CN114361545A - Cross-temperature-zone membrane electrode and proton exchange membrane fuel cell thereof - Google Patents

Cross-temperature-zone membrane electrode and proton exchange membrane fuel cell thereof Download PDF

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CN114361545A
CN114361545A CN202210020153.7A CN202210020153A CN114361545A CN 114361545 A CN114361545 A CN 114361545A CN 202210020153 A CN202210020153 A CN 202210020153A CN 114361545 A CN114361545 A CN 114361545A
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裴素朋
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a temperature-span region membrane electrode and a proton exchange membrane fuel cell thereof, wherein the membrane electrode comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a sealing component; the anode catalyst layer and the cathode catalyst layer simultaneously contain fluorine-containing ion exchange resin, a carrier, a catalyst active component loaded on the carrier and an anti-reversal material; the anode catalyst layer and the cathode catalyst layer comprise the following components in percentage by mass: 1-80 wt% of fluorine-containing ion exchange resin, 10-99 wt% of carrier, 0.1-60 wt% of catalyst active component loaded on the carrier and 0-10 wt% of anti-counter electrode material; the proton exchange membrane comprises fluorine-containing ion exchange resin and a porous fiber polymer matrix, and the anode gas diffusion layer and the cathode gas diffusion layer respectively comprise a porous substrate layer and a microporous layer; the invention has high proton conductivity under high temperature and low temperature environment, good mechanical property and long service life.

Description

Cross-temperature-zone membrane electrode and proton exchange membrane fuel cell thereof
[ technical field ]
The invention belongs to the field of proton exchange membrane fuel cells, and particularly relates to a membrane electrode with a cross-temperature region (cross-freezing point and cross-boiling point) working capacity and a proton exchange membrane fuel cell thereof.
[ background art ]
Proton Exchange Membrane Fuel Cells (PEMFC) are efficient, clean and environment-friendly power generation devices, and have wide application prospects in the fields of electric vehicles, decentralized power stations, submarines, spacecrafts and the like. At present, the widely used PEMFC is a perfluorosulfonic acid proton exchange membrane represented by Nafion and a perfluorosulfonic acid resin, and because of being limited by the influence of proton conduction and physicochemical characteristics of sulfonic acid groups, such PEMFC is difficult to conduct protons when operated at temperatures above 100 ℃ or in low humidity environments, and thus the fuel cell performance is low. In addition, the limitation of working temperature makes it face problems of poor CO tolerance, difficult water management of the system, low catalyst activity, etc. in practical operation. In order to solve the problems of the current fuel cell, such as enhancing the CO poisoning resistance of the catalyst, improving the activity and durability of the catalyst, and improving the flooding problem of the system, the most effective and feasible method is to increase the operating temperature of the fuel cell to more than 100 ℃, namely a high-temperature proton exchange membrane fuel cell (HT-PEMFC).
In view of the attractive development prospect of the high-temperature proton exchange membrane fuel cell, research work on HT-PEMFC key materials, including a high-temperature proton exchange membrane, high-temperature ion exchange resin, a catalyst, a carrier and the like, has been widely carried out at home and abroad, and a series of research results are obtained, particularly in the field of high-temperature proton exchange membranes. At present, research on high-temperature proton exchange membranes is mainly focused on phosphoric acid doped Polybenzimidazole (PBI) (CN 111244513A), and the membranes have the defects of simple preparation process and strong high-temperature proton conductivity, but low-temperature working efficiency, incapability of quick start, poor stability, short service life and the like. Although the degradation problem of the high temperature proton membrane is alleviated by cross-linking protection of the terminal amino groups on the PBI main chain, in the deluxe (CN 200710171866.9, CN 200710171865.4, CN 200710171867.3) and prunus et al, the low temperature cold start problem is still not improved.
In order to overcome the problem of low-temperature cold start of a high-temperature fuel cell, the proton exchange membrane and the polymer resin with a perfluoro phosphoric acid/sulfonic acid structure coexisting are constructed by the technology. According to the proton conduction principle and the physicochemical characteristics of sulfonic acid groups and phosphoric acid groups, the perfluorosulfonic acid proton membrane and the resin can conduct protons at the temperature of-40-80 ℃, and when the temperature exceeds 100 ℃, the proton conduction capability is obviously reduced, so that the ion conduction requirement cannot be met. The perfluoro phosphoric acid proton membrane and the resin can effectively conduct protons at 100-150 ℃, and the proton conduction is difficult when the temperature is lower than 100 ℃. The construction of the perfluorophosphoric acid/sulfonic acid coexisting structure can simultaneously make up the defects that a perfluorosulfonic acid structure proton membrane and resin cannot run at high temperature and the defects that the perfluorophosphoric acid proton membrane and the resin cannot run at low temperature, and realize the wide service temperature of-40-150 ℃. Therefore, the implementation of the invention can form revolutionary hydrogen fuel cell technology and promote the deep revolution of the global hydrogen energy application field.
[ summary of the invention ]
The invention aims to solve the defects and provide a temperature-crossing region membrane electrode which has high proton conductivity in high-temperature and low-temperature environments, good mechanical property and long service life, and a fuel cell stack assembled by the temperature-crossing region membrane electrode not only realize cold start in a range of-40 to 0 ℃, but also have good power generation performance and high CO poisoning resistance in a high-temperature region of 100 to 150 ℃.
The temperature-span region membrane electrode comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a sealing component, wherein the anode catalyst layer is arranged on the anode catalyst layer; the anode catalyst layer and the cathode catalyst layer simultaneously contain fluorine-containing ion exchange resin, a carrier, a catalyst active component loaded on the carrier and an anti-reversal material, wherein the fluorine-containing ion exchange resin is used for conducting protons, the carrier is used for conducting electrons, and the catalyst active component loaded on the carrier is used for catalyzing electrochemical reaction; the anode catalyst layer and the cathode catalyst layer comprise the following components in percentage by mass: 1-80 wt% of fluorine-containing ion exchange resin, 10-99 wt% of carrier, 0.1-60 wt% of catalyst active component loaded on the carrier and 0-10 wt% of anti-pole material; the proton exchange membrane comprises fluorine-containing ion exchange resin and a porous fiber polymer matrix, and the anode gas diffusion layer and the cathode gas diffusion layer respectively comprise a porous substrate layer and a microporous layer.
