. In order to solve this problem, development of a membrane electrode having a self-humidifying function is one of important approaches. However, the current self-humidification fuel cell technology still faces many problems, for example, the cell performance is seriously attenuated due to the slow proton conduction rate in the proton exchange membrane under the self-humidification condition, and in addition, the water retention performance of the membrane electrode is also a key factor influencing the composite membrane under the low humidity working condition.
Studies have shown that the formation of acid-base pairings in proton exchange membranes helps to increase the proton conduction rate of the proton exchange membrane, especially in the absence of water or water, since the proton donor (acid group) and the proton acceptor (basic group) spontaneously assemble to form a basic pair, protons can be transported between the donor and acceptor based on the Grottuss mechanism without the need for water molecules. Many studies have investigated acid-base paired composite membranes by adding additives (low molecular weight acids/bases) directly to the basic/acidic membranes, however since the additives are in the free mode, these membranes often suffer from leaching of the additives during operation, resulting in a decrease in proton conductivity.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a self-humidifying proton exchange membrane based on hollow polydopamine, and a preparation method and application thereof, and aims to solve the problems that the proton exchange membrane in the prior art has poor proton conduction rate and serious membrane electrode performance attenuation under the condition of low humidity or no water.
The technical scheme of the invention is as follows:
a preparation method of a self-humidifying proton exchange membrane based on hollow polydopamine comprises the following steps:
adding dopamine solution to SiO 2 In the dispersion, the generated polydopamine is coated on SiO after stirring 2 On the surface, polydopamine-coated silica particles, denoted as SiO, are formed 2 @PDA；
Adding the polydopamine coated silica particles into an HF solution, performing ultrasonic dispersion treatment, and performing magnetic stirring treatment to obtain a polydopamine hollow microsphere structure, which is marked as Hol-PDA;
adding the polydopamine hollow microsphere structure into H 2 PtCl 6 ·H 2 Dropwise adding an alkaline solution into the O solution until the pH value is a preset value, performing ultrasonic dispersion treatment and then performing microwave heating treatment to generate a polydopamine hollow microsphere structure with Pt particles deposited on the surface, and marking the polydopamine hollow microsphere structure as Hol-PDA-Pt;
dispersing Hol-PDA-Pt in a first organic solvent to obtain a Hol-PDA-Pt dispersion liquid;
dissolving SPEEK or Nafion in a second organic solvent to obtain a resin solution;
mixing the Hol-PDA-Pt dispersion liquid with a resin solution, and stirring after ultrasonic dispersion treatment to obtain a mixed solution;
and casting the mixed solution on glass, and performing drying treatment and curing treatment to obtain the self-humidifying proton exchange membrane based on the hollow polydopamine.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine comprises the following steps of:
mixing SiO 2 Dispersing the particles in Tris buffer solution and performing ultrasonic dispersion treatment to obtain SiO 2 A dispersion liquid;
dissolving dopamine in a Tris buffer solution to obtain a dopamine solution;
dripping the dopamine solution into SiO through a constant-pressure dropping funnel 2 In the dispersion, after the mechanical stirring reaction for 4 to 48 hours, the mixture is put into SiO 2 And (3) generating a polydopamine coating on the surface of the particle, washing with deionized water, and then drying under a vacuum condition to obtain the polydopamine-coated silica particle.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine is characterized in that the SiO 2 The particle size of the particles is 20-500nm.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine comprises the step of preparing the polydopamine-coated silicon dioxide particles 2 The mass ratio of the granules to the dopamine is 50.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine is characterized in that the concentration of the HF solution is 3-10wt%.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine is characterized in that H is 2 PtCl 6 ·H 2 The concentration of the O solution is 0.01-0.5 g/mL; and/or the concentration of the alkaline solution is 0.01-0.5 g/mL; and/or the preset value is 9-11.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine comprises the following steps of heating by microwave for 60-240s, wherein in the microwave heating treatment, the microwave power is 800 w.
The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine comprises the steps of casting the mixed solution onto glass, firstly drying for 2-8 hours at 60 ℃, then drying for 2-12 hours at 70-80 ℃ and finally curing for 4-12 hours at 100 ℃ in the steps of drying and curing.
The invention discloses a self-humidifying proton exchange membrane based on hollow polydopamine, which is prepared by the preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine.
The invention discloses an application of a self-humidifying proton exchange membrane based on hollow polydopamine, wherein the self-humidifying proton exchange membrane based on hollow polydopamine is used for preparing a proton exchange membrane fuel cell.
