CN115241505A - Membrane electrode based on molten proton conductor electrolyte membrane and preparation method thereof - Google Patents

Membrane electrode based on molten proton conductor electrolyte membrane and preparation method thereof Download PDF

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CN115241505A
CN115241505A CN202210840927.0A CN202210840927A CN115241505A CN 115241505 A CN115241505 A CN 115241505A CN 202210840927 A CN202210840927 A CN 202210840927A CN 115241505 A CN115241505 A CN 115241505A
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proton conductor
phosphoric acid
catalyst
molten
fuel cell
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李海滨
邢以晶
李一凡
付志永
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a membrane electrode based on a molten proton conductor electrolyte membrane and a preparation method thereof, wherein the preparation method of the membrane electrode comprises the following steps: s1, preparing a polybenzimidazole doped molten proton conductor electrolyte membrane; s2, preparing catalyst slurry containing a proton conductor, coating the catalyst slurry containing the proton conductor on one side of a microporous layer of the gas diffusion layer, and drying to obtain a gas diffusion electrode with a catalyst layer containing the proton conductor attached to the gas diffusion layer; and S3, placing gas diffusion electrodes on two sides of the polybenzimidazole doped molten proton conductor electrolyte membrane of the step S1 to assemble a fuel cell membrane electrode. By introducing the proton conductor into the catalyst slurry, the proton conductor can be uniformly distributed in the gas diffusion electrode catalyst layer to form a continuous proton transmission channel, so that the proton transmission resistance in the catalyst layer is reduced, and the electrical output performance of the membrane electrode is improved.

Description

Membrane electrode based on molten proton conductor electrolyte membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a membrane electrode based on a molten proton conductor electrolyte membrane and a preparation method thereof.
Background
The fuel cell, as an energy conversion device, can directly convert chemical energy in fuel into electric energy through electrochemical reaction in the membrane electrode. Compared with the conventional low-temperature proton exchange membrane fuel cell (LT-PEMFC) which works below 100 ℃, the high-temperature proton exchange membrane fuel cell (HT-PEMFC) which works at 100-250 ℃ has special advantages: (1) the CO poisoning resistance of the membrane electrode is obviously improved; (2) the electrochemical reaction activity is increased, and the catalytic efficiency is improved; and (3) simplifying a water and heat management system. HT-PEMFC has huge application potential and market value.
The electrolyte membrane in a fuel cell, in which Polybenzimidazole (PBI) is doped with phosphoric acid (H), determines the operating temperature of the fuel cell 3 PO 4 ) The high-temperature proton exchange membrane is a proton exchange membrane commonly used in HT-PEMFC. In the PBI-doped phosphoric acid high-temperature proton exchange membrane, a proton conductor is phosphoric acid which is in a liquid state from room temperature to working temperature (180 ℃), and the liquid phosphoric acid is easy to run off particularly at low temperature; moreover, the swelling ratio is as high as 200-300%, the mechanical strength is remarkably reduced and is only 13.6MPa.
On the other hand, chinese patent CN107331883A and publication 1 (A proton conductor based on molten CsH) 5 (PO 4 ) 2 for interface-temperature fuel cells, RSC advaves, 2018,8,5225-5232, reports PBI doped molten proton conductor electrolyte membranes and methods of making the same, wherein the doped proton conductor (CsH) 5 (PO 4 ) 2 、KH 5 (PO 4 ) 2 ) The room temperature is solid, the liquid melt is transformed when the temperature is higher than the melting point, the melt has high proton conductivity, and the loss is not easy to occur because the liquid melt is solid below the melting point; meanwhile, the PBI doped molten proton conductor membrane has low swelling ratio, can keep good mechanical strength, and is compared with PBI doped phosphoric acid high-temperature proton exchangeTensile strength of the membrane, PBI doped molten proton conductor electrolyte membrane, was improved by 7 times. However, the peak output power density of the membrane electrode based on the molten proton conductor electrolyte membrane does not exceed 120mW/cm 2 The expected good output performance of the fuel cell is not shown because the membrane electrode is prepared by a conventional membrane electrode preparation method based on a PBI doped phosphoric acid high-temperature proton exchange membrane, and the catalytic layer of the gas diffusion electrode does not contain a proton conductor, but only contains a catalyst and a binder (having a water repellent function), and it is expected that the molten proton conductor doped in the electrolyte membrane can diffuse to the catalytic layer like phosphoric acid to provide proton conduction, but the viscosity of the molten proton conductor is much higher than that of liquid phosphoric acid and is difficult to diffuse to the catalytic layer like phosphoric acid, so that the catalytic layer lacks a proton conductor, which results in very low electrical output performance of the fuel cell, and this also becomes a great obstacle for the application of the technology industry.