Furthermore, the fluorine-containing ion exchange resin in the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending one or more of A, B components in a certain proportion: A. the fluorine-containing ion exchange resin simultaneously contains sulfonic acid and phosphoric acid groups; B. the fluorine-containing sulfonic acid resin containing sulfonic acid groups and/or the fluorine-containing phosphoric acid resin containing phosphoric acid groups are obtained by blending according to a certain proportion; the thickness of the cathode catalyst layer is 0.05-200um, preferably 1-30um, wherein the loading amount of the catalyst active component is 0.001-20mg/cm2Preferably 0.1 to 1mg/cm2(ii) a The thickness of the anode catalyst layer is 0.05-200um, preferably 0.5-20um, wherein the loading amount of the catalyst active component is 0.001-20mg/cm2Preferably 0.01 to 0.5mg/cm2。
Further, the carriers in the anode catalyst layer and the cathode catalyst layer are one or more combinations of conductive carbon materials and conductive ceramic materials; wherein the conductive carbon material is selected from but not limited to carbon black, ketjen black, acetylene black, Vulcan carbon, porous carbon, carbon nanotube, carbon nanosphere, carbon nanohorn, graphene, carbon nanofiber, carbon sheet and one or more combinations of the carbon materials doped with hetero atoms thereof, and the hetero atoms are not limited to S, N, P, B; the conductive ceramic material comprises one or more of transition metal oxide, transition metal carbide and transition metal nitride; the transition metal oxide is selected from but not limited to titanium oxide, tin dioxide, zirconium oxide, iridium oxide, tungsten oxide, zinc oxide, aluminum oxide, cerium oxide, nickel oxide, magnesium oxide, molybdenum oxide, manganese dioxide, lanthanum oxide and one or more combinations of alkaline earth metal or rare earth metal mono-doped, double-doped or multi-doped oxides thereof; transition metal carbides are selected from, but not limited to, one or more combinations of titanium carbide, zirconium carbide, tungsten carbide, molybdenum carbide, tantalum carbide, cobalt carbide, iron carbide, chromium carbide, vanadium carbide, hafnium carbide, and alkaline earth or rare earth singly, doubly or multiply doped carbides thereof, and the like; the transition metal nitride is selected from but not limited to one or more combinations of titanium nitride, zirconium nitride, tungsten nitride, molybdenum nitride, tantalum nitride, cobalt nitride, iron nitride, chromium nitride, vanadium nitride, hafnium nitride, and alkaline earth metal or rare earth metal mono-doped, di-doped or multi-doped nitrides thereof, and the like.
Further, the catalyst active components in the anode catalyst layer and the cathode catalyst layer are one or more of Pt-based catalysts and non-Pt-based catalysts; the Pt-based catalyst comprises Pt and PtM alloy, wherein M in the PtM alloy is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al; the non-Pt-based catalyst comprises metal, single metal atom and nonmetal, wherein the metal catalyst is mostly transition metal and is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, the molecular formula of the single metal atom catalyst is written as M-N/S/P-C, M is mostly transition metal and is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, and the nonmetal catalyst is selected from one or more of carbon material and hetero atom doped carbon material; the anti-reversal material in the anode catalysis layer is selected from one or more of, but not limited to, ethylene oxide, ruthenium dioxide, cerium dioxide and nickel oxide.
Further, the preparation method of the anode catalysis layer and the cathode catalysis layer comprises the following steps: mixing fluorine-containing ion exchange resin solution, a catalyst, an anti-reversal material, deionized water, organic matter solution and the like, processing by one or more processes of magnetic stirring, water bath ultrasound, ultrasonic bar, shearing emulsification, homogenization and ball milling to obtain uniformly dispersed catalyst slurry, and preparing an anode catalyst layer and a cathode catalyst layer by one of spraying, bar coating, blade coating, slit coating, window coating, roll-to-roll coating and dipping; the preparation method comprises the following materials in proportion: the solid content of the catalyst slurry is 0.1-70 wt%, preferably 2-50 wt%; wherein the mass ratio of the perfluorinated ion resin to the carrier is 0.05-5, preferably 0.1-2; the mass ratio of the organic matter to the water is 1:99-70:30, preferably 1:99-50: 50; the mass ratio of the anti-electrode material is 0-10 wt%, preferably 0-1 wt%; the organic solution in the preparation method is formed by one or more of methanol, ethanol, ethylene glycol, isopropanol, N-propanol, propylene glycol, glycerol, N-butanol, N-pentanol, 2-ethylhexanol, cyclohexanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide through blending.
Further, the porous fiber polymer matrix of the proton exchange membrane is made of one or more materials selected from polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene, polypropylene, polyethylene-propylene copolymer, polyether sulfone, polyether ketone, polyimide, polybenzimidazole and sulfonated and phosphorylated derivatives thereof; the thickness of the proton exchange membrane is 5-300um, the thickness of the porous fiber polymer matrix is 2-30um, the number of used porous foreguard polymer matrix layers is 0-30 layers, the porous fiber polymer matrix is a homogeneous membrane when being 0 layer, and the porous fiber polymer matrix is a composite reinforced membrane when being 1-30 layers; the sealing component comprises a pressure-sensitive adhesive type frame material and a hot melt adhesive type frame material, wherein the pressure-sensitive adhesive type frame material is selected from but not limited to acrylate copolymer, styrene-isoprene-styrene and styrene-butadiene-styrene block copolymer, organic silicon copolymer, polyurethane and a new substance formed by modifying the pressure-sensitive adhesive type frame material, and the hot melt adhesive type frame material is selected from but not limited to ethylene-vinyl acetate, polyamides, polyesters, polyurethanes, polyolefins and rubbers.
Further, the total thickness of the anode gas diffusion layer and the cathode gas diffusion layer is 1-1000um, preferably 100-400 um; the thickness of the microporous layer in the anode gas diffusion layer and the cathode gas diffusion layer is 0-500um, preferably 20-100 um; the porous substrate layer in the anode gas diffusion layer and the cathode gas diffusion layer contains 30-99 wt% of conductive carbon material and 1-70 wt% of hydrophobic agent, the conductive carbon material is preferably 50-95 wt%, the conductive carbon material is selected from but not limited to carbon paper, carbon cloth, carbon felt and non-woven fabric, and the hydrophobic agent is preferably 5-50 wt%; the aperture of the porous substrate layer is 10-200um, the contact angle is 30-160 degrees, preferably 120-160 degrees; the microporous layer in the anode gas diffusion layer and the cathode gas diffusion layer contains 30-99 wt% of carbon black and 1-70 wt% of a hydrophobic agent, the carbon black is preferably 50-95 wt%, and the hydrophobic agent is preferably 5-50 wt%; the aperture of the microporous layer is 0.01-200um, the contact angle is 30-160 degrees, preferably 120-160 degrees; the hydrophobic agent in both the porous substrate layer and the microporous layer is selected from, but not limited to, polytetrafluoroethylene, fluorinated ethylene propylene, perfluoropolyethers, polyvinylidenefluorides, perfluorohydroxyls, polydimethylsiloxanes.