Has the advantages that: in the invention, polydopamine with a hollow structure is introduced in the process of preparing the self-humidifying proton exchange membrane, the polydopamine has more terminal amino functional groups, and can form acid-base pairs with acid sulfonic acid groups in Nafion or SPEEK, thereby ensuring better proton conductivity under the condition of low humidity or no water; the nano Pt particles are deposited on the outer surface of the polydopamine hollow microsphere structure, the hollow microsphere structure provides a large surface area for the large amount of nano Pt particles to be attached, and the amino functional groups on the surface of the polydopamine are beneficial to anchoring and dispersion of the nano Pt particles, so that the self-humidifying proton exchange membrane prepared by the method can be attached with more nano Pt particles in a unit area, and the self-humidifying performance of the proton exchange membrane is improved; furthermore, the hollow structure of the polydopamine also improves the storage capacity of water, so that the proton conductivity of the proton exchange membrane under the conditions of low humidity and no water is improved.
Drawings
Fig. 1 is a flow chart of a preparation method of a self-humidifying proton exchange membrane based on hollow polydopamine.
Fig. 2 is a schematic diagram of a preparation method of a self-humidifying proton exchange membrane based on hollow polydopamine.
FIG. 3 shows SiO prepared in example 1 of the present invention 2 SEM image of @ PDA.
FIG. 4 is an SEM photograph of Hol-PDA prepared in example 1 of the present invention.
Fig. 5 is a comparative graph showing the water absorption test results of the proton exchange membranes prepared in examples 1 to 2 and comparative example 1.
Fig. 6 is a graph comparing the results of proton conductivity tests of the proton exchange membranes prepared in example 2 and comparative example 1.
Detailed Description
The invention provides a self-humidifying proton exchange membrane based on hollow polydopamine, and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, the research of the self-humidifying membrane electrode is mostly carried out by adding Pt nano particles into a proton exchange membrane and catalyzing H diffused into the membrane from a cathode and an anode 2 And O 2 Water is generated in situ in the proton exchange membrane and is stored by the addition of some hydrophilic metal/non-metal oxides. However, most additives have limited storage capacity for water and lead to a low overall proton conductivity of the composite membrane due to poor proton conductivity of the metal/metalloid oxide introduced. Although acid-base paired composite membranes have been investigated by adding low molecular weight acids/bases directly to the basic/acidic membrane. However, since the additives are mostly in the free mode, these membranes often suffer from leaching of the additives during operation, resulting in a decrease in proton conductivity.
Based on the above, the invention provides a preparation method of a self-humidifying proton exchange membrane based on hollow polydopamine, as shown in fig. 1, which comprises the following steps:
s10, adding dopamine solution into SiO 2 In the dispersion, the generated polydopamine is coated on SiO after stirring 2 On the surface, polydopamine-coated silica particles, denoted as SiO, are formed 2 @PDA；
S20, adding the polydopamine coated silica particles into an HF solution, performing ultrasonic dispersion treatment, and performing magnetic stirring treatment to obtain a polydopamine hollow microsphere structure, wherein the structure is marked as Hol-PDA;
s30, adding the polydopamine hollow microsphere structure into H 2 PtCl 6 ·H 2 Dropwise adding an alkaline solution into the O solution until the pH value is a preset value, performing ultrasonic dispersion treatment and then performing microwave heating treatment to generate a polydopamine hollow microsphere structure with Pt particles deposited on the surface, and marking the polydopamine hollow microsphere structure as Hol-PDA-Pt;
s40, dispersing Hol-PDA-Pt in a first organic solvent to obtain a Hol-PDA-Pt dispersion liquid;
s50, dissolving SPEEK or Nafion in a second organic solvent to obtain a resin solution;
s60, mixing the Hol-PDA-Pt dispersion liquid with a resin solution, and stirring after ultrasonic dispersion treatment to obtain a mixed solution;
s70, casting the mixed solution on glass, and performing drying treatment and curing treatment to obtain the self-humidifying proton exchange membrane based on the hollow polydopamine.
Specifically, as shown in fig. 2, in this example, a polydopamine coating layer is formed on the surface of a silica particle to form a polydopamine-coated silica particle SiO 2 @ PDA, then to SiO using HF solution 2 Eroding silicon dioxide particles in the @ PDA to obtain a hollow polydopamine microsphere structure Hol-PDA; depositing nano Pt particles on the surface of the Hol-PDA to prepare Hol-PDA-Pt; and finally, mixing the Hol-PDA-Pt dispersion liquid with a resin solution, casting the mixture on the surface of glass, and performing drying and curing treatment, wherein in the process, amino functional groups on the surface of the Hol-PDA-Pt are combined with acid sulfonic acid groups in the resin solution to form acid-base pairs, so that the self-humidifying proton exchange membrane based on the hollow polydopamine is prepared.