Disclosure of Invention
The invention provides a membrane electrode preparation method based on a molten proton conductor electrolyte membrane, aiming at the problem that a catalyst layer of a membrane electrode of a fuel cell prepared based on a PBI doped molten proton conductor electrolyte membrane in the prior art is lack of a proton conductor.
According to the method, the catalyst slurry containing the proton conductor is coated on the surface of the gas diffusion layer to obtain the gas diffusion electrode containing the proton conductor, and then the gas diffusion electrode containing the proton conductor is attached to two sides of the PBI-doped molten proton conductor electrolyte membrane to prepare the membrane electrode, so that the proton transmission in the catalytic layer is improved, the interface resistance between the catalytic layer and the electrolyte membrane is reduced, the electrical output performance of the membrane electrode of the fuel cell is effectively improved, the process flow is simplified, and the membrane electrode preparation efficiency is improved.
In order to achieve the above object, the present invention provides a method for preparing a membrane electrode based on a molten proton conductor electrolyte membrane, comprising the steps of:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane;
s2, preparing catalyst slurry containing a proton conductor, coating the catalyst slurry containing the proton conductor on one side of a microporous layer of the gas diffusion layer, and drying to obtain a gas diffusion electrode with a catalyst layer containing the proton conductor attached to the gas diffusion layer;
and S3, placing the gas diffusion electrodes on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane to assemble the fuel cell membrane electrode.
In step S1, the preparation method of the polybenzimidazole-doped molten proton conductor electrolyte membrane is as follows:
1) Melting the molten proton conductor at a temperature 0-30 ℃ higher than the melting point of the molten proton conductor to convert the molten proton conductor into a molten proton conductor;
2) And soaking the polybenzimidazole membrane in a molten proton conductor, taking out the polybenzimidazole membrane after soaking is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the polybenzimidazole doped molten proton conductor electrolyte membrane.
The molten proton conductor is MH 5 (PO 4 ) 2 Wherein M is Cs or K.
Preferably, in step S1, the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane is prepared as follows:
1) MH (hydrogen iodide) is prepared 5 (PO 4 ) 2 (M is Cs or K) is melted at a temperature 0-30 ℃ higher than the melting point of the proton conductor to convert the proton conductor into a molten state;
2) And soaking the polybenzimidazole membrane in a molten proton conductor for 6-72h, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane.
Preferably, in step S2, the catalyst slurry includes: a catalyst slurry containing phosphoric acid and/or a catalyst slurry containing phosphoric acid and a molten proton conductor;
when the catalyst slurry is a catalyst slurry containing phosphoric acid and a molten proton conductor, the catalyst slurry containing phosphoric acid and a molten proton conductor is coated on the microporous layer side of the gas diffusion layer, and then the catalyst slurry containing phosphoric acid is coated.
The phosphoric acid-containing catalyst slurry includes: catalyst, binder, phosphoric acid, deionized water and alcohol.
The preparation method of the catalyst slurry containing phosphoric acid comprises the following steps: catalyst, binder, phosphoric acid, deionized water and alcohol are mixed according to the mass ratio of 1:0.01 to 0.1:0.1 to 1:1 to 10: 5-50, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid; wherein the binder is one or more of Polytetrafluoroethylene (PTFE), PBI and polyvinylidene fluoride (PVDF); the alcohol is one or more of ethanol, methanol, isopropanol and n-propanol; the catalyst is a carbon-supported platinum catalyst, wherein the mass ratio of platinum to the carbon carrier is (1-9): (9-1).
The catalyst slurry containing phosphoric acid and a molten proton conductor includes: catalyst, binder, phosphoric acid and molten proton conductor, deionized water.
The preparation method of the catalyst slurry containing phosphoric acid and a molten proton conductor comprises the following steps: mixing a catalyst, a binder, phosphoric acid, a molten proton conductor and deionized water according to a mass ratio of 1:0.01 to 0.1:0.1 to 1: 5-50, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid and a molten proton conductor; wherein the mass ratio of the phosphoric acid to the molten proton conductor is 1:1 to 10; the binder is one or more of PTFE, PBI and PVDF; the catalyst is a carbon-supported platinum catalyst, wherein the mass ratio of platinum to the carbon carrier is (1-9): (9-1). The molten proton conductor is MH 5 (PO 4 ) 2 Wherein M is Cs or K.