The invention also provides a preparation method of the membrane electrode in the temperature-crossing region, which comprises the following steps:
1) preparation of catalyst slurry: firstly, mixing a perfluorinated ion resin solution, catalyst particles, a carrier, an anti-reversal material, deionized water and an organic solvent according to the mixture ratio, and then carrying out one or more processes of magnetic stirring, water bath ultrasound, ultrasonic bar, shearing emulsification, homogenization and ball milling to obtain uniformly dispersed catalyst slurry;
2) preparation of the catalytic layer: coating the uniformly dispersed catalyst slurry on a polytetrafluoroethylene flexible substrate, or a proton exchange membrane, or a microporous layer of a gas diffusion layer through one of spraying, wire bar coating, blade coating, slit coating, window coating, roll-to-roll coating and dipping, and drying to obtain a cathode catalyst layer and an anode catalyst layer; the anode catalyst layer and the cathode catalyst layer comprise the following components in percentage by mass: 1-80 wt% of fluorine-containing ion exchange resin, 10-99 wt% of carrier, 0.1-60 wt% of catalyst active component loaded on the carrier and 0-10 wt% of anti-pole material; the thickness of the cathode catalyst layer is 0.05-200um, and the loading capacity of the catalyst particles is 0.001-20mg/cm2(ii) a The thickness of the anode catalyst layer is 0.05-200um, and the loading capacity of the catalyst particles is 0.001-20mg/cm2；
3) Assembling a membrane electrode: the membrane electrode comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a frame, wherein the assembly mode among the layers is any one of the following five modes:
the first method is as follows: if at least one of the cathode catalyst layer or the anode catalyst layer is coated on a flexible substrate of polytetrafluoroethylene, step 1) firstly, one side of the catalyst layer is close to a proton exchange membrane, and a membrane coated with the catalyst layer, namely CCM, is obtained after thermal transfer printing treatment; step 2) respectively attaching the frame to the anode catalytic layer side and the cathode catalytic layer side, and assembling the frames together in a hot pressing or gluing mode; step 3), enabling the microporous layer of the anode gas diffusion layer to face the anode catalyst layer and the microporous layer of the cathode gas diffusion layer to face the cathode catalyst layer, and then assembling the microporous layers in a hot-pressing mode or a two-side dispensing mode or a four-side dispensing mode to obtain a membrane electrode; the step 2) and the step 3) can be replaced, namely the frame can be arranged between the catalyst layer and the gas diffusion layer or at the outer side of the gas diffusion layer;
the second method comprises the following steps: if the anode catalyst layer and the cathode catalyst layer are directly coated on two sides of the proton exchange membrane, the membrane electrode assembly is directly carried out in the steps 2) and 3) in the first use mode; likewise, step 2) and step 3) are replaceable;
the third method comprises the following steps: if only one of the anode catalyst layer and the cathode catalyst layer is directly coated on one side of the proton exchange membrane, the other catalyst layer and the anode catalyst layer are required to be subjected to heat transfer printing treatment to obtain CCM; then assembling the membrane electrode by the steps 2) and 3) in the first use mode;
the method is as follows: if the anode catalyst layer and the cathode catalyst layer are directly coated on the gas diffusion layer, the two gas diffusion layers with the catalyst layers are respectively placed on two sides of the proton exchange membrane, one sides of the catalyst layers are close to the proton exchange membrane, after hot-pressing treatment, the frames are respectively placed on the carbon paper sides of the anode gas diffusion layer and the cathode gas diffusion layer, and then membrane electrodes are prepared in a hot-pressing or gluing mode;
the fifth mode is as follows: if one of the anode catalyst layer and the cathode catalyst layer is directly coated on the gas diffusion layer, the gas diffusion layer with the catalyst layer and the other independent catalyst layer are respectively arranged on two sides of the proton exchange membrane, the CCM with the gas diffusion layer on one side is obtained after hot-pressing treatment, then the microporous layer of the other gas diffusion layer is attached to the catalyst layer, after hot-pressing treatment, the frames are respectively arranged on the carbon paper sides of the anode gas diffusion layer and the cathode gas diffusion layer, and then the membrane electrode is prepared through hot-pressing or gluing.
The invention also provides a proton exchange membrane fuel cell, which consists of the membrane electrode or the membrane electrode prepared by one of the preparation methods, a cathode plate, an anode plate and a sealing assembly, wherein the anode plate, the cathode plate and the periphery of the membrane electrode form a sealing space which is filled with a sealing material; the anode plate and the cathode plate are one or more composite plates of a graphite plate, a titanium plate, a stainless steel plate and an aluminum plate; the sealing component is one of rubber, plastic and metal composite sealing gaskets, preferably but not limited to silicon rubber, tetrafluoroethylene-propylene rubber, perfluororubber, fluorosilicone rubber, ethylene-propylene rubber, polytetrafluoroethylene and perfluoroethylene-propylene copolymer; the sealing component has good sealing performance in a wide service temperature range of-40-150 ℃.
The invention also provides a proton exchange membrane fuel cell stack which is formed by connecting a plurality of proton exchange membrane fuel cells in series.
Compared with the prior art, the invention provides a membrane electrode with a temperature-crossing region working capacity, which comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer and a cathode gas diffusion layer, wherein the resins used in the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane simultaneously have sulfonic acid groups and phosphoric acid groups or are a blend of perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin, and the resin has high proton conductivity, good mechanical property and long service life in high-temperature and low-temperature environments; the fuel cell and the fuel cell stack assembled by the membrane electrode not only realize cold start within the range of minus 40-0 ℃, but also have good power generation performance and higher CO poisoning resistance in a high-temperature area of 100-150 ℃, and realize good operation at a wide service temperature of minus 40-150 ℃.
[ description of the drawings ]
FIG. 1 is a polarization diagram of example 1 of the present invention;
FIG. 2 shows the results of inventive example 1 at-20 ℃ and 0.88A (0.02A cm)-2) A graph of voltage versus time during constant current discharge;
FIG. 3 shows the voltage @1A cm at different CO concentrations for example 1 of the present invention-2；
FIG. 4 is a graph comparing polarization curves of examples 2 to 7 of the present invention and comparative example 1;
FIG. 5 shows inventive examples 2 to 7 and comparative example 1 at-20 ℃ and 0.88A (0.02A cm)-2) The time elapsed from the constant current discharge to a voltage of 0;
FIG. 6 shows inventive examples 2 to 7 and comparative example 1 at-20 ℃ and 0.88A (0.02A cm)-2) The product water was produced by constant current discharge to a voltage of 0.
[ detailed description of the invention ]
The invention relates to a membrane electrode with a cross-temperature-zone (cross-freezing-point and cross-boiling-point) working capacity, in particular to a membrane electrode, wherein resins used by a cathode catalyst layer, an anode catalyst layer and a proton exchange membrane related to the membrane electrode are proton polymer resins containing a perfluoro phosphoric acid/sulfonic acid structure coexisting, and a proton exchange membrane fuel cell assembled based on the membrane electrode can show good performance at a wide service temperature of-40-150 ℃.
The invention aims to provide a membrane electrode with a cross-temperature-zone working capacity, which comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer and a cathode gas diffusion layer. The resins used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane are perfluorinated ion exchange resins with the proton conductivity in a temperature-crossing region, and the resins have both sulfonic acid groups and phosphoric acid groups, have high proton conductivity in high-temperature and low-temperature environments, and have good mechanical properties and long service life.
Another object of the present invention is to provide a method for preparing a membrane electrode with a cross-temperature-zone working capability, comprising: the preparation method comprises the steps of catalyst slurry preparation, catalyst layer coating preparation, and assembly of proton exchange membrane, catalyst layer and gas diffusion layer.
The invention further aims to provide a proton exchange membrane fuel cell with the temperature-crossing working capacity, and the performance of the proton exchange membrane fuel cell is evaluated, so that the proton exchange membrane fuel cell not only realizes quick cold start within the range of-40-0 ℃, but also has good power generation performance and higher CO poisoning resistance at the temperature of 100-150 ℃.
It is yet another object of the present invention to provide a pem fuel cell stack having a cross-temperature zone operating capability.
The above object of the present invention is achieved by the following technical solutions:
first, membrane electrode
In one aspect, the invention provides a membrane electrode with a temperature-crossing region working capacity, which consists of an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a sealing component. The preparation process comprises the following steps:
(1) preparation of catalyst slurry: firstly, mixing a perfluorinated ion resin solution, catalyst particles, a carrier, an anti-reversal material, deionized water and an organic solvent according to the material proportion in the table 1, and then carrying out one or more processes of magnetic stirring, water bath ultrasound, an ultrasonic rod, shearing emulsification, homogenization and ball milling to obtain uniformly dispersed catalyst slurry.