In the embodiment, polydopamine with a hollow structure is introduced in the process of preparing the self-humidifying proton exchange membrane, and the polydopamine has more terminal amino functional groups and can form an acid-base pair with acid sulfonic acid groups in Nafion or SPEEK to be combined together, so that better proton conductivity is ensured under the condition of low humidity or no water; the nano Pt particles are deposited on the outer surface of the polydopamine hollow microsphere structure, the hollow microsphere structure provides a large surface area for a large amount of nano Pt particles to be attached, and the amino functional groups on the surface of the polydopamine are beneficial to anchoring and dispersing of the nano Pt particles, so that the self-humidifying proton exchange membrane prepared by the method can be attached with more nano Pt particles in a unit area, and the self-humidifying performance of the proton exchange membrane is improved; furthermore, the hollow structure of the polydopamine also improves the storage capacity of water, so that the proton conductivity of the proton exchange membrane is improved.
In some embodiments, the preparation of the polydopamine coated silica particles specifically comprises the steps of: mixing SiO 2 Dispersing the particles in Tris buffer solution and performing ultrasonic dispersion treatment to obtain SiO 2 A dispersion liquid; dissolving dopamine in a Tris buffer solution to obtain a dopamine solution; dripping the dopamine solution into SiO through a constant-pressure dropping funnel 2 In the dispersion, after the mechanical stirring reaction for 4 to 48 hours, the mixture is put into SiO 2 And (3) generating a polydopamine coating on the surface of the particle, washing with deionized water, and then drying under a vacuum condition to obtain the polydopamine-coated silica particle.
Because dopamine can generate oxidative self-polymerization reaction to generate polydopamine under the condition of oxygen and weak base, in this embodiment, dopamine solution is slowly dripped into SiO through a constant pressure dropping funnel 2 In the process of dispersing and stirring, the dopamine gradually undergoes self-polymerization to generate polydopamine, and the polydopamine has strong adhesion performance, so that the polydopamine generated in the embodiment can adhere to the surfaces of the silica particles to form polydopamine-coated silica particles. In this embodiment, the SiO 2 The pH value of the dispersion liquid is between 8 and 9, so that the oxidation self-polymerization reaction of the dopamine is facilitated.
In some embodiments, the SiO 2 The particle size of the particles is 20-500nm. In the process of preparing polydopamine-coated silica particles, the SiO 2 The mass ratio of the granules to the dopamine is 50-20.
In some embodiments, the SiO is 2 @ PDA is added to a 3-10 wt.% HF solutionPerforming ultrasonic dispersion for 5-20min, then magnetically stirring for 6-72h, and after the reaction is finished, performing SiO reaction by using the HF solution 2 And finishing erosion of the silica particles in the @ PDA, washing the silica particles for multiple times by using deionized water, and drying the silica particles for 24 hours under the condition of vacuum drying at the temperature of 60 ℃ to obtain the hollow polydopamine microsphere structure Hol-PDA.
In some embodiments, the Hol-PDA is dispersed in H at a concentration of 0.01-0.5 g/mL 2 PtCl 6 ·H 2 Adding 0.1-0.5 mol/L NaOH or KOH solution dropwise into O glycol solution, adjusting the pH value of the solution to 9-11, performing ultrasonic dispersion for 5-30 min, placing the mixed solution in a 800W microwave reactor for reaction for 60-240s, centrifuging after the reaction is finished, washing the mixed solution for multiple times by using deionized water, and finally drying the mixed solution in a vacuum drying oven at 60 ℃ for 24h to generate a polydopamine hollow microsphere structure with Pt particles deposited on the surface, wherein the polydopamine hollow microsphere structure is marked as Hol-PDA-Pt.
In this embodiment, nano Pt particles are deposited on the outer surface of the hollow poly-dopamine microsphere structure, the hollow poly-dopamine microsphere structure provides a large surface area for a large number of nano Pt particles to be attached, and the amino functional groups on the surface of poly-dopamine are favorable for anchoring and dispersing the nano Pt particles, so that the self-humidifying proton exchange membrane prepared in this embodiment can attach more nano Pt particles in a unit area, and the nano Pt particles can catalyze H diffused into the proton exchange membrane from the cathode and the anode respectively 2 And O 2 And water is generated through in-situ reaction in the proton exchange membrane, and the more the nano Pt particles are attached to the proton exchange membrane in a unit area, the higher the catalytic efficiency is, and the self-humidifying performance of the proton exchange membrane can be improved.