Containing phosphoric acid and a molten proton conductor (MH) 5 (PO 4 ) 2 (M is Cs or K)) is that the catalyst slurry contains no alcohol, since alcohol can lead to MH 5 (PO 4 ) 2 And (4) precipitating crystals.
Preferably, in the preparation method of the fuel cell membrane electrode, in step S2, drying refers to drying at 60-200 ℃.
Preferably, the gas diffusion electrode, after-treatment: spraying phosphoric acid on the surface, wherein the phosphoric acid content is 1-10mg/cm 2 。
Preferably, in step S2, the proton conductor-containing catalyst slurry is coated by spraying, knife coating, or slot extrusion coating.
Compared with the prior art, the invention has the following beneficial effects:
1) A PBI-based molten proton conductor doped electrolyte membrane is prepared by coating a catalyst slurry containing a proton conductor on the surface of a gas diffusion layer, and drying to obtain a gas diffusion electrode with a catalyst layer containing a proton conductor attached to the gas diffusion layer. The catalyst slurry contains phosphoric acid proton conductor or phosphoric acid and MH 5 (PO 4 ) 2 (M is Cs and/or K) mixed proton conductor. The method introduces proton conductors into the catalyst slurry, can realize the uniform distribution of the proton conductors in the catalyst layer, form a continuous proton transmission channel, reduce the proton transmission resistance in the catalyst layer, and construct a three-phase (reaction gas/proton conductor/catalyst) interface of electrode reaction.
2) Alternatively, both phosphoric acid and MH are present in the catalytic layer of the gas diffusion electrode 5 (PO 4 ) 2 (M is Cs and/or K), and the liquid phosphoric acid can inhibit CsH 5 (PO 4 ) 2 Or KH 5 (PO 4 ) 2 And low-temperature crystallization is carried out, so that the stability of the proton conductor in the catalyst layer is ensured, and the proton conduction capability and the proton conduction stability in the catalyst layer are provided. And MH contained in the catalyst layer 5 (PO 4 ) 2 (M is Cs and/or K), MH at high temperature 5 (PO 4 ) 2 (M is Cs and/or K) becomes a molten proton conductor, has high viscosity, is not easy to volatilize and run off, and improves the stability of the fuel cell.
3) Alternatively, a proton conductor-containing gas diffusion electrode is obtained by sequentially coating two kinds of catalyst pastes containing different proton conductors on the surface of a gas diffusion layer, the catalyst paste near the gas diffusion layer containing phosphoric acid and MH 5 (PO 4 ) 2 (M is Cs and/or K), and MH in molten state in the operating temperature region of the fuel cell 5 (PO 4 ) 2 The membrane electrode has high viscosity and is not easy to volatilize, the loss of proton conductors can be relieved, and the proton conductivity stability in the membrane electrode are improved. Catalyst slurry adjacent to electrolyte membraneThe middle proton conductor is phosphoric acid, and liquid phosphoric acid can form liquid-solid contact between the catalyst layer and the electrolyte membrane interface, so that high-efficiency proton conduction is realized, the transmission resistance between the catalyst layer and the electrolyte membrane interface is reduced, and the electrical output performance of the fuel cell is improved.
4) The catalyst slurry containing the proton conductor is directly coated on the gas diffusion layer to form the gas diffusion electrode with the catalyst layer containing the proton conductor, so that the membrane electrode is convenient to assemble, the rapid and efficient preparation of the membrane electrode can be realized, the preparation time of the membrane electrode is shortened, and the preparation efficiency of the membrane electrode is improved.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of the membrane electrode preparation in the method of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
As shown in fig. 1, the present invention provides a method for preparing a membrane electrode of a fuel cell, comprising the steps of:
s1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane;
and S2, preparing catalyst slurry containing a proton conductor, coating the catalyst slurry containing the proton conductor on one side of the microporous layer of the gas diffusion layer, and drying at 60-200 ℃ to obtain the gas diffusion electrode with the catalyst layer containing the proton conductor attached to the gas diffusion layer.
And S3, placing gas diffusion electrodes containing proton conductors on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble a membrane electrode of the fuel cell.