TABLE 1 catalyst slurry materials ratio
Figure BDA0003462060470000101
(2) Preparation of the catalytic layer: coating the uniformly dispersed catalyst slurry on (a) a flexible substrate of polytetrafluoroethylene by one of spraying, wire bar coating, blade coating, slot coating, window coating, roll-to-roll coating, dipping; or (b) a proton exchange membrane; or (c) a microporous layer of the gas diffusion layer and drying to obtain a cathode catalytic layer and an anode catalytic layer. Wherein the anode catalyst layer and the cathode catalyst layer comprise the following components in percentage by mass: 1-80 wt% of fluorine-containing ion exchange resin, 10-99 wt% of carrier, 0.1-60 wt% of catalyst active component loaded on the carrier and 0-10 wt% of anti-pole material; the thickness of the cathode catalyst layer is 0.05-200um, and the loading capacity of the catalyst particles is as follows: 0.001-20mg/cm2(ii) a The thickness of the anode catalyst layer is 0.05-200um, and the loading capacity of catalyst particles is as follows: 0.001-20mg/cm2；
(3) Assembling a membrane electrode: the membrane electrode comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a frame, wherein the assembly modes among the layers are as follows:
the first method is as follows: if at least one of the cathode catalyst layer or the anode catalyst layer is coated on a flexible substrate of polytetrafluoroethylene, 1) firstly, attaching one side of the catalyst layer to a proton exchange membrane, and obtaining a membrane coated with the catalyst layer, namely CCM after thermal transfer printing treatment; 2) respectively attaching the frame to the anode catalytic layer side and the cathode catalytic layer side, and assembling the frames together in a hot pressing or gluing mode; 3) and (3) enabling the microporous layer of the anode gas diffusion layer to face the anode catalyst layer and the microporous layer of the cathode gas diffusion layer to face the cathode catalyst layer, and then assembling the membrane electrode in a hot pressing mode or a two-side dispensing mode or a four-side dispensing mode. In the method, the step 2) and the step 3) can be replaced, namely the frame can be arranged between the catalytic layer and the gas diffusion layer or on the outer side of the gas diffusion layer.
The second method comprises the following steps: and if the anode catalyst layer and the cathode catalyst layer are directly coated on two sides of the proton exchange membrane, the membrane electrode assembly is directly carried out in the steps 2) and 3) in the first use mode. Likewise, steps 2) and 3) can be replaced.
The third method comprises the following steps: if only one of the anode catalyst layer and the cathode catalyst layer is directly coated on one side of the proton exchange membrane, the other catalyst layer and the anode catalyst layer are required to be subjected to heat transfer printing treatment to obtain CCM; and then assembling the membrane electrode by the steps 2) and 3) in the first use mode.
The method is as follows: if the anode catalyst layer and the cathode catalyst layer are directly coated on the gas diffusion layer, the two gas diffusion layers with the catalyst layers are respectively arranged on two sides of the proton exchange membrane, one side of the catalyst layer is close to the proton exchange membrane, after hot-pressing treatment, the frames are respectively arranged on the carbon paper sides of the anode gas diffusion layer and the cathode gas diffusion layer, and then membrane electrodes are prepared in a hot-pressing or gluing mode.
The fifth mode is as follows: if one of the anode catalyst layer and the cathode catalyst layer is directly coated on the gas diffusion layer, the gas diffusion layer with the catalyst layer and the other independent catalyst layer are respectively arranged on two sides of the proton exchange membrane, the CCM with the gas diffusion layer on one side is obtained after hot-pressing treatment, then the microporous layer of the other gas diffusion layer is attached to the catalyst layer, after hot-pressing treatment, the frames are respectively arranged on the carbon paper sides of the anode gas diffusion layer and the cathode gas diffusion layer, and then the membrane electrode is prepared through hot-pressing or gluing.
In step (1), the solid content of the catalyst slurry is 2 to 50% by weight, more preferably 5 to 30% by weight. The mass ratio of the perfluorinated ion resin to the carrier is 0.1-2, and more preferably 0.3-1. The mass ratio of the organic solvent to the water is 1:99-50: 50; more preferably from 10:90 to 30: 70; the organic solvent is one or more of methanol, ethanol, ethylene glycol, isopropanol, N-propanol, glycerol, N-butanol, N-pentanol, 2-ethylhexanol, cyclohexanol, N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), and N, N-dimethylacetamide (DMAc) dimethyl sulfoxide (DMSO). Preferably one or more of methanol, ethanol, ethylene glycol, isopropanol, N-propanol, glycerol, N-butanol, N-pentanol, 2-ethylhexanol, cyclohexanol, and N-methylpyrrolidone, and more preferably one or more of ethanol, ethylene glycol, isopropanol, N-propanol, glycerol, N-butanol, and N-methylpyrrolidone. The mass ratio of the anode anti-counter electrode material is 0-1 wt%, and more preferably 0.2-0.6 wt%; the mass ratio of the cathode anti-counter electrode material is 0-1 wt%, and more preferably 0-0.6 wt%. The catalyst slurry dispersing process comprises one or more of magnetic stirring, water bath ultrasonic treatment, ultrasonic rod treatment and homogenization. The fluorine-containing ion exchange resin is prepared by blending A, B one or more of two components according to a certain proportion:
A. the fluorine-containing ion exchange resin simultaneously contains sulfonic acid and phosphoric acid groups;
B. the fluorine-containing sulfonic acid resin containing sulfonic acid groups and/or the fluorine-containing phosphoric acid resin containing phosphoric acid groups are obtained by certain blending.
In the step (1), the carrier in the catalytic layer is one or a combination of more of conductive carbon materials and conductive ceramic materials. 1) The conductive carbon material is selected from, but not limited to, carbon black, Ketjen black (Ketjen black), Acetylene black (Acetylene black), Vulcan carbon, porous carbon, carbon nanotube, carbon nanosphere, carbon nanohorn, graphene, carbon nanofiber, carbon sheet, and hetero atoms thereof (e.g., S, N, P, ga, and a, ga, and a mixture thereof,B, etc.) one or more combinations of doped carbon, etc. 2) The conductive ceramic material includes one or more of transition metal oxides, transition metal carbides, transition metal nitrides, and the like. The transition metal oxide is selected from, but not limited to, titanium oxide (TiO)X) Tin dioxide (SnO)2) Zirconium oxide (ZrO)2) Iridium oxide (IrO)2) Tungsten oxide (WO)3) Zinc oxide (ZnO), aluminum oxide (Al)2O3) Cerium oxide (CeO)2) Nickel oxide (NiO)x) Magnesium oxide (MgO), molybdenum oxide (MoO)3) Manganese dioxide (MnO)2) Lanthanum oxide (La)2O3) And one or more of alkaline earth metal or rare earth metal singly doped, doubly doped or multiply doped oxides thereof; the transition metal carbide is selected from, but not limited to, titanium carbide (TiC)x) Zirconium carbide (ZrC)x) Tungsten carbide (WC)x) Molybdenum carbide (MoC)x) Tantalum carbide (TaC)x) Cobalt carbide (CoC)x) Iron carbide (FeC)x) Chromium carbide (CrC)x) Vanadium Carbide (VC)x) Hafnium carbide (HfC)x) And one or more combinations of alkaline earth metal or rare earth metal single-doped, double-doped or multi-doped carbides thereof; the transition metal nitride is selected from, but not limited to, titanium nitride (TiN)x) Zirconium nitride (ZrN)x) Tungsten nitride (WN)x) Molybdenum nitride (MoN)x) Tantalum nitride (TaN)x) Cobalt nitride (CoN)x) Iron nitride (FeN)x) Chromium nitride (CrN)x) Vanadium Nitride (VN)x) Hafnium nitride (HfN)x) And one or more of alkaline earth metal or rare earth metal mono-doped, double-doped or multi-doped nitrides thereof.