In some embodiments, the first organic solvent and the second organic solvent may both be DMF, but are not limited thereto. Specifically, the present example prepares composite films with different doping contents by a solvent casting method. Firstly, hol-PDA-Pt is dispersed in a DMF solution, ultrasonic dispersion is carried out for 30min, and then magnetic stirring is carried out for 1-8 h, so as to prepare Hol-PDA-Pt dispersion liquid; dissolving SPEEK or Nafion in a certain amount of DMF, and magnetically stirring until the SPEEK or Nafion is completely dissolved to obtain a resin solution; then mixing the Hol-PDA-Pt dispersion liquid with a resin solution, carrying out ultrasonic dispersion for 20-40 min, and stirring for 1-6 h at room temperature to obtain a mixed solution; and then casting the mixed solution on transparent glass, drying for 2-8h at 60 ℃, then drying for 2-12h at 70-80 ℃, and finally curing for 4-12 h at 100 ℃ to prepare the self-humidifying proton exchange membrane based on the hollow polydopamine.
In this embodiment, as shown in fig. 2, the polydopamine with a hollow microsphere structure has more terminal amino functional groups (basic groups), which can form an acid-base pair with acidic sulfonic acid groups in Nafion or SPEEK, and since the proton donor (acidic group) and the proton acceptor (basic group) can spontaneously assemble to form an acid-base pair, protons can be transported between the proton donor and the proton acceptor based on the Grottuss mechanism without water molecules, this embodiment can ensure that the prepared self-humidifying proton exchange membrane has better proton conductivity under low humidity or no water.
In some embodiments, the invention further provides a self-humidifying hollow polydopamine-based proton exchange membrane, wherein the membrane is prepared by the preparation method of the self-humidifying hollow polydopamine-based proton exchange membrane.
In some embodiments, the invention also provides a use of the self-humidifying hollow polydopamine-based proton exchange membrane for preparing a proton exchange membrane fuel cell. In the invention, because the proton exchange membrane provided by the invention has better self-humidifying effect and can improve the conductivity of protons, the volume of a proton exchange membrane fuel cell system can be greatly reduced, the power density of the proton exchange membrane fuel cell is improved, and the manufacturing cost of the fuel cell is effectively reduced.
The invention is further illustrated by the following specific examples:
example 1
A preparation method of a self-humidifying proton exchange membrane comprises the following steps:
1) Synthetic dopamine hollow microspheres
a. Coated dopamine
Taking SiO with the grain diameter of 300 nm purchased in the market 2 The pellet, 0.5g, was washed three times with 30 mL of 10 mM Tris buffer, then dispersed in 20-100 mL Tris buffer, and sonicated for 10 minutes. 0.1g of dopamine was dissolved in 10 mL of Tris buffer and slowly added dropwise to SiO through a constant pressure dropping funnel 2 Dispersing Tris buffer solution, mechanically stirring, reacting for 24h at normal temperature, washing with deionized water for three times after the reaction is finished, and drying for 24h under the condition of vacuum drying at 60 ℃ to obtain SiO 2 @ PDA, said SiO 2 SEM images of the @ PDA are shown in FIG. 3.
b. Synthetic dopamine hollow microspheres
Taking the above SiO 2 0.5g of @ PDA particles are added into 50 mL of 5wt% HF solution, ultrasonically dispersed for 10min, then magnetically stirred for 10h, and after the reaction is finished, the mixture is washed for many times by deionized water and dried for 24h under the vacuum drying condition at 60 ℃, and the mark is Hol-PDA, and the SEM picture of the Hol-PDA is shown in figure 4.
2) Surface deposition of Pt
0.5g of hollow PDA microspheres were dispersed in 80 mL of H 2 PtCl 6 ·H 2 Adding 0.3 mol/L KOH solution dropwise into O glycol solution (the concentration is 0.25 g/mL), adjusting the pH value of the solution to 10.0, performing ultrasonic dispersion for 20min, placing the mixed solution into a 800W microwave reactor for reaction for 120 s, centrifuging after the reaction is finished, washing for many times by deionized water, and finally placing the mixed solution into a vacuum drying oven for drying for 24h at 60 ℃, wherein the product is marked as Hol-PDA-Pt.