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1
The preparation method of the fuel cell membrane electrode of the embodiment specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film with thickness of 35 μm is soaked in molten CsH 5 (PO 4 ) 2 And (4) soaking for 48h at the temperature of 150 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode:
1) Carbon-supported platinum catalyst with platinum content of 40wt%, PTFE binder, phosphoric acid and CsH 5 (PO 4 ) 2 And deionized water according to the mass ratio of 1:0.02:0.24:20, wherein phosphoric acid is mixed with CsH 5 (PO 4 ) 2 The mass ratio of (1): 3, obtaining the mixture containing phosphoric acid and CsH by ultrasonic stirring 5 (PO 4 ) 2 The catalyst slurry of (4); carrying out carbon-supported platinum catalyst with platinum content of 40wt%, PTFE binder, phosphoric acid, deionized water and isopropanol according to a mass ratio of 1:0.02:0.24:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid;
2) The phosphoric acid and CsH containing solution prepared in the step 1) 5 (PO 4 ) 2 The catalyst slurry and the catalyst slurry containing phosphoric acid are sequentially coated on the surface of the microporous layer of the gas diffusion layer, and are dried at 150 ℃ after coating to form a catalyst layer, so that the gas diffusion electrode is prepared;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Example 2
The preparation method of the fuel cell membrane electrode of the embodiment specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film 35 μm thick was dip-soaked (21) in molten CsH 5 (PO 4 ) 2 And (4) soaking for 48h at the temperature of 150 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode:
1) Firstly, a carbon-supported platinum catalyst with platinum content of 40wt%, a PTFE binder, phosphoric acid and CsH 5 (PO 4 ) 2 And deionized water according to the mass ratio of 1:0.02:0.24:20, wherein phosphoric acid is mixed with CsH 5 (PO 4 ) 2 The mass ratio of (1): 3, obtaining the mixture containing phosphoric acid and CsH by ultrasonic stirring 5 (PO 4 ) 2 A catalyst slurry;
2) The phosphoric acid and CsH prepared in the step 1) are added 5 (PO 4 ) 2 Coating the catalyst slurry on the surface of the microporous layer of the gas diffusion layer, and drying at 150 ℃ to form a catalyst layer so as to prepare a gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Example 3
The preparation method of the fuel cell membrane electrode of the embodiment specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film (21) having a thickness of 35 μm was immersed in molten CsH 5 (PO 4 ) 2 And (4) soaking for 48h at the temperature of 150 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode:
1) Carrying out carbon-supported platinum catalyst with platinum content of 40wt%, PTFE binder, phosphoric acid, deionized water and isopropanol according to a mass ratio of 1:0.02:0.24:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid;
2) Coating the phosphoric acid-containing catalyst slurry prepared in the step 1) on the surface of a microporous layer of a gas diffusion layer, and drying at 150 ℃ to form a catalyst layer, thereby preparing a gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Example 4
The preparation method of the fuel cell membrane electrode of the embodiment specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film with a thickness of 35 μm was dipped (21) in KH molten state 5 (PO 4 ) 2 And (4) soaking for 48h at 130 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
S2, preparing a gas diffusion electrode:
1) Carbon-supported platinum catalyst with platinum content of 40wt%, PTFE binder, phosphoric acid and KH 5 (PO 4 ) 2 And deionized water is mixed according to the mass ratio of 1:0.02:0.24:20, wherein phosphoric acid is mixed with KH 5 (PO 4 ) 2 The mass ratio of (1): 3, ultrasonically stirring to obtain phosphoric acid and KH 5 (PO 4 ) 2 A catalyst slurry; carrying out a reaction on a carbon-supported platinum catalyst with platinum content of 40wt%, a PTFE (polytetrafluoroethylene) binder, phosphoric acid, deionized water and isopropanol according to a mass ratio of 1:0.02:0.24:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid;
2) Mixing the phosphoric acid prepared in the step 1) with KH 5 (PO 4 ) 2 Sequentially coating the catalyst slurry and the catalyst slurry containing phosphoric acid on the surface of the microporous layer of the gas diffusion layer, and drying at 130 ℃ after coating to form a catalyst layer, thereby preparing the gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Example 5
The preparation method of the fuel cell membrane electrode of the embodiment specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI membrane (21) with thickness of 35 μm is soaked in molten KH 5 (PO 4 ) 2 And (4) soaking for 48h at 130 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode:
1) Firstly, a carbon-supported platinum catalyst with platinum content of 40wt%, a PTFE binder, phosphoric acid and KH 5 (PO 4 ) 2 And deionized water according to the mass ratio of 1:0.02:0.24:20, wherein phosphoric acid is mixed with KH 5 (PO 4 ) 2 The mass ratio of (1): 3, ultrasonically stirring to obtain phosphoric acid and KH 5 (PO 4 ) 2 A catalyst slurry;
2) Mixing the phosphoric acid prepared in the step 1) with KH 5 (PO 4 ) 2 Coating the catalyst slurry on the surface of the microporous layer of the gas diffusion layer, and drying at 130 ℃ to form a catalyst layer so as to prepare a gas diffusion electrode;
and S3, placing gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble a fuel cell membrane electrode.