In the step (1), the active component in the catalyst layer is one or more of a Pt-based catalyst and a non-Pt-based catalyst. 1) The Pt-based catalyst comprises Pt and PtM alloy, wherein M in the PtM alloy is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, and M is preferably one or more of Co, Ni, Ru, Pd, V and Fe; 2) the non-Pt-based catalyst comprises metal, single metal atom and nonmetal, wherein the metal catalyst is mostly transition goldThe catalyst is characterized by being prepared from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, preferably Co, Ni, Ru, Pd, Au, Ag, Ir and Fe, and having a single metal atom catalyst formula which can be written as M-N/S/P-C, wherein M is mostly transition metal and is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, M is preferably selected from one or more of Co, Ni, Fe and Mn, and a nonmetal catalyst is selected from one or more of carbon materials and heterogeneous atom-doped carbon materials. The anti-counter electrode material is selected from but not limited to yttrium dioxide (IrO)2) Rubidium dioxide (RuO)2) Cerium oxide (CeO)2) One or more of nickel oxide (NiO), preferably IrO2。
In the step (2), the preparation method of the catalyst layer comprises spraying, wire bar coating and roll-to-roll coating, and the coating substrate is made of polytetrafluoroethylene material. The catalyst layer comprises the following components in percentage by mass: the fluorine-containing ion exchange resin is 5 to 60 wt%, more preferably 10 to 45 wt%, the carrier is 20 to 80 wt%, more preferably 30 to 65 wt%, and the catalyst active component supported on the carrier is 5 to 60 wt%, more preferably 10 to 40 wt%. The mass percent of the anti-electrode material is 0-1 wt%, and more preferably 0-0.6 wt%. The thickness of the cathode catalytic layer is 1-30um, more preferably 5-20um, and the catalyst loading capacity of the cathode catalytic layer is 0.1-1mg/cm2More preferably 0.15 to 0.8mg/cm2(ii) a The thickness of the anode catalytic layer is 0.5-20um, more preferably 1-8um, and the catalyst loading capacity of the anode catalytic layer is 0.01-0.5mg/cm2More preferably 0.05 to 0.15mg/cm2。
In the step (3), the proton exchange membrane comprises fluorine-containing ion exchange resin and a porous fiber polymer matrix. The thickness of the proton exchange membrane is 5-300um, preferably 8-150um, more preferably 8-50 um. Wherein the fluorine-containing ion exchange resin is formed by mixing one or two of fluorine-containing ion exchange resin with coexisting sulfonic acid/phosphoric acid groups, perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin according to a certain proportion. The porous fiber polymer matrix is made of one or more materials selected from polytetrafluoroethylene, polyvinylidene fluoride-Co-hexafluoropropylene, polyethylene, polypropylene, polyethylene-Co-propylene, polyether sulfone, polyether ketone, polyimide, polybenzimidazole and sulfonated and phosphorylated derivatives thereof. The porous fibrous polymer matrix has a thickness of 2-30um, preferably 5-20 um. The porous fibrous polymer matrix is used in a number of layers from 0 to 30, preferably from 0 to 10, more preferably from 0 to 5. The porous fiber polymer matrix is a homogeneous film when the number of the porous fiber polymer matrix is 0, and is a composite reinforced film when the number of the porous fiber polymer matrix is 1-30.
In the step (3), the thickness of the gas diffusion layer is 100-400um, more preferably 150-300um, and the contact angle is preferably 120-160 °. The gas diffusion layer is composed of a porous substrate layer and a microporous layer, wherein the porous substrate layer contains 50-95 wt% of a conductive carbon material (preferably 60-90 wt%), preferably one of carbon paper and carbon cloth, and 5-50 wt% of a hydrophobic agent (preferably 10-40 wt%), preferably one or more of Polytetrafluoroethylene (PTFE) and Fluorinated Ethylene Propylene (FEP).
In the step (3), the sealing component material is a pressure sensitive adhesive type or a hot melt adhesive type. The pressure sensitive adhesive type frame material is selected from but not limited to acrylate copolymer, styrene-isoprene-styrene (SIS) and styrene-butadiene-styrene (SBS) block copolymer, organic silicon copolymer, polyurethane and modified to form new substances. The hot melt adhesive type frame material is selected from, but not limited to, ethylene-vinyl acetate (EVA) type, Polyamide (PA) type, Polyester (PET) type, Polyurethane (PU) type, polyolefin type, and rubber type. The membrane electrode assembly in this step is preferably the first membrane electrode assembly described above.
Proton exchange membrane fuel cell
In another aspect, the invention provides a proton exchange membrane fuel cell, which comprises the membrane electrode, a cathode plate, an anode plate and a sealing component. The anode plate and the cathode plate are one of a graphite plate and a titanium metal plate or a composite plate. The sealing component is high-temperature-resistant fluororubber or a metal composite sealing gasket.
Three, proton exchange membrane fuel cell stack
In another aspect, the present invention provides a pem fuel cell stack, which is formed by connecting a plurality of pem fuel cells in series.
The invention will be further described with reference to the following specific examples and drawings:
example 1:
preparation of membrane electrode 1: the membrane electrode is composed of an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a sealing component. The preparation process comprises the following steps:
(1) preparing a cathode catalytic layer: firstly, mixing a fluorine-containing ion resin solution containing both sulfonic acid groups and phosphoric acid groups with a certain amount of deionized water and n-propanol, stirring for 10min by magnetic force, adding a Pt/C catalyst into the mixed solution by spoon, and then carrying out magnetic stirring and ultrasonic bar treatment for 90min to obtain uniformly dispersed catalyst slurry, wherein the corresponding material ratio is shown in table 2. Coating the catalyst slurry on a flexible polytetrafluoroethylene substrate in a wire bar coating mode, and drying to obtain a Pt loading capacity of 0.33-0.40mg/cm2And the cathode catalyst layer is 8-15um thick.
TABLE 2 Material proportioning in catalyst slurries
Figure BDA0003462060470000151
Figure BDA0003462060470000161
(2) Preparing an anode catalyst layer: firstly, mixing fluorine-containing ion resin solution containing sulfonic acid group and phosphoric acid group with deionized water and normal propyl alcohol, stirring for 10min by magnetic force, and then adding Pt/C catalyst and anti-counter electrode material iridium dioxide (IrO) one by one2) And then, after magnetic stirring and ultrasonic bar treatment for 90min, uniformly dispersed catalyst slurry was obtained, and the corresponding material ratios are shown in table 2. Then coating the catalyst slurry on a flexible polytetrafluoroethylene substrate in a wire bar coating mode and drying to obtain the Pt loaded amount of 0.08-0.10mg/cm2And the anode catalyst layer with the thickness of 2-4 um.
(3) Assembling a membrane electrode: 1) respectively attaching a cathode catalyst layer and an anode catalyst layer to two sides of a proton exchange membrane, and obtaining the proton exchange membrane (CCM) with the catalyst layers attached to the two sides through a heat transfer printing process of 3.8MPa, 150 ℃ and 180s, wherein the resin used by the proton exchange membrane is resin simultaneously containing sulfonic acid groups and phosphoric acid groups; 2) cutting the CCM into 5.5cm by 11cm, attaching a gas diffusion layer microporous layer with the size of 5cm by 10.5cm to the anode catalytic layer and the cathode catalytic layer, and assembling the gas diffusion layer microporous layer and the cathode catalytic layer together through hot pressing; 3) then, the frame is respectively attached to the anode gas diffusion layer and the cathode gas diffusion layer and is bonded together through glue, and the effective area is 44.4cm2(4.44cm x 10cm) membrane electrode.