3) Preparation of self-humidifying proton exchange membrane
Preparing self-humidifying proton exchange membranes with different doping contents by a solvent casting method, taking Hol-PDA-Pt to disperse in a DMF solution, ultrasonically dispersing for 30min, and then magnetically stirring for 4h. Dissolving Nafion in a certain amount of DMF, magnetically stirring until completely dissolving, mixing the two solutions, ultrasonically dispersing for 30min, and stirring at room temperature for 3h. And then, casting the obtained solution on transparent glass, drying for 5 hours at the temperature of 60 ℃, then drying for 7 hours at the temperature of 80 ℃, and finally curing for 8 hours at the temperature of 100 ℃ to prepare the self-humidifying proton exchange membrane.
Example 2
A method of preparing a self-humidifying proton exchange membrane, comprising the steps of:
1) Synthetic dopamine hollow microspheres
a. Coated dopamine
Using commercially available SiO with different particle sizes of 200nm 2 The pellet, 0.5g, was washed three times with 30 mL of 10 mM Tris buffer, then dispersed in 100 mL Tris buffer, and sonicated for 10 minutes. 0.2g of dopamine was dissolved in 10 mL of Tris buffer and slowly added dropwise to SiO through a constant pressure dropping funnel 2 Mechanically stirring in dispersed Tris buffer solution, reacting at normal temperature for 30h, washing with deionized water for three times after the reaction is finished, and drying at 60 ℃ for 24h under vacuum drying condition to obtain SiO 2 @PDA。
b. Synthetic dopamine hollow microspheres
Taking the above SiO 2 0.5g of @ PDA particles are added into 50 mL of 8 wt% HF solution, ultrasonically dispersed for 10min, then magnetically stirred for 60h, washed for many times by deionized water after the reaction is finished, and dried for 24h under the condition of vacuum drying at 60 ℃, and the mark is Hol-PDA.
2) Surface deposition of Pt
0.5g of hollow PDA microspheres were dispersed in 100 mL of H 2 PtCl 6 ·H 2 Adding 0.5 mol/L NaOH solution dropwise into O glycol solution (the concentration is 0.4 g/mL), adjusting the pH value of the solution to 10.0, performing ultrasonic dispersion for 20min, placing the mixed solution in a 800W microwave reactor for reaction for 200 s, centrifuging after the reaction is finished, washing for many times by deionized water, and finally drying in a vacuum drying oven at 60 ℃ for 24h, wherein the mark is Hol-PDA-Pt.
3) Preparation of self-humidifying proton exchange membrane
Preparing self-humidifying proton exchange membranes with different doping contents by a solvent casting method, taking Hol-PDA-Pt to disperse in a DMF solution, ultrasonically dispersing for 30min, and then magnetically stirring for 1-8 h. Dissolving SPEEK in DMF, magnetically stirring until completely dissolved, mixing the two solutions, ultrasonically dispersing for 30min, and stirring at room temperature for 5 h. And then, casting the obtained solution on transparent glass, drying for 6h at the temperature of 60 ℃, then drying for 10h at the temperature of 70 ℃, and finally curing for 10h at the temperature of 100 ℃ to prepare the self-humidifying proton exchange membrane.
Comparative example 1
And (2) dissolving the SPEEK in DMF, magnetically stirring until the SPEEK is completely dissolved to obtain a SPEEK solution, casting the SPEEK solution on transparent glass, drying for 6 hours at the temperature of 60 ℃, then drying for 10 hours at the temperature of 70 ℃, and finally curing for 8 hours at the temperature of 100 ℃ to obtain the proton exchange membrane.
The proton exchange membranes prepared in the above examples 1 to 2 and comparative example 1 were subjected to a water absorption test under the same environment, and the results are shown in fig. 5, and it can be seen from the results of fig. 5 that the water absorption of the proton exchange membranes in examples 1 and 2 is higher than that of the proton exchange membranes in comparative example 1, and the water absorption of example 2 is the highest.
The proton conductivity tests of the proton exchange membranes prepared in example 2 and comparative example 1 are performed under the same environment, and the results are shown in fig. 6, and it can be seen from the results of fig. 6 that the proton conductivity of the proton exchange membrane in example 2 is significantly higher than that of the proton exchange membrane in comparative example 1.