Example 6
The preparation method of the fuel cell membrane electrode of the embodiment specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI membrane (21) with the thickness of 35 μm is soaked in molten KH 5 (PO 4 ) 2 Soaking for 48h at 130 deg.C, taking out PBI membrane, and removing excessive proton conductor on the membrane surface to obtain PBI-doped molten proton conductor (KH) 5 (PO 4 ) 2 ) An electrolyte membrane (22).
Step S2, preparing a gas diffusion electrode:
1) Carrying out carbon-supported platinum catalyst with platinum content of 40wt%, PTFE binder, phosphoric acid, deionized water and isopropanol according to a mass ratio of 1:0.02:0.24:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid;
2) Coating the phosphoric acid-containing catalyst slurry prepared in the step 1) on the surface of a microporous layer of a gas diffusion layer, and drying at 130 ℃ to form a catalyst layer, thereby preparing a gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Comparative example 1
The present comparative example is different from example 3 in that the catalytic layer does not contain a proton conductor.
The preparation method of the membrane electrode of the fuel cell of the comparative example specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film (21) having a thickness of 35 μm was immersed in molten CsH 5 (PO 4 ) 2 And (4) soaking for 48h at the temperature of 150 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode:
1) Carrying out carbon-supported platinum catalyst with platinum content of 40wt%, PTFE binder, deionized water and isopropanol according to a mass ratio of 1:0.02:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry without proton conductors;
2) Coating the catalyst slurry which is prepared in the step 1) and does not contain a proton conductor on the surface of a microporous layer of a gas diffusion layer, and drying at 150 ℃ to form a catalyst layer, thereby preparing a gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Comparative example 2
This comparative example differs from example 3 in that the catalytic layer does not contain a proton conductor, but rather a gas diffusion electrode post-treatment, i.e., phosphoric acid spray, is performed on the gas diffusion electrode.
The preparation method of the membrane electrode of the fuel cell of the comparative example specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film (21) having a thickness of 35 μm was immersed in molten CsH 5 (PO 4 ) 2 And (4) soaking for 48h at the temperature of 150 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode:
1) Mixing a carbon-supported platinum catalyst with platinum content of 40wt%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to a mass ratio of 1:0.02:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry without proton conductors;
2) Coating the catalyst slurry which is prepared in the step 1) and does not contain a proton conductor on the surface of a microporous layer of a gas diffusion layer, and drying at 150 ℃ to form a catalyst layer, thereby preparing a gas diffusion electrode;
and S3, performing gas diffusion electrode post-treatment: an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio = 1:4) was sprayed onto the surface of the catalytic layer on the gas diffusion electrode using a spray gun in an amount of 3mg/cm 2 ). Then, the gas diffusion electrodes subjected to the post-treatment were placed on both sides of the PBI-doped molten proton conductor electrolyte membrane to assemble a fuel cell membrane electrode.
Comparative example3
This comparative example differs from example 2 in that: the catalytic layer contains phosphoric acid and CsH 5 (PO 4 ) 2 The gas diffusion electrode is replaced by a catalytic layer containing CsH 5 (PO 4 ) 2 The gas diffusion electrode of (1).
The preparation method of the membrane electrode of the fuel cell of the comparative example specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI film (21) having a thickness of 35 μm was immersed in molten CsH 5 (PO 4 ) 2 Soaking at 150 deg.C for 48 hr, taking out PBI membrane, and removing membrane surfaceThe proton conductor in the amount to obtain a PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a catalyst coating film: 1) Firstly, a carbon-supported platinum catalyst with platinum content of 40wt%, a PTFE binder and CsH 5 (PO 4 ) 2 And deionized water according to the mass ratio of 1:0.02:0.24:20, and ultrasonically stirring to obtain the CsH-containing material 5 (PO 4 ) 2 A catalyst slurry; 2) The CsH-containing solution prepared in the step 1) 5 (PO 4 ) 2 Coating the catalyst slurry on the surface of the microporous layer of the gas diffusion layer, and drying at 150 ℃ to form a catalyst layer so as to prepare a gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Comparative example 4
This comparative example is different from example 6 in that the catalytic layer does not contain a proton conductor.