Fuel cell assembly and performance evaluation based on membrane electrode 1: the membrane electrode 1, the anode plate, the cathode plate, the end plate and the sealing material are assembled into an effective area of 44.4cm2The following performance tests were performed on the cells of (1):
1) high-temperature fuel cell performance evaluation: the polarization curve test was performed on the fuel cell assembled with the membrane electrode 1 under the following conditions, and the results are shown in fig. 1.
Testing the working condition: the battery temperature is 100 ℃ and 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A.
2) Cold start capability assessment: placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current is discharged until the voltage is 0 (at this time, the reaction gas channel is completely blocked by the freezing of the water generated by the reaction), and then the water capacity of the membrane electrode, namely the cold start capability below zero of the membrane electrode can be calculated according to the discharge capacity, as shown in fig. 2.
3) Evaluation of CO tolerance: test condition 1 (high temperature): introducing mixed gas of carbon monoxide and hydrogen (carbon monoxide content is selected from 0, 10ppm, 20ppm, 50ppm, 100ppm, 1000ppm, 1500ppm and 2000ppm) into the anode, introducing air into the cathode at a flow rate of 2slpm, introducing air into the cathode at a flow rate of 5slpm and introducing air into the cathode at a pressure of 150 kPa; the temperature of the battery is 100℃,120 ℃; no humidification of gas; after the working condition is reached, the current is tested as follows: 44A (1A cm)-2) The current was run for 5min to obtain voltages at different CO concentrations, as shown in figure 3.
Example 2:
preparation of the membrane electrode 2: the membrane electrode 2 was prepared substantially in the same manner as the membrane electrode 1 in example 1, except that: the resins used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane are perfluorinated phosphoric acid resin. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) The cold start test comprises placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged to a voltage of 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Example 3:
preparation of the membrane electrode 3: the membrane electrode 3 was prepared substantially in the same manner as the membrane electrode 1 in example 1, except that: the resin used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin according to the mass ratio of 1: 4. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) Cold start test of the fuel cell after dry gas purgingPlacing in a low temperature box, freezing to-20 deg.C, keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged to a voltage of 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Example 4:
preparation of the membrane electrode 4: the membrane electrode 4 was prepared substantially in the same manner as the membrane electrode 1 in example 1, except that: the resin used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin according to the mass ratio of 1: 2. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) The cold start test comprises placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged to a voltage of 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Example 5:
preparation of the membrane electrode 5: the membrane electrode 5 was prepared substantially in the same manner as the membrane electrode 1 in example 1, except that: the resin used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin according to the mass ratio of 1: 1. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) The cold start test comprises placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged to a voltage of 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Example 6:
preparation of the membrane electrode 6: the membrane electrode 6 was prepared substantially in the same manner as the membrane electrode 1 in example 1, except that: the resin used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin according to the mass ratio of 2: 1. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) The cold start test comprises placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged until the voltage was 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Example 7:
preparation of the membrane electrode 7: the membrane electrode 7 was prepared substantially in the same manner as the membrane electrode 1 in example 1, except that: the resin used by the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending perfluorinated sulfonic acid resin and perfluorinated phosphoric acid resin according to the mass ratio of 4: 1. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) The cold start test comprises placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged until the voltage was 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Comparative example 1:
the membrane electrode preparation process of comparative example 1 was substantially the same as that of membrane electrode 1 in example 1 except that: the resins used by the cathode catalyst layer, the anode catalyst layer and the proton exchange membrane are perfluorinated sulfonic acid ionic polymers. A fuel cell was then assembled according to the method of example 1 and the following performance tests were performed:
1) polarization curve test, test condition: the temperature of the battery is 120 ℃; introducing hydrogen to the anode at the flow rate of 2 slpm; air is introduced into the cathode, and the flow rate is 5 slpm; the gas is not humidified; after the working condition is achieved, the following currents are used: gradient current test is carried out at 88A/71A/66A/44A/22A/10A/5A/2A/1A/0A, and the corresponding polarization curve is shown in figure 4.
2) The cold start test comprises placing the fuel cell in a low temperature box, freezing to-20 deg.C, and keeping the temperature constant, and placing the fuel cell at 0.88A (0.02A cm)-2) The lower constant current was discharged until the voltage was 0, and the time elapsed when the constant current was discharged to 0 and the amount of product water were counted, as shown in fig. 5 and 6.
Table 3 shows the mass ratio of perfluorosulfonic acid resin to perfluorophosphoric acid resin in the cathode catalyst layer, the anode catalyst layer, and the proton exchange membrane in examples 2 to 7 and comparative example 1:
table 3
Cathode catalyst layer Anode catalyst layer Proton exchange membrane
Example 2 0:1 0:1 0:1
Example 3 1:4 1:4 1:4
Example 4 1:2 1:2 1:2
Example 5 1:1 1:1 1:1
Example 6 2:1 2:1 2:1
Example 7 4:1 4:1 4:1
Comparative example 1 1:0 1:0 1:0
As shown in fig. 1, a polarization curve diagram of example 1 is shown. The test results show that example 1 has good power generation performance at high temperature (100 ℃ and 120 ℃), 2A cm-2The output power at the current density is 1.26W cm-2. If 10 single sheets are used, the effective area is 300cm2The single cells are assembled together, so that a 3780W fuel cell stack can be obtained.
As shown in FIG. 2, the sample is prepared in example 1 at-20 deg.C, 0.88A (0.02A cm)-2) Graph of voltage versus time for constant current discharge. The test results show that example 1 spends 6min discharging to a voltage of 0 at-20 ℃ at 0.88A (0.02A cm-2) constant current. The discharge capacity was 325.6C from Q ═ I × t, i.e. the amount of product water was 1.65 mmol.
As shown in FIG. 3, the voltage @1A cm at different CO concentrations for example 1-2. The test results show that example 1 exhibits good resistance when run at high temperatures (100 ℃ and 120 ℃), and the higher the temperature, the stronger the resistance. The voltage drops significantly only when the CO concentration exceeds 500 ppm.
As shown in FIG. 4, a graph comparing polarization curves of examples 2 to 7 and comparative example 1 is shown. The results show that the component ratio of the perfluorinated phosphoric acid resin in the cathode catalyst layer, the anode catalyst layer and the proton exchange membrane is very important when the membrane is operated at high temperature. The power generation performance of the fuel cell gradually decreases with the decrease of the content of the perfluorophosphoric acid resin, 2A cm-2Output power of from 1.25W cm-2Down to 0.9W cm-2. When the mass ratio of the perfluorosulfonic acid resin to the perfluorophosphoric acid resin was more than 1, the performance was more remarkably decreased, while the performance of the membrane electrode comprising only the perfluorosulfonic acid resin (comparative example 1) was rapidly deteriorated, and the maximum output was less than 0.1W cm-2。
As shown in figure 5 and attached drawings6 for examples 2-7 and comparative example 1 at-20 deg.C, 0.88A (0.02A cm)-2) The time elapsed from constant current discharge to voltage of 0 and the amount of product water produced. The results show that the component proportion of the perfluorinated sulfonic acid resin in the cathode catalyst layer, the anode catalyst layer and the proton exchange membrane is more important than the success of cold start. As the perfluorosulfonic acid resin content decreases, the cold start capability of the fuel cell decreases.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.

