CN117895001A - Preparation method of cathode double-catalytic layer, membrane electrode and high-temperature proton exchange membrane fuel cell - Google Patents
Preparation method of cathode double-catalytic layer, membrane electrode and high-temperature proton exchange membrane fuel cell Download PDFInfo
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Classifications
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- 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 preparation method of a cathode double-catalytic layer, a membrane electrode and a high-temperature proton exchange membrane fuel cell. The cathode double-catalysis layer comprises a cathode outer catalysis layer and a cathode inner catalysis layer; the preparation method of the cathode outer catalytic layer comprises the steps of dropwise adding an ionomer solution into a first catalyst solution, and dropwise adding a binder, so that the binder is dispersed in the first catalyst with the ionomer film in gaps to obtain a cathode outer catalyst, and coating the cathode outer catalyst on the surface of the cathode diffusion layer to form the cathode outer catalytic layer. The preparation method of the cathode inner catalytic layer comprises the steps of dropwise adding a binder into the second catalyst solution, and dropwise adding an ionomer solution to enable ionomer gaps to be dispersed in the second catalyst with a binder network structure, so as to obtain a cathode inner catalytic layer, and coating the cathode inner catalytic layer on the surface of the cathode outer catalytic layer to form the cathode inner catalytic layer. In the cathode double-catalytic layer provided by the invention, ionomer and binder are distributed differently, so that the catalyst utilization rate, the performance of the high-temperature proton exchange membrane fuel cell and the service life of the high-temperature proton exchange membrane fuel cell can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of high-temperature proton exchange membrane fuel cells, and particularly relates to a preparation method of a cathode double-catalytic layer, a membrane electrode and a high-temperature proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high energy conversion efficiency, high power density, no pollutant emission, relatively simple design, etc., and are considered to be promising power sources for the next generation. The PEMFC is classified into a low temperature PEMFC (LT-PEMFC) based on a Nafion membrane and a high temperature PEMFC (HT-PEMFC) based on a Phosphoric Acid (PA) -doped Polybenzimidazole (PBI) membrane according to the operating temperature.
HT-PEMFCs operating at temperatures up to 200℃are now attracting considerable attention due to their high tolerance to impurities, faster electrode reaction kinetics, large amounts of reusable thermal energy and simplified water management. However, due to the slow kinetics of the Oxygen Reduction Reaction (ORR), and catalyst deactivation by PA adsorption, a large amount of platinum catalyst must be used on the cathode to ensure satisfactory performance. This causes a serious high cost problem, which is a major obstacle to commercialization of HT-PEMFCs. Therefore, the utilization efficiency of platinum is improved, the performance of HT-PEMFC is improved, and the development of HT-PEMFC is hopeful to be promoted.
The traditional cathode Single Catalytic Layer (SCL) applied to the high-temperature proton exchange membrane is coated with the same catalyst slurry on the GDL (gas diffusion layer), and the catalyst layer structure is uniformly distributed, but the acid flooding of the catalyst is caused by relatively more acid content on one side close to the PEM (proton exchange membrane), so that the active sites of the catalyst are reduced; and the diffusion difficulty of air or oxygen is increased due to outward diffusion of phosphoric acid at one side close to the GDL, so that the mass transfer resistance is greatly improved, and the performance and the service life of the high-temperature proton exchange membrane fuel cell are greatly influenced. The more viscous phosphoric acid acts as a proton conductor due to the absence of liquid water in the HT-PEMFC, and the coverage and poisoning of the catalyst active sites by phosphoric acid are more serious than other types of fuel cells.
Disclosure of Invention
In order to solve the problems of uneven phosphoric acid distribution and low catalyst utilization rate of a traditional high-temperature proton exchange membrane fuel cell catalytic layer in the operation of the cell, the invention aims to design an HT-PEMFC catalytic layer structure with cathode ionomer-binder differential distribution, control the uniform distribution of phosphoric acid in the catalytic layer and improve the utilization rate of the catalyst so as to adapt to the high-temperature phosphoric acid environment.
In order to achieve the above purpose, the present invention provides a method for preparing a cathode double catalytic layer, wherein the cathode double catalytic layer is formed on the surface of a cathode diffusion layer and comprises a cathode outer catalytic layer and a cathode inner catalytic layer; the preparation method of the cathode double catalytic layer comprises the following steps:
s1, preparing an external cathode catalytic layer:
s1.1, uniformly dispersing a first noble metal catalyst with a carbon carrier in a solvent to obtain a first catalyst solution;
s1.2, dropwise adding an ionomer solution, and uniformly dispersing to obtain a first catalyst with an ionomer film;
s1.3, dropwise adding a binder, uniformly dispersing, so that the binder is dispersed in the first catalyst with the ionomer film in gaps, and carrying out solid-liquid separation to obtain a cathode outer layer catalyst;
s1.4, dispersing the cathode outer catalyst in a solvent, coating the catalyst on the surface of the cathode diffusion layer, and drying to form the cathode outer catalyst layer;
s2, preparing an internal cathode catalytic layer:
s1.1, uniformly dispersing a second noble metal catalyst with a carbon carrier in a solvent to obtain a second catalyst solution;
s1.2, dropwise adding a binder, and uniformly dispersing to obtain a second catalyst with a binder network structure;
s1.3, dropwise adding an ionomer solution, uniformly dispersing, so that ionomer gaps are dispersed in the second catalyst with the binder network structure, and carrying out solid-liquid separation to obtain a cathode inner layer catalyst;
s1.4, dispersing the cathode inner layer catalyst in a solvent, coating the catalyst on the surface of the cathode outer catalytic layer, and drying to form the cathode inner catalytic layer.
Optionally, in the cathode outer catalytic layer, the mass ratio of the ionomer to the carbon support in the first catalyst is 10% -50%, and the mass ratio of the binder to the carbon support in the first catalyst is 10% -50%.
Optionally, in the cathode internal catalytic layer, the mass ratio of the ionomer to the carbon support in the second catalyst is 10% -50%, and the mass ratio of the binder to the carbon support in the second catalyst is 10% -50%.
Optionally, the binder is a hydrophobic binder, including at least one of PTFE, PVDF, FEP, ECTE, ETFE, PFA or PDMS.
Alternatively, the ionomer is an ionic polymer capable of adsorbing phosphoric acid or conducting protons, mPBI, oPBI, F x At least one of PBI and PWN, wherein x represents the atomic proportion of F.
Optionally, the first catalyst is at least one of Pt/C, ptFe/C or PtCo/C; in the first catalyst, the mass fraction of Pt is 5wt.% to 70wt.%; the second catalyst is at least one of Pt black, ptCo/C or PtNi/C.
Another object of the present invention is to provide a membrane electrode comprising: a cathode, a proton exchange membrane, and an anode, the cathode comprising: the cathode double catalytic layer; wherein the hydrophobic angle of the cathode outer catalytic layer is 75-95 degrees; the hydrophobic angle of the catalytic layer in the cathode is 45-65 degrees;
the loading of noble metal in the outer and inner catalytic layers is 0.05-2.0mg cm -2 And the noble metal loading in the cathode inner catalytic layer is higher than the noble metal loading in the cathode outer catalytic layer.
Optionally, the membrane electrode is formed by sequentially arranging a cathode diffusion layer, a cathode outer catalytic layer, a cathode inner catalytic layer, a proton exchange membrane, an anode catalytic layer and an anode diffusion layer, wherein the proton exchange membrane is a phosphoric acid