In conclusion, in the process of preparing the self-humidifying proton exchange membrane, polydopamine with a hollow structure is introduced, and the polydopamine has more terminal amino functional groups and can form acid-base pairs with acid sulfonic acid groups in Nafion or SPEEK, so that better proton conductivity is ensured under the condition of low humidity or no water; the nano Pt particles are deposited on the outer surface of the polydopamine hollow microsphere structure, the hollow microsphere structure provides a large surface area for the large amount of nano Pt particles to be attached, and the amino functional groups on the surface of the polydopamine are beneficial to anchoring and dispersion of the nano Pt particles, so that the self-humidifying proton exchange membrane prepared by the method can be attached with more nano Pt particles in a unit area, and the self-humidifying performance of the proton exchange membrane is improved; furthermore, the hollow structure of the polydopamine also improves the storage capacity of water, so that the proton conductivity of the proton exchange membrane is improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a self-humidifying proton exchange membrane based on hollow polydopamine is characterized by comprising the following steps:
adding dopamine solution to SiO 2 In the dispersion, the generated polydopamine is coated on SiO after stirring 2 On the surface, polydopamine-coated silica particles, denoted as SiO, are formed 2 @PDA；
Adding the polydopamine coated silica particles into an HF solution, performing ultrasonic dispersion treatment, and performing magnetic stirring treatment to obtain a polydopamine hollow microsphere structure, which is marked as Hol-PDA;
adding the polydopamine hollow microsphere structure to H 2 PtCl 6 ·H 2 Dropwise adding an alkaline solution into the O solution until the pH value is a preset value, performing ultrasonic dispersion treatment and then performing microwave heating treatment to generate a polydopamine hollow microsphere structure with Pt particles deposited on the surface, and marking the polydopamine hollow microsphere structure as Hol-PDA-Pt;
dispersing Hol-PDA-Pt in a first organic solvent to obtain a Hol-PDA-Pt dispersion liquid;
dissolving SPEEK or Nafion in a second organic solvent to obtain a resin solution;
mixing the Hol-PDA-Pt dispersion liquid with a resin solution, and stirring after ultrasonic dispersion treatment to obtain a mixed solution;
and casting the mixed solution on glass, and performing drying treatment and curing treatment to obtain the self-humidifying proton exchange membrane based on the hollow polydopamine.
2. The method for preparing a self-humidifying hollow polydopamine-based proton exchange membrane according to claim 1, wherein the preparation of the polydopamine-coated silica particles specifically comprises the steps of:
mixing SiO 2 Dispersing the particles in Tris buffer solution and performing ultrasonic dispersion treatment to obtain SiO 2 A dispersion liquid;
dissolving dopamine in a Tris buffer solution to obtain a dopamine solution;
dripping the dopamine solution into SiO by a constant pressure dropping funnel 2 In the dispersion, after the mechanical stirring reaction is carried out for 4 to 48 hours, the mixture is put into SiO 2 And (3) generating a polydopamine coating on the surface of the particle, washing with deionized water, and drying under a vacuum condition to obtain the polydopamine-coated silica particle.
3. The method of claim 2, wherein the SiO is selected from the group consisting of 2 The particle size of the particles is 50-500nm.
4. The method of claim 2, wherein the SiO is coated with a silicon dioxide during the process of preparing the polydopamine-coated silica particles 2 The mass ratio of the granules to the dopamine is 50.
5. The method for preparing a self-humidifying hollow polydopamine-based proton exchange membrane according to claim 1, wherein the concentration of the HF solution is 3-10wt%.
6. The method of claim 1, wherein the H is selected from the group consisting of 2 PtCl 6 ·H 2 The concentration of the O solution is 0.01-0.5 g/mL; and/or the concentration of the alkaline solution is 0.01-0.5 g/mL; and/or the preset value is 9-11.
7. The method for preparing the self-humidifying hollow polydopamine-based proton exchange membrane according to claim 6, wherein in the microwave heating treatment, the microwave power is 800w, and the heating time is 60-240s.
8. The preparation method of the self-humidifying proton exchange membrane based on the hollow polydopamine, as claimed in claim 1, is characterized in that the step of casting the mixed solution on glass, firstly drying at 60 ℃ for 2-8h, then drying at 70-80 ℃ for 2-12h, and finally curing at 100 ℃ for 4-12 h.
9. A self-humidifying hollow polydopamine-based proton exchange membrane, which is characterized by being prepared by the preparation method of the self-humidifying hollow polydopamine-based proton exchange membrane according to any one of claims 1 to 8.
10. Use of a hollow polydopamine-based self-humidifying proton exchange membrane according to claim 9 for the preparation of a proton exchange membrane fuel cell.
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