Claims (10)

1. A temperature-spanning region membrane electrode, characterized in that: comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a sealing component; the anode catalyst layer and the cathode catalyst layer simultaneously contain fluorine-containing ion exchange resin, a carrier, a catalyst active component loaded on the carrier and an anti-reversal material, wherein the fluorine-containing ion exchange resin is used for conducting protons, the carrier is used for conducting electrons, and the catalyst active component loaded on the carrier is used for catalyzing electrochemical reaction; the anode catalyst layer and the cathode catalyst layer comprise the following components in percentage by mass: 1-80 wt% of fluorine-containing ion exchange resin, 10-99 wt% of carrier, 0.1-60 wt% of catalyst active component loaded on the carrier and 0-10 wt% of anti-pole material; the proton exchange membrane comprises fluorine-containing ion exchange resin and a porous fiber polymer matrix, and the anode gas diffusion layer and the cathode gas diffusion layer respectively comprise a porous substrate layer and a microporous layer.
2. The trans-temperature zone membrane electrode of claim 1, wherein: the fluorine-containing ion exchange resin in the anode catalyst layer, the cathode catalyst layer and the proton exchange membrane is obtained by blending one or more of A, B components in a certain proportion: A. in the fluorine-containing ion exchange resinContaining sulfonic acid and phosphoric acid groups; B. the fluorine-containing sulfonic acid resin containing sulfonic acid groups and/or the fluorine-containing phosphoric acid resin containing phosphoric acid groups are obtained by blending according to a certain proportion; the thickness of the cathode catalyst layer is 0.05-200um, preferably 1-30um, wherein the loading amount of the catalyst active component is 0.001-20mg/cm2Preferably 0.1 to 1mg/cm2(ii) a The thickness of the anode catalyst layer is 0.05-200um, preferably 0.5-20um, wherein the loading amount of the catalyst active component is 0.001-20mg/cm2Preferably 0.01 to 0.5mg/cm2。
3. The trans-temperature zone membrane electrode of claim 1, wherein: the carriers in the anode catalyst layer and the cathode catalyst layer are one or a combination of more of conductive carbon materials and conductive ceramic materials; wherein the conductive carbon material is selected from but not limited to carbon black, ketjen black, acetylene black, Vulcan carbon, porous carbon, carbon nanotube, carbon nanosphere, carbon nanohorn, graphene, carbon nanofiber, carbon sheet and one or more combinations of the carbon materials doped with hetero atoms thereof, and the hetero atoms are not limited to S, N, P, B; the conductive ceramic material comprises one or more of transition metal oxide, transition metal carbide and transition metal nitride; the transition metal oxide is selected from but not limited to titanium oxide, tin dioxide, zirconium oxide, iridium oxide, tungsten oxide, zinc oxide, aluminum oxide, cerium oxide, nickel oxide, magnesium oxide, molybdenum oxide, manganese dioxide, lanthanum oxide and one or more combinations of alkaline earth metal or rare earth metal mono-doped, double-doped or multi-doped oxides thereof; transition metal carbides are selected from, but not limited to, one or more combinations of titanium carbide, zirconium carbide, tungsten carbide, molybdenum carbide, tantalum carbide, cobalt carbide, iron carbide, chromium carbide, vanadium carbide, hafnium carbide, and alkaline earth or rare earth singly, doubly or multiply doped carbides thereof, and the like; the transition metal nitride is selected from but not limited to one or more combinations of titanium nitride, zirconium nitride, tungsten nitride, molybdenum nitride, tantalum nitride, cobalt nitride, iron nitride, chromium nitride, vanadium nitride, hafnium nitride, and alkaline earth metal or rare earth metal mono-doped, di-doped or multi-doped nitrides thereof, and the like.
4. The trans-temperature zone membrane electrode of claim 1, wherein: the catalyst active components in the anode catalyst layer and the cathode catalyst layer are one or more of Pt-based catalysts and non-Pt-based catalysts;
the Pt-based catalyst comprises Pt and PtM alloy, wherein M in the PtM alloy is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al; the non-Pt-based catalyst comprises metal, single metal atom and nonmetal, wherein the metal catalyst is mostly transition metal and is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, the molecular formula of the single metal atom catalyst is written as M-N/S/P-C, M is mostly transition metal and is selected from one or more of Co, Ni, Ru, Pd, Rh, Au, Ag, V, Ti, W, Ir, Fe, Cr, Cu, Mn and Al, and the nonmetal catalyst is selected from one or more of carbon material and hetero atom doped carbon material; the anti-reversal material in the anode catalysis layer is selected from one or more of, but not limited to, ethylene oxide, ruthenium dioxide, cerium dioxide and nickel oxide.
5. The trans-temperature zone membrane electrode of claim 1, wherein: the preparation method of the anode catalyst layer and the cathode catalyst layer comprises the following steps: mixing fluorine-containing ion exchange resin solution, a catalyst, an anti-reversal material, deionized water, organic matter solution and the like, processing by one or more processes of magnetic stirring, water bath ultrasound, ultrasonic bar, shearing emulsification, homogenization and ball milling to obtain uniformly dispersed catalyst slurry, and preparing an anode catalyst layer and a cathode catalyst layer by one of spraying, bar coating, blade coating, slit coating, window coating, roll-to-roll coating and dipping; the preparation method comprises the following materials in proportion: the solid content of the catalyst slurry is 0.1-70 wt%, preferably 2-50 wt%; wherein the mass ratio of the perfluorinated ion resin to the carrier is 0.05-5, preferably 0.1-2; the mass ratio of the organic matter to the water is 1:99-70:30, preferably 1:99-50: 50; the mass ratio of the anti-electrode material is 0-10 wt%, preferably 0-1 wt%; the organic solution in the preparation method is formed by one or more of methanol, ethanol, ethylene glycol, isopropanol, N-propanol, propylene glycol, glycerol, N-butanol, N-pentanol, 2-ethylhexanol, cyclohexanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide through blending.
6. The trans-temperature zone membrane electrode of claim 1, wherein: the porous fiber polymer matrix of the proton exchange membrane is made of one or more materials selected from polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene, polypropylene, polyethylene-propylene copolymer, polyether sulfone, polyether ketone, polyimide, polybenzimidazole and sulfonated and phosphorylated derivatives thereof; the thickness of the proton exchange membrane is 5-300um, the thickness of the porous fiber polymer matrix is 2-30um, the number of used porous foreguard polymer matrix layers is 0-30 layers, the porous fiber polymer matrix is a homogeneous membrane when being 0 layer, and the porous fiber polymer matrix is a composite reinforced membrane when being 1-30 layers; the sealing component comprises a pressure-sensitive adhesive type frame material and a hot melt adhesive type frame material, wherein the pressure-sensitive adhesive type frame material is selected from but not limited to acrylate copolymer, styrene-isoprene-styrene and styrene-butadiene-styrene block copolymer, organic silicon copolymer, polyurethane and a new substance formed by modifying the pressure-sensitive adhesive type frame material, and the hot melt adhesive type frame material is selected from but not limited to ethylene-vinyl acetate, polyamides, polyesters, polyurethanes, polyolefins and rubbers.
