CN111554955A - Self-humidifying composite proton exchange membrane preparation method, membrane electrode and fuel cell - Google Patents
Self-humidifying composite proton exchange membrane preparation method, membrane electrode and fuel cell Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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Abstract
The invention provides a preparation method of a self-humidifying composite proton exchange membrane, a membrane electrode and a fuel cell, wherein the preparation method comprises the following steps: and casting or spraying the Pt-containing proton exchange membrane resin homogeneous liquid onto the porous reinforced membrane to prepare the Pt-containing porous reinforced membrane, and drying the Pt-containing porous reinforced membrane to prepare the self-humidifying composite proton exchange membrane. The method is simple to operate, the synthesized self-humidifying composite proton exchange membrane effectively solves the problem of self-humidifying of the proton exchange membrane, ensures that the self-humidifying composite proton exchange membrane can not generate electronic short circuit in the membrane, has high proton conductivity, does not influence gas mass transfer, and can reduce the cost of the membrane electrode.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a self-humidifying composite proton exchange membrane, a membrane electrode and a fuel cell.
Background
A Fuel Cell, especially a Proton Exchange Membrane Fuel Cell (PEMFC), is an energy conversion device that can directly convert chemical energy in Fuel and oxidant into electrical energy, and has the advantages of high energy conversion rate, high energy density, no pollution, low operating temperature, etc., and is considered as one of the most promising clean energy technologies in the future. Proton Exchange Membrane (PEM) is one of the key components of PEMFCs, and its performance directly affects the cell performance and lifetime of PEMFCs. It is well known that hydrogen ions or protons are transported in a proton exchange membrane to be able to have a high proton conductivity while maintaining sufficient water therein. Therefore, maintaining sufficient moisture in the PEM is critical to the performance of the PEMFC. In addition, maintaining uniform moisture in the PEM helps prevent localized drying or localized heating, thereby effectively avoiding the occurrence of higher localized impedance. In summary, dehydration of the PEM results in increased impedance, degradation of the PEM, and significant performance degradation.
Currently, the humidification mode of PEMFCs mainly includes two modes, namely external humidification and internal humidification. External humidification is to humidify the gas entering the cell by using a gas humidifier (for example, U.S. Pat. No.6,403,249, jun.11,2002), which can achieve effective humidification of the PEM, but also makes the structure of the cell system more complicated, increases energy consumption, and reduces the net output power of the fuel cell. The internal humidification is mainly to humidify the PEM by utilizing water generated in the process of electrochemical reaction of the fuel cell during operation. This self-humidification maintains the proper operation of the battery without the aid of external equipment. US6207312 discloses a self-humidifying fuel cell which uses water produced at the cathode as moisture for humidifying the PEM, which method avoids the use of external equipment. However, such PEMFCs require complex bipolar plate flow channel designs and structures. EP0926754 uses presynthesized nano SiO2The powder is mixed into the proton exchange membrane resin solution to form a membrane, and the membrane can keep higher conductivity at 145 ℃, but the nano SiO2The powder is easy to agglomerate in the phase transfer process, the grain diameter is difficult to control, and the mechanical strength of the film is low. CN101145614A discloses coating an inorganic hydrophilic material with moisture retention function on one side of a diffusion layer to form a constant moisture layer on one side of the diffusion layer, then coating a catalyst on the constant moisture layer, and then hot-pressing the constant moisture layer to two sides of a PEM, which improves the moisture retention performance of the PEM, but increases the internal resistance of the membrane electrode due to the poor proton conductivity of the inorganic hydrophilic material, and secondly, the moisture retention layer may hinder the diffusion of gas into the catalyst layer, thereby reducing the electrical performance of the cell, and finally, there is great difficulty in preparing a uniform inorganic hydrophilic material on the surface of the PEM.
Therefore, a new technical solution is urgently needed to solve the problems of increased impedance, PEM degradation and significant performance degradation caused by dehydration of a Proton Exchange Membrane (PEM) on the premise of ensuring the performance of a fuel cell.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a self-humidifying composite proton exchange membrane, and the proton exchange membrane prepared by the method not only effectively solves the problem of PEM dehydration through self-humidifying of the proton exchange membrane, but also ensures that no electronic short circuit occurs in the membrane while ensuring the self-humidifying of the PEM, has high proton conductivity, does not influence gas mass transfer, and can reduce the cost of the membrane electrode.