The preparation method of the membrane electrode of the fuel cell of the comparative example specifically comprises the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane: PBI membrane (21) with the thickness of 35 μm is soaked in molten KH 5 (PO 4 ) 2 And (4) soaking for 48h at 130 ℃, taking out the PBI membrane after the soaking time is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane.
Step S2, preparing a gas diffusion electrode: 1) Mixing a carbon-supported platinum catalyst with platinum content of 40wt%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to a mass ratio of 1:0.02:3:25, mixing, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid; 2) Coating the catalyst slurry which is prepared in the step 1) and does not contain a proton conductor on the surface of a microporous layer of a gas diffusion layer, and drying at 130 ℃ to form a catalyst layer, thereby preparing a gas diffusion electrode;
and S3, placing the gas diffusion electrodes on two sides of the PBI-doped molten proton conductor electrolyte membrane to assemble the membrane electrode of the fuel cell.
Performance testing of examples and comparative examples
The membrane electrode-assembled fuel cell unit cells prepared in each example and comparative example were tested for output performance and stability.
1. Test method
Method for testing output performance of fuel cell: the membrane electrodes obtained in the examples and the comparative examples are assembled into a single cell for testing, oxygen and hydrogen are respectively introduced into the cathode and the anode of the single cell without back pressure, the gas flow rates of the hydrogen and the oxygen are both 0.4L/min, and the I-V curve is tested by using a chrysanthemum water electronic load (PLZ 164 WA) to obtain the output performance of the fuel cell. And, the PBI-based doped molten proton conductor (CsH) 5 (PO 4 ) 2 ) The operation temperature of the fuel cell assembled by the membrane electrode of the electrolyte membrane is 180 ℃; PBI-based doped fused proton conductor (KH) 5 (PO 4 ) 2 ) The fuel cell equipped with the membrane electrode of the electrolyte membrane was operated at 160 ℃.
The stability test method comprises the following steps:
the test conditions were as above, at 0.2A/cm 2 The operation was continued for 48 hours at the rated current density to confirm the voltage stability.
2. Test results
The numbers and main features of the membrane electrodes of the fuel cells prepared in each of the examples and comparative examples, and the output performance of the fuel cell using the membrane electrode assemblies prepared are shown in table 1.
TABLE 1
Figure BDA0003751015340000101
Fuel cell output performance: particularly excellent (the peak power density is more than or equal to 600 mW/cm) 2 ) High quality (peak power density is more than or equal to 400 and less than or equal to 600 mW/cm) 2 ) Middle (peak power density is more than or equal to 200 and less than or equal to 400 mW/cm) 2 ) Difference (peak power density is less than or equal to 200 mW/cm) 2 )；
Stability of fuel cell: particularly excellent (the voltage attenuation rate is less than or equal to 0.2 mV/h), excellent (the voltage attenuation rate is less than or equal to 0.2mV/h and less than or equal to 1 mV/h) and medium (the voltage attenuation rate is more than or equal to 1 mV/h).