7. The trans-temperature zone membrane electrode of claim 1, wherein: the total thickness of the anode gas diffusion layer and the cathode gas diffusion layer is 1-1000um, preferably 100-400 um; the thickness of the microporous layer in the anode gas diffusion layer and the cathode gas diffusion layer is 0-500um, preferably 20-100 um; the porous substrate layer in the anode gas diffusion layer and the cathode gas diffusion layer contains 30-99 wt% of conductive carbon material and 1-70 wt% of hydrophobic agent, the conductive carbon material is preferably 50-95 wt%, the conductive carbon material is selected from but not limited to carbon paper, carbon cloth, carbon felt and non-woven fabric, and the hydrophobic agent is preferably 5-50 wt%; the aperture of the porous substrate layer is 10-200um, the contact angle is 30-160 degrees, preferably 120-160 degrees; the microporous layer in the anode gas diffusion layer and the cathode gas diffusion layer contains 30-99 wt% of carbon black and 1-70 wt% of a hydrophobic agent, the carbon black is preferably 50-95 wt%, and the hydrophobic agent is preferably 5-50 wt%; the aperture of the microporous layer is 0.01-200um, the contact angle is 30-160 degrees, preferably 120-160 degrees; the hydrophobic agent in both the porous substrate layer and the microporous layer is selected from, but not limited to, polytetrafluoroethylene, fluorinated ethylene propylene, perfluoropolyethers, polyvinylidenefluorides, perfluorohydroxyls, polydimethylsiloxanes.
8. The preparation method of the trans-temperature-zone membrane electrode according to any one of claims 1 to 7, characterized by comprising the following steps:
1) preparation of catalyst slurry: firstly, mixing a perfluorinated ion resin solution, catalyst particles, a carrier, an anti-reversal material, deionized water and an organic solvent according to the mixture ratio, and then carrying out one or more processes of magnetic stirring, water bath ultrasound, ultrasonic bar, shearing emulsification, homogenization and ball milling to obtain uniformly dispersed catalyst slurry;
2) preparation of the catalytic layer: coating the uniformly dispersed catalyst slurry on a polytetrafluoroethylene flexible substrate, or a proton exchange membrane, or a microporous layer of a gas diffusion layer through one of spraying, wire bar coating, blade coating, slit coating, window coating, roll-to-roll coating and dipping, and drying to obtain a cathode catalyst layer and an anode catalyst layer; the anode catalyst layer and the cathode catalyst layer comprise the following components in percentage by mass: 1-80 wt% of fluorine-containing ion exchange resin, 10-99 wt% of carrier, 0.1-60 wt% of catalyst active component loaded on the carrier and 0-10 wt% of anti-pole material; the thickness of the cathode catalyst layer is 0.05-200um, and the loading capacity of the catalyst particles is 0.001-20mg/cm2(ii) a The thickness of the anode catalyst layer is 0.05-200um, and the loading capacity of the catalyst particles is 0.001-20mg/cm2；
3) Assembling a membrane electrode: the membrane electrode comprises an anode catalyst layer, a cathode catalyst layer, a proton exchange membrane, an anode gas diffusion layer, a cathode gas diffusion layer and a frame, the assembly mode among the layers is any one of the following five modes,
the first method is as follows: if at least one of the cathode catalyst layer or the anode catalyst layer is coated on a flexible substrate of polytetrafluoroethylene, step 1) firstly, one side of the catalyst layer is close to a proton exchange membrane, and a membrane coated with the catalyst layer, namely CCM, is obtained after thermal transfer printing treatment; step 2) respectively attaching the frame to the anode catalytic layer side and the cathode catalytic layer side, and assembling the frames together in a hot pressing or gluing mode; step 3), enabling the microporous layer of the anode gas diffusion layer to face the anode catalyst layer and the microporous layer of the cathode gas diffusion layer to face the cathode catalyst layer, and then assembling the microporous layers in a hot-pressing mode or a two-side dispensing mode or a four-side dispensing mode to obtain a membrane electrode; the step 2) and the step 3) can be replaced, namely the frame can be arranged between the catalyst layer and the gas diffusion layer or at the outer side of the gas diffusion layer;
the second method comprises the following steps: if the anode catalyst layer and the cathode catalyst layer are directly coated on two sides of the proton exchange membrane, the membrane electrode assembly is directly carried out in the steps 2) and 3) in the first use mode; likewise, step 2) and step 3) are replaceable;
the third method comprises the following steps: if only one of the anode catalyst layer and the cathode catalyst layer is directly coated on one side of the proton exchange membrane, the other catalyst layer and the anode catalyst layer are required to be subjected to heat transfer printing treatment to obtain CCM; then assembling the membrane electrode by the steps 2) and 3) in the first use mode;
the method is as follows: if the anode catalyst layer and the cathode catalyst layer are directly coated on the gas diffusion layer, the two gas diffusion layers with the catalyst layers are respectively placed on two sides of the proton exchange membrane, one sides of the catalyst layers are close to the proton exchange membrane, after hot-pressing treatment, the frames are respectively placed on the carbon paper sides of the anode gas diffusion layer and the cathode gas diffusion layer, and then membrane electrodes are prepared in a hot-pressing or gluing mode;
the fifth mode is as follows: if one of the anode catalyst layer and the cathode catalyst layer is directly coated on the gas diffusion layer, the gas diffusion layer with the catalyst layer and the other independent catalyst layer are respectively arranged on two sides of the proton exchange membrane, the CCM with the gas diffusion layer on one side is obtained after hot-pressing treatment, then the microporous layer of the other gas diffusion layer is attached to the catalyst layer, after hot-pressing treatment, the frames are respectively arranged on the carbon paper sides of the anode gas diffusion layer and the cathode gas diffusion layer, and then the membrane electrode is prepared through hot-pressing or gluing.
9. A proton exchange membrane fuel cell, characterized by: the membrane electrode, the cathode plate, the anode plate and the sealing component, which are prepared by the membrane electrode according to any one of claims 1 to 7 or the preparation method according to claim 8, wherein the anode plate, the cathode plate and the membrane electrode form a sealing space with the periphery of the membrane electrode, and the sealing space is filled with a sealing material; the anode plate and the cathode plate are one or more composite plates of a graphite plate, a titanium plate, a stainless steel plate and an aluminum plate; the sealing component is one of rubber, plastic and metal composite sealing gaskets, preferably but not limited to silicone rubber, tetrafluoroethylene-propylene rubber, perfluororubber, fluorosilicone rubber, ethylene-propylene rubber, polytetrafluoroethylene and perfluoroethylene-propylene copolymer.
10. A proton exchange membrane fuel cell stack, comprising: a plurality of pem fuel cells according to claim 9 connected in series.
CN202210020153.7A 2022-01-10 2022-01-10 Cross-temperature-zone membrane electrode and proton exchange membrane fuel cell thereof Pending CN114361545A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117543038A (en) * 2024-01-10 2024-02-09 武汉科技大学 Modification preparation process of bipolar plate of proton exchange membrane fuel cell
EP4358196A1 (en) * 2022-10-18 2024-04-24 Carl Freudenberg KG Gas diffusion layer with low plastic deformability and high surface quality and method for the production thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4358196A1 (en) * 2022-10-18 2024-04-24 Carl Freudenberg KG Gas diffusion layer with low plastic deformability and high surface quality and method for the production thereof
WO2024083601A1 (en) * 2022-10-18 2024-04-25 Carl Freudenberg Kg Gas diffusion layer with low plastic deformability and high surface quality, and method for its production
CN117543038A (en) * 2024-01-10 2024-02-09 武汉科技大学 Modification preparation process of bipolar plate of proton exchange membrane fuel cell
CN117543038B (en) * 2024-01-10 2024-04-12 武汉科技大学 Modification preparation process of bipolar plate of proton exchange membrane fuel cell

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