In order to achieve the above object, the invention adopts the following technical scheme: a preparation method of a self-humidifying composite proton exchange membrane comprises the following steps: and casting or spraying the Pt-containing proton exchange membrane resin homogeneous liquid onto the porous reinforced membrane to prepare the Pt-containing porous reinforced membrane, and drying the Pt-containing porous reinforced membrane to prepare the self-humidifying composite proton exchange membrane. The noble metal Pt is added in the self-humidifying composite proton exchange membrane, which is beneficial to trace H permeated from the cathode and the anode2And O2Water is generated through the catalytic reaction of noble metal Pt, so that the effects of maintaining the moisture in the membrane and improving the open-circuit voltage are achieved; meanwhile, the casting/spraying method is beneficial to the uniform dispersion of the noble metal Pt in the self-humidifying composite proton exchange membrane, and effectively avoids the formation of a local electronic channel in the membrane, so that the phenomenon of electronic short circuit cannot occur in the membrane.
Further optionally, the drying treatment comprises drying for 12-36 hours at 30-50 ℃ under vacuum.
Further alternatively, the preparation of the Pt-containing proton exchange membrane resin homogeneous solution comprises: dissolving Pt supported catalyst in the homogeneous resin solution of proton exchange membrane, and oscillating, ultrasonic treating and stirring.
Further optionally, the oscillating, ultrasonic and stirring treatment comprises oscillating for 24 hours, ultrasonic for 0.5-6 hours and stirring for 0.5-6 hours.
Further optionally, the mass ratio of Pt in the homogeneous solution of the Pt-containing proton exchange membrane resin to the proton exchange membrane resin is 0.01: 1-0.2: 0.01. The self-humidifying performance and the proton conduction rate of the self-humidifying composite proton exchange membrane prepared by the method are improved.
Further optionally, the preparing of the proton exchange membrane resin homogeneous solution includes dissolving the proton exchange membrane resin in an organic solution to prepare the proton exchange membrane resin homogeneous solution.
Further optionally, the content of the proton exchange membrane resin homogeneous liquid is 7% to 13%. The performance of the prepared self-humidifying composite proton exchange membrane, such as proton conductivity, is improved.
Further optionally, the pore size of the porous reinforced membrane is 0.2 μm to 0.7 μm; the thickness of the porous reinforced membrane is 5-155 mu m; the porosity of the porous reinforced membrane is 60-90%. The porous reinforced membrane improves the distribution uniformity of Pt in the prepared self-humidifying composite proton exchange membrane, improves the proton conduction rate and reduces the internal resistance.
Further optionally, the method further comprises: and heating the dried Pt-containing porous reinforced membrane under the inert gas condition. The proton exchange membrane resin in the Pt-containing porous reinforced membrane is activated by heating treatment, so that the pore channel of the Pt-containing porous reinforced membrane is opened, the internal resistance is reduced, and the permeability of water and protons is better.
Further optionally, the heating process comprises: heating for 8-12 hours at the temperature of 110 ℃. The effect of better activating the performance of the self-humidifying composite proton exchange membrane is realized.
Further optionally, the method further comprises the step of sequentially placing the Pt-containing porous reinforced membrane after the heating treatment in H2O2Solution and dilute H2SO4Ultrasonic treatment is carried out in the solution. The step is used for carrying out pretreatment on the prepared Pt-containing porous reinforced membrane, so that the internal resistance of the Pt-containing porous reinforced membrane is reduced, and the permeability of the Pt-containing porous reinforced membrane to water and protons is improved.
Further optionally, the sonication comprises: at 3% -5% H2O2Ultrasonic treatment is carried out for 1-3 hours in the solution, the solution is taken out and washed by deionized water, and then the solution is placed in dilute H2SO4Ultrasonic treatment is carried out for 2-3 hours at medium and normal temperature, and finally deionized water is used for cleaning.
Further optionally, the method further comprises the step of subjecting the porous reinforced membrane containing Pt after ultrasonic treatment to performance enhancement treatment by using a graphene oxide solution. The thermal stability of the Pt-containing porous reinforced membrane is improved, the internal resistance of the porous reinforced membrane is greatly reduced, the water back-diffusion coefficient of the membrane is accelerated, the proton conduction rate is accelerated, the battery performance is improved, and the battery cost is reduced.
Further optionally, comprising: 1) dissolving a Pt supported catalyst in a uniform solution of a proton exchange membrane resin, oscillating for 24 hours, carrying out ultrasonic treatment for 0.5-6 hours, and stirring for 0.5-6 hours to prepare a uniform solution of the Pt-containing proton exchange membrane resin; 2) casting or spraying the homogeneous solution of the Pt-containing proton exchange membrane resin on a porous reinforced membrane by a casting or spraying method, and drying for 12-36 hours at 30-50 ℃ under vacuum to obtain the self-humidifying composite proton exchange membrane; 3) heating the self-humidifying composite proton exchange membrane for 8-12 hours at 110 ℃ under the protection of inert gas; 4) placing the self-humidifying composite proton exchange membrane after heating treatment in 3-5% H2O2Performing ultrasonic treatment in the solution for 1-3 hours, taking out the solution, cleaning the solution with deionized water, and placing the solution in dilute H2SO4Carrying out ultrasonic treatment for 2-3 hours at a medium normal temperature, and finally cleaning with deionized water; 5) and spraying the graphene oxide solution onto the self-humidifying composite proton exchange membrane.
The invention also provides a membrane electrode which comprises a proton exchange membrane, wherein the proton exchange membrane is prepared by adopting the self-humidifying composite proton exchange membrane preparation method.
The invention also provides a fuel cell, which comprises the proton exchange membrane prepared by adopting the self-humidifying composite proton exchange membrane preparation method and/or the membrane electrode.
Further optionally, the fuel cell is a proton exchange membrane fuel cell.
Has the advantages that:
the proton exchange membrane prepared by the method not only can realize the self-humidifying effect, but also can simplify the gas flow field design of a fuel cell, increase the self-humidifying operation stability and improve the cell performance of the PEMFC by introducing the noble metal Pt into the proton exchange membrane to prepare the self-humidifying membrane, and simultaneously, the Pt is uniformly distributed in the membrane, so that the local electronic channel is effectively prevented from being formed in the membrane, and the phenomenon of electronic short circuit cannot occur in the membrane; the introduction of the graphene oxide improves the thermal stability of the proton exchange membrane, and simultaneously, the oxidation-reduction function of the graphene oxide is utilized, so that oxygen is more easily generated on the surface of the graphene oxide and water is generated with protons, and the self-humidifying performance of the proton exchange membrane is further improved.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings. The drawings described below are merely exemplary embodiments of the present disclosure, and other drawings may be derived by those skilled in the art without inventive effort.
FIG. 1 is a schematic structural diagram of a self-humidifying composite proton exchange membrane according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of the operation of a self-humidifying composite proton exchange membrane according to an embodiment of the present invention;
fig. 3 is a performance test analysis curve of a single cell of a pem fuel cell under a full humidification condition and a no external humidification condition in accordance with an embodiment of the present invention.
In the figure:
1-porous reinforced membrane containing Pt; 2-graphene oxide flakes
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and "a" and "an" generally include at least two, but do not exclude at least one, unless the context clearly dictates otherwise.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
In order to overcome the problems that the dehydration of a Proton Exchange Membrane (PEM) of a fuel cell, especially a PEMFC (PEMFC), causes the increase of impedance, the degradation of the PEM and the obvious reduction of performance, in the prior art, an external humidification mode is adopted, mainly a gas humidifier is used for humidifying gas which is about to enter a cell, the method can realize the effective humidification of the PEM, but also makes the structure of a cell system more complex, increases energy consumption and reduces the net output power of the fuel cell; the adopted internal humidification mode is mainly to humidify the PEM by utilizing water generated in the process of electrochemical reaction of the fuel cell in the operation process, but also has the problems of causing the cell structure to be complex, reducing the cell performance and even causing the cell to fail. In view of the above, the invention provides a preparation method of a self-humidifying composite proton exchange membrane, the self-humidifying composite proton exchange membrane prepared by the method can realize the self-humidifying effect, and a membrane electrode and a fuel cell with the proton exchange membrane, especially a proton exchange membrane fuel cell, have good performances. In order to better understand the technical solution of the present invention, the following examples are given.
Example 1
The embodiment provides a preparation method of a self-humidifying composite proton exchange membrane, which comprises the following steps: casting or spraying the Pt-containing proton exchange membrane resin homogeneous liquid onto the porous reinforced membrane to prepare the Pt-containing porous reinforced membrane 1, and drying the Pt-containing porous reinforced membrane 1 to prepare the self-humidifying composite proton exchange membrane.
As shown in figure 2, the self-humidifying composite proton exchange membrane is internally provided with a noble metal Pt, and the design can lead H which is permeated with each other2And O2Water is generated under the catalytic action of noble metal Pt, and cathode back diffusion water in the cell humidifies the proton exchange membrane together, so that the mixed potential of permeating gas generated on the electrode is effectively eliminated, the polarization of the oxygen electrode is obviously reduced, the Open Circuit Voltage (OCV) of the cell is improved, and moreover, the introduction of the noble metal Pt can prevent H from being generated2And O2Permeation and diffusion in the membrane, effective inhibition of HO2And HO, etc., effectively eliminating the mixed overpotential from the risk of membrane degradation caused by the attack of oxidative radicals on the polymerThereby improving the open circuit voltage and the battery performance of the battery. The casting/spraying method used in the invention is beneficial to the uniform dispersion of the noble metal Pt in the self-humidifying composite proton exchange membrane, and effectively avoids the formation of a local electronic channel in the membrane, so that the phenomenon of electronic short circuit cannot occur in the membrane. The synthesis method of the self-humidifying composite proton exchange membrane is simple, and adopts a casting or spraying method in the aspect of the membrane casting process, so that the complex synthesis steps are not needed, the complex equipment requirements are avoided, and the operation is simple, convenient and quick.
There are various drying methods, and in order to achieve a better drying effect, it is preferable in this embodiment that the drying treatment is performed for 12 to 36 hours under vacuum at 30 to 50 ℃.
In the preparation method of the homogeneous solution of proton exchange membrane resin containing Pt in the above step, preferably, the Pt-supported catalyst is dissolved in the homogeneous solution of proton exchange membrane resin, and then subjected to vibration, ultrasonic treatment and stirring treatment. Further preferably, the oscillating, ultrasonic and stirring treatment comprises oscillating for 24 hours, ultrasonic for 0.5-6 hours and stirring for 0.5-6 hours. The active component of the catalyst is one or more of Pt, Au, Pd and Ag, Pt is preferable in the implementation, and the catalyst uses SO-2 4/FeO3、SO-2 4/ZrO2、SO-2 4/TiO2、SO-2 4/(WO3-ZrO2) One or more of the compounds is used as a carrier, and Pt is loaded on the carrier, so that the catalyst is the most common catalyst on the market at present, the acquisition route is easy, and the cost is low. More preferably, the carrier of the Pt supported catalyst is SO-2 4/ZrO2The prepared catalyst is a supported catalyst Pt/(SO)-2 4/ZrO2)。
In order to improve the self-humidifying effect and proton conductivity of the self-humidifying composite proton exchange membrane, in the present embodiment, the mass ratio of Pt in the homogeneous liquid of the Pt-containing proton exchange membrane resin to the proton exchange membrane resin is preferably 0.01:1 to 0.2: 0.01.
The proton exchange membrane resin homogeneous solution is completely the same in the content of the proton exchange membrane resin at each position of the solution, namely the composition and the property of the solution, and the homogeneous solution has strong stability, namely, when the temperature is not changed and the solvent amount is not changed, the solute and the solvent can not be separated for a long time. The preparation of the homogeneous proton exchange membrane resin solution preferably used in this embodiment includes dissolving the proton exchange membrane resin in an organic solution to obtain the homogeneous proton exchange membrane resin solution, that is, the homogeneous proton exchange membrane resin and the organic solution are uniformly mixed and form a multi-component system with mutually dispersed molecules to form a uniform and stable mixed solution. In order to improve the performance of the prepared self-humidifying composite proton exchange membrane, in the implementation, the content of the proton exchange membrane resin in the homogeneous solution of the proton exchange membrane resin is preferably 7-13%.
In the present study, the proton exchange membrane resin material is all polymer resin, and the proton exchange membrane using the polymer resin structure is favorable for the transmission of water and protons in the membrane, and in this embodiment, the proton exchange membrane resin material is preferably any one of perfluorosulfonic acid resin (such as Nafion, Flemien, Aciplex, or Dow resin), Sulfonated Polyarylether Sulfone (SPSU), sulfonated polyether ether ketone (SPEEK), partially fluorinated Sulfonated Polystyrene (SPFS), partially fluorinated sulfonated polyarylether sulfone, or partially fluorinated sulfonated polyarylether ketone. The proton exchange membrane resin homogeneous solution is prepared by utilizing the characteristic that the high molecular resin material is used in the organic solvent, and in the implementation, any one of the organic solvents of isopropanol, glycerol and glycol is preferred. Further preferably, the organic solvent is isopropanol.
The porous reinforced membrane in the preparation method not only provides a supporting function, but also has gaps for allowing protons and water to pass through so as to meet the normal work of the fuel cell, and Pt is uniformly distributed in the prepared self-humidifying composite proton exchange membrane, preferably, the pore diameter of the porous reinforced membrane is 0.2-0.7 mu m; the thickness of the porous reinforced film is 5-155 μm; the porosity of the porous reinforced membrane is 60-90%. More preferably, the porous reinforcing membrane is a polytetrafluoroethylene porous membrane.
In order to further improve the performance of the prepared self-humidifying composite proton exchange membrane, in the implementation, the dried porous reinforced membrane 1 containing Pt is preferably subjected to inert gasAnd (4) performing heating treatment. The heating treatment can activate the proton exchange membrane resin in the self-humidifying composite proton exchange membrane, so that the pore channel of the proton exchange membrane is opened, the internal resistance is reduced, and the permeability of water and protons is better. The operation under the inert gas condition is to prevent the self-humidifying composite proton exchange membrane from being oxidized at high temperature. Preferably, the inert gas is Ar or N2One kind of (1). Preferably, the heat treatment comprises: heating for 8-12 hours at the temperature of 110 ℃.
Furthermore, in the present embodiment, the proton exchange membrane resin in the self-humidifying composite proton exchange membrane is subjected to a pretreatment, and preferably, the porous reinforced membrane 1 containing Pt after the heat treatment is sequentially subjected to H2O2Solution and dilute H2SO4Ultrasonic treatment is carried out in the solution. Further preferably, the sonication comprises: at 3% -5% H2O2Ultrasonic treatment is carried out for 1-3 hours in the solution, the solution is taken out and washed by deionized water, and then the solution is placed in dilute H2SO4Ultrasonic treatment is carried out for 2-3 hours at medium and normal temperature, and finally deionized water is used for cleaning. More preferably, H with the PH of 0.3-0.8 is adopted2SO4. The operation ensures that the permeability of water and protons of the proton exchange membrane resin is higher, and the internal resistance of the self-humidifying composite proton exchange membrane is reduced. The self-humidifying composite proton exchange membrane is prepared by the treatment, preferably, the thickness of the self-humidifying composite proton exchange membrane is 25 mu m, the conductivity is poor, and the loading amount of Pt is 0.08mg/cm2The electrochemical repeated test proves that the Pt dispersibility is good, and meanwhile, the carrier in the proton exchange membrane is an inorganic substance which is not an electronic conductor, so that the generation of electronic short circuit in the composite membrane can be effectively avoided.
The self-humidifying composite proton exchange membrane prepared by the method comprises a composite structure of a proton exchange membrane and a porous reinforced membrane; in order to further improve the thermal stability and self-humidification performance of the self-humidification composite proton exchange membrane, as shown in fig. 1, in the present embodiment, it is preferable that the porous enhancement membrane 1 containing Pt after the ultrasonic treatment is subjected to performance enhancement treatment by using a graphene oxide solution. And generating graphene oxide sheets on two surfaces of the Pt-containing porous reinforced membrane after ultrasonic treatment. The thermal stability of the self-humidifying composite proton exchange membrane is improved, and meanwhile, the existence of the graphene oxide sheets 2 enables the proton exchange membrane to have a good oxidation-reduction function, so that oxygen and water are generated by protons on the surface of the graphene oxide more easily, and the self-humidifying performance of the proton exchange membrane is further improved. The self-humidifying composite proton exchange membrane prepared in the step is additionally provided with a graphene oxide sheet layer on the composite structure, the graphene oxide sheet layer is distributed on two surfaces of the composite structure of the proton exchange membrane layer and the porous reinforced membrane, and finally the three-layer self-humidifying composite proton exchange membrane is prepared. In the above preferred embodiment, the composite structure of the self-humidifying composite proton exchange membrane is not limited to the above one, and a graphene oxide sheet layer may be added to one surface of the composite structure of the self-humidifying composite proton exchange membrane to prepare a two-layer self-humidifying composite proton exchange membrane.
Graphene oxide is generally obtained by oxidizing graphite with a strong acid, and in the present embodiment, it is preferable to add graphite flakes to H2SO4：H3PO44: 1 ratio of the acid mixture, potassium permanganate was then added and the mixture was stirred continuously for 3 days, then 36% H was added to it2O2And continuously stirring for reaction for 3 days, and after the reaction is finished, centrifuging and then washing with HCl and deionized water to obtain the graphene oxide. Preferably, the performance enhancement treatment comprises spraying or painting of a graphene oxide solution onto the surface of the porous enhancement film 1 containing Pt after the ultrasonic treatment. Further preferably, the graphene oxide solution is sprayed onto the self-humidifying composite proton exchange membrane. Preferably, the graphene oxide sheet 2 has a thickness of 5 μm. In the preparation process, the graphene oxide sheet 2 obtained after preparation can be characterized, and in the embodiment, preferably, FTIR is carried out on the graphene oxide sheet 2 at 1236cm-1And 825cm-1An asymmetric stretching peak and a symmetric stretching peak belonging to an alkene ether bond appear at 1045cm-1The C-O stretching vibration peak belonging to pure hydroxyl appears and is at 1504cm-1The peak belonging to C-N appears, and the successful preparation of GO, namely the successful preparation of the graphene oxide sheet 2 is proved。
In the preparation method of the self-humidifying composite proton exchange membrane provided by the embodiment, the self-humidifying composite proton exchange membrane prepared by the preparation method introduces the precious metal Pt, which is beneficial to the trace amount of H permeating from the cathode and the anode2And O2Water is generated through the catalytic reaction of noble metal Pt, so that the effects of maintaining the moisture in the membrane and improving the open-circuit voltage are achieved; meanwhile, Pt is uniformly distributed, so that the problem of electronic short circuit in a proton exchange membrane is solved; meanwhile, the porous reinforced membrane containing Pt is subjected to treatment such as heating and ultrasonic treatment, so that the proton conductivity of the self-humidifying composite proton exchange membrane is enhanced, and the internal resistance of the self-humidifying composite proton exchange membrane is reduced. Meanwhile, the graphene oxide sheet is introduced, so that the thermal stability and the self-humidifying performance of the self-humidifying composite proton exchange membrane are improved.
Example 2
The embodiment provides a preparation method of a self-humidifying composite proton exchange membrane, which comprises the following steps:
the method comprises the following steps: cleaning the porous reinforced membrane with ethanol or acetone, and fixing the porous reinforced membrane on a mold; preferably, the pore diameter of the porous reinforced membrane is 0.2-0.7 μm; the thickness is 5-155 μm; the porosity is 60-90%.
Step two: dissolving proton exchange resin in an organic solution to prepare a uniform solution with the polymer content of 7-13%; preferably, the proton exchange membrane resin includes any one of perfluorosulfonic acid resin (Nafion), sulfonated polyether ether ketone (SPEEK) among Sulfonated Polyarylethersulfones (SPSU).
Step three: dissolving a Pt supported catalyst in a uniform solution of the proton exchange membrane resin, oscillating for 24 hours, carrying out ultrasonic treatment for 0.5-6 hours, and stirring for 0.5-6 hours to prepare a uniform solution of the Pt-containing proton exchange membrane resin.
Step four: and casting or spraying the homogeneous solution of the Pt-containing proton exchange membrane resin on a porous reinforced membrane by a casting or spraying method, and drying for 12-36 hours at the temperature of 30-50 ℃ in vacuum to obtain the self-humidifying composite proton exchange membrane.
Step five: and (3) heating the self-humidifying composite proton exchange membrane for 8-12 hours at the temperature of 110 ℃ under the protection of inert gas.
Step six: placing the self-humidifying composite proton exchange membrane after heating treatment in 3-5% H2O2Performing ultrasonic treatment in the solution for 1-3 hours, taking out the solution, cleaning the solution with deionized water, and placing the solution in dilute H2SO4And (4) carrying out ultrasonic treatment for 2-3 hours at a medium normal temperature, and finally cleaning with deionized water.
Step seven: adding graphite flake to H2SO4：H3PO44: 1 ratio of the acid mixture, potassium permanganate was then added and the mixture was stirred continuously for 3 days, then 36% H was added to it2O2And continuously stirring for reaction for 3 days, and after the reaction is finished, centrifuging and then washing with HCl and deionized water to obtain the graphene oxide.
Step eight: and spraying the graphene oxide solution on the self-humidifying composite proton exchange membrane.
The preparation method of the self-humidifying composite proton exchange membrane provided by the embodiment is simple in synthesis method, adopts a casting or spraying method in the aspect of membrane casting process, does not need complicated synthesis steps, does not have complex equipment requirements, and is simple, convenient and rapid to operate and high in production efficiency.
Example 3
The present application provides a proton exchange membrane fuel cell, comprising a membrane electrode and a proton exchange membrane, wherein the membrane electrode comprises a self-humidifying composite proton exchange membrane prepared by the method of example 1 or example 2; the proton exchange membrane is prepared by the method of example 1 or example 2.
The present embodiment also addresses the above Pt/(SO) load-2 4/ZrO2) The cell performance of the single cell of the proton exchange membrane fuel cell of the self-humidifying composite membrane is detected under the conditions of full humidification and no external humidification, and the mass of Pt contained in the proton exchange membrane of each square centimeter of the single cell as a sample is 0.65mg, mPt＝0.65mg/cm2And the hydrogen utilization ratio of the sample single cell>90 percent, and the oxygen utilization rate is 52 percent; effective area of 5cm2. The specific test conditions were as follows: h in the dry state2/O2(ii) a The operation pressure is 0.01-0.3 MPa; operating temperatureUnder the temperature of 60-80 ℃.
The specific test results are shown in fig. 3, wherein RH-100% represents the test curve of the performance of the sample single cell under the full-humidification condition; the cell performance test curve of the sample without external humidification condition represented by RH ═ 0%, as can be seen from fig. 3, the cell performance of the pem fuel cell provided in this example under the conditions of full humidification and no humidification is very close, i.e. the pem fuel cell itself has very good humidification effect.
According to the proton exchange membrane fuel cell provided by the embodiment, the self-humidifying composite proton exchange membrane is adopted, and Pt is introduced, so that the performance and the self-humidifying performance of the proton exchange membrane fuel cell are improved, meanwhile, the gas flow field design of the proton exchange membrane fuel cell is simplified, the self-humidifying operation stability is improved, and the cell performance is improved. Meanwhile, the thickness of the self-humidifying composite proton exchange membrane is thin, so that the reverse diffusion effect of water is facilitated, the reverse diffusion rate is increased, the aim of wetting the membrane in time is fulfilled, the performance of the battery is improved, and the battery is suitable for rapidly changing loads.
In summary, the present invention provides a method for preparing a self-humidifying composite proton exchange membrane, which comprises: and casting or spraying the Pt-containing proton exchange membrane resin homogeneous liquid onto the porous reinforced membrane to prepare the Pt-containing porous reinforced membrane, and drying the Pt-containing porous reinforced membrane to prepare the self-humidifying composite proton exchange membrane. The method is simple to operate, the synthesized self-humidifying composite proton exchange membrane effectively solves the problem of self-humidifying of the proton exchange membrane, ensures that the self-humidifying composite proton exchange membrane can not generate electronic short circuit in the membrane, has high proton conductivity, does not influence gas mass transfer, and can reduce the cost of the membrane electrode.
Exemplary embodiments of the present disclosure are specifically illustrated and described above. It is to be understood that the present disclosure is not limited to the precise arrangements, instrumentalities, or instrumentalities described herein; on the contrary, the disclosure is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (17)
1. A preparation method of a self-humidifying composite proton exchange membrane is characterized by comprising the following steps: casting or spraying Pt-containing proton exchange membrane resin homogeneous liquid onto a porous reinforced membrane to prepare a Pt-containing porous reinforced membrane (1), and drying the Pt-containing porous reinforced membrane (1) to prepare the self-humidifying composite proton exchange membrane.
2. The method of claim 1, wherein the drying comprises drying at 30-50 ℃ under vacuum for 12-36 hours.
3. The method for preparing a self-humidifying composite proton exchange membrane according to claim 1, wherein the preparation of the Pt-containing proton exchange membrane resin homogeneous solution comprises the following steps: dissolving Pt supported catalyst in the homogeneous resin solution of proton exchange membrane, and oscillating, ultrasonic treating and stirring.
4. The method for preparing a self-humidifying composite proton exchange membrane as claimed in claim 3, wherein the oscillating, ultrasonic and stirring treatment comprises oscillating for 24 hours, ultrasonic for 0.5-6 hours and stirring for 0.5-6 hours.
5. The method for preparing a self-humidifying composite proton exchange membrane as claimed in claim 1, wherein the mass ratio of Pt to the proton exchange membrane resin in the homogeneous solution of the Pt-containing proton exchange membrane resin is 0.01: 1-0.2: 0.01.
6. The method of claim 1, wherein the step of preparing the homogeneous proton exchange membrane resin solution comprises dissolving a proton exchange membrane resin in an organic solvent to obtain the homogeneous proton exchange membrane resin solution.
7. The method for preparing a self-humidifying composite proton exchange membrane as claimed in claim 6, wherein the content of the homogeneous liquid of the proton exchange membrane resin is 7-13%.
8. The method of claim 1, wherein the porous reinforced membrane has a pore size of 0.2 μm to 0.7 μm; the thickness of the porous reinforced membrane is 5-155 mu m; the porosity of the porous reinforced membrane is 60-90%.
9. The method of preparing a self-humidifying composite proton exchange membrane as claimed in any one of claims 1 to 8, further comprising: and (3) carrying out heating treatment on the dried Pt-containing porous reinforced membrane (1) under the inert gas condition.
10. The method of claim 9 wherein said heat treating comprises: heating for 8-12 hours at the temperature of 110 ℃.
11. The method for preparing a self-humidifying composite proton exchange membrane as claimed in claim 9, further comprising sequentially placing the porous reinforced membrane (1) containing Pt after heat treatment in H2O2Solution and dilute H2SO4Ultrasonic treatment is carried out in the solution.
12. The method of preparing a self-humidifying composite proton exchange membrane as claimed in claim 11, wherein the ultrasonic treatment comprises: at 3% -5% H2O2Ultrasonic treatment is carried out for 1-3 hours in the solution, the solution is taken out and washed by deionized water, and then the solution is placed in dilute H2SO4Ultrasonic treatment is carried out for 2-3 hours at medium and normal temperature, and finally deionized water is used for cleaning.
13. The method for preparing a self-humidifying composite proton exchange membrane according to claim 11, further comprising performing performance enhancement treatment on the porous enhanced membrane (1) containing Pt after ultrasonic treatment by using a graphene oxide solution.
14. The method of preparing a self-humidifying composite proton exchange membrane as claimed in any one of claims 1 to 13, comprising:
1) dissolving a Pt supported catalyst in a uniform solution of a proton exchange membrane resin, oscillating for 24 hours, carrying out ultrasonic treatment for 0.5-6 hours, and stirring for 0.5-6 hours to prepare a uniform solution of the Pt-containing proton exchange membrane resin;
2) casting or spraying the homogeneous solution of the Pt-containing proton exchange membrane resin on a porous reinforced membrane by a casting or spraying method, and drying for 12-36 hours at 30-50 ℃ under vacuum to obtain the self-humidifying composite proton exchange membrane;
3) heating the self-humidifying composite proton exchange membrane for 8-12 hours at the temperature of 110 ℃ under the protection of inert gas;
4) placing the self-humidifying composite proton exchange membrane after heating treatment in 3-5% H2O2Performing ultrasonic treatment in the solution for 1-3 hours, taking out the solution, cleaning the solution with deionized water, and placing the solution in dilute H2SO4Carrying out ultrasonic treatment for 2-3 hours at a medium normal temperature, and finally cleaning with deionized water;
5) and spraying the graphene oxide solution onto the self-humidifying composite proton exchange membrane.
15. A membrane electrode comprising a proton exchange membrane, wherein the proton exchange membrane is prepared by the self-humidifying composite proton exchange membrane preparation method of any one of claims 1-14.
16. A fuel cell comprising a proton exchange membrane prepared by the self-humidifying composite proton exchange membrane preparation method of any one of claims 1 to 14 and/or a membrane electrode of claim 15.
17. A fuel cell according to claim 16, wherein the fuel cell is a proton exchange membrane fuel cell.
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