Examples 1, 2, 3, all based on Polybenzimidazole (PBI) doped fused proton conductor (CsH) 5 (PO 4 ) 2 ) The electrolyte membrane and the catalyst slurry containing the proton conductor are adopted, so that the gas diffusion electrode catalyst layers contain the proton conductor, and the comparison of the output performance of the fuel cell shows that the electrolyte membrane and the catalyst slurry containing the proton conductor are superior. The proton conductor is directly added into the catalyst slurry to obtain the catalyst layer containing the proton conductor, so that the proton conductor can be uniformly distributed in the catalyst layer, a continuous proton transmission channel is formed, the proton transmission resistance in the catalyst layer can be reduced, and a three-phase interface of the electrochemical reaction of the fuel cell is established. In further comparison, in example 3 (the fuel cell has excellent output performance and excellent stability), the catalyst layer only contains a phosphoric acid proton conductor, the phosphoric acid is liquid, the viscosity is low, the risk of loss is caused in the operation process of the fuel cell, and the stability of the fuel cell is inferior to that of examples 1 and 2; example 2 (excellent fuel cell output performance and excellent stability), the catalyst layer contained phosphoric acid and CsH 5 (PO 4 ) 2 Proton conductor, fuel cell operating state, csH in molten state 5 (PO 4 ) 2 Has high viscosity and is not easy to volatilize, can fix phosphoric acid and slow down the loss of phosphoric acid, and the phosphoric acid can ensure MH 5 (PO 4 ) 2 Crystallization separation is avoided, proton conductivity and proton conduction stability in the membrane electrode are improved, and the operation stability of the fuel cell is ensured; example 1 (excellent fuel cell output performance and excellent stability), the catalyst layer contained phosphoric acid and CsH 5 (PO 4 ) 2 A proton conductor (first layer) and a phosphoric acid proton conductor (second layer), wherein two kinds of catalyst slurries containing different proton conductors are sequentially coated on the surface of a gas diffusion layer to obtain the gas diffusion electrode containing the proton conductor, and a catalyst layer close to the gas diffusion layer contains phosphoric acid and CsH 5 (PO 4 ) 2 Proton conductor, csH in molten state in fuel cell operation 5 (PO 4 ) 2 Has high viscosity and is not easy to volatilize, can relieve the loss of proton conductors, improve the proton conductivity and the proton conductivity stability in the membrane electrode, and ensure the operation stability of the fuel cell. In the catalyst layer close to the electrolyte membrane, the proton conductor is phosphoric acid, and liquid phosphoric acid can form liquid-solid contact between the catalyst layer and the electrolyte membrane interface, so that high-efficiency proton conduction is realized, the proton transmission resistance between the catalyst layer and the electrolyte membrane interface is reduced, and the electrical output performance and the fuel cell stability of the fuel cell are excellent.
Comparative examples 1 and 2, although again based on Polybenzimidazole (PBI) doped molten proton conductor (CsH) 5 (PO 4 ) 2 ) An electrolyte membrane, however, in comparative example 1, the catalyst slurry contained no proton conductor, so that the catalyst layer of the obtained gas diffusion electrode contained no proton conductor, and a three-phase interface required for an electrochemical reaction could not be provided for the fuel cell, resulting in poor performance in comparative example 1; in comparative example 2, the catalyst slurry also does not contain a proton conductor, so that the catalytic layer obtained does not contain a proton conductor, but phosphoric acid is sprayed on the gas diffusion electrode through gas diffusion electrode post-treatment, the phosphoric acid diffuses to the catalytic layer and supplements the proton conductor for the catalytic layer, but the proton conductor in the catalytic layer is unevenly distributed, so that the output performance and the stability of the fuel cell are middle and inferior to those of examples 1, 2 and 3.
The main difference between comparative example 3 and comparative examples 1, 2 and 3 is that the proton conductor in the catalyst paste in comparative example 3 is CsH 5 (PO 4 ) 2 . During the test of the fuel cell, the electrical output performance of the fuel cell is found to be poor, the membrane electrode is disassembled after the test is finished, and the surface of the catalyst layer is found to have white CsH 5 (PO 4 ) 2 And (4) crystal precipitation. This can be explained by CsH 5 (PO 4 ) 2 Precipitates from the catalytic layer at room temperature, and CsH 5 (PO 4 ) 2 The crystals may cause insulation between the catalytic layer and the gas diffusion layer, so the electrical output performance of the fuel cell test is poor, and the stability is difficult to test.
KH was used in examples 4, 5 and 6 corresponding to examples 1, 2 and 3, respectively 5 (PO 4 ) 2 Replacement of CsH 5 (PO 4 ) 2 All based on Polybenzimidazole (PBI) doped fused proton conductors (KH) 5 (PO 4 ) 2 ) Electrolyte membraneThe catalyst layers respectively contain phosphoric acid and CsH 5 (PO 4 ) 2 Proton conductor (first layer) and phosphoric acid proton conductor (second layer), phosphoric acid and KH 5 (PO 4 ) 2 Proton conductors, and phosphoric acid proton conductors. The output performance and stability of the fuel cell of the prepared membrane electrode are both superior. Comparative example 4, although also based on Polybenzimidazole (PBI) doped fused proton conductor (KH), is compared to examples 4, 5, 6 5 (PO 4 ) 2 ) The electrolyte membrane, however, the catalyst slurry of comparative example 4 did not contain a proton conductor, so that the catalytic layer obtained did not contain a proton conductor and failed to provide a three-phase interface for the electrochemical reaction of the fuel cell, resulting in poor output performance of the fuel cell of comparative example 4.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (10)

1. The preparation method of the membrane electrode of the fuel cell is characterized by comprising the following steps:
s1, preparing a polybenzimidazole doped molten proton conductor electrolyte membrane;
s2, preparing catalyst slurry containing a proton conductor, coating the catalyst slurry containing the proton conductor on one side of a microporous layer of the gas diffusion layer, and drying to obtain a gas diffusion electrode with a catalyst layer containing the proton conductor attached to the gas diffusion layer;
and S3, placing gas diffusion electrodes on two sides of the polybenzimidazole doped molten proton conductor electrolyte membrane of the step S1 to assemble a fuel cell membrane electrode.
2. The method for producing a fuel cell membrane electrode according to claim 1, wherein in step S1, the method for producing the polybenzimidazole-doped molten proton conductor electrolyte membrane is as follows:
1) Melting the molten proton conductor at a temperature 0-30 ℃ higher than the melting point of the molten proton conductor to convert the molten proton conductor into a molten proton conductor;
2) And soaking the polybenzimidazole membrane in a molten proton conductor, taking out the polybenzimidazole membrane after soaking is finished, and removing the excessive proton conductor on the surface of the membrane to obtain the polybenzimidazole doped molten proton conductor electrolyte membrane.
3. The method for producing a fuel cell membrane electrode assembly according to claim 1, wherein in step S2, the catalyst paste includes: a catalyst slurry containing phosphoric acid and/or a catalyst slurry containing phosphoric acid and a molten proton conductor;
when the catalyst slurry is a catalyst slurry containing phosphoric acid and a molten proton conductor, the catalyst slurry containing phosphoric acid and a molten proton conductor is coated on the microporous layer side of the gas diffusion layer, and then the catalyst slurry containing phosphoric acid is coated.
4. The method for preparing a fuel cell membrane electrode assembly according to claim 3, wherein said phosphoric acid-containing catalyst slurry comprises: catalyst, binder, phosphoric acid, deionized water and alcohol.
5. The method for producing a fuel cell membrane electrode assembly according to claim 4, characterized in that the phosphoric acid-containing catalyst slurry is produced by:
catalyst, binder, phosphoric acid, deionized water and alcohol are mixed according to the mass ratio of 1:0.01 to 0.1:0.1 to 1:1 to 10: 5-50, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid; wherein the binder is one or more of polytetrafluoroethylene, polybenzimidazole and polyvinylidene fluoride; the alcohol is one or more of ethanol, methanol, isopropanol and n-propanol; the catalyst is a carbon-supported platinum catalyst, wherein the mass ratio of platinum to the carbon carrier is 1-9:9-1.
6. The method for producing a fuel cell membrane electrode assembly according to claim 3, wherein the catalyst slurry containing phosphoric acid and a molten proton conductor comprises: catalyst, binder, phosphoric acid and molten proton conductor, deionized water.
7. The method for producing a fuel cell membrane electrode assembly according to claim 6, wherein the method for producing the catalyst slurry containing phosphoric acid and a molten proton conductor is: mixing a catalyst, a binder, phosphoric acid, a molten proton conductor and deionized water according to a mass ratio of 1:0.01 to 0.1:0.1 to 1: 5-50, and ultrasonically stirring to obtain catalyst slurry containing phosphoric acid and a molten proton conductor; wherein the mass ratio of the phosphoric acid to the molten proton conductor is 1:1 to 10; wherein the binder is one or more of polytetrafluoroethylene, polybenzimidazole and polyvinylidene fluoride; the catalyst is a carbon-supported platinum catalyst, wherein the mass ratio of platinum to the carbon carrier is 1-9:9-1; the molten proton conductor is MH 5 (PO 4 ) 2 Wherein M is Cs or K.
8. The method for producing a fuel cell membrane electrode assembly according to claim 1, wherein in step S2, the proton conductor-containing catalyst slurry is applied by one of spray coating, blade coating, and slit extrusion coating.
9. The method for producing a fuel cell membrane electrode assembly according to claim 1, wherein the drying in step S2 is drying at 60 to 200 ℃.
10. A membrane electrode produced by the method for producing a fuel cell membrane electrode according to any one of claims 1 to 9.
CN202210840927.0A 2022-07-18 2022-07-18 Membrane electrode based on molten proton conductor electrolyte membrane and preparation method thereof Pending CN115241505A (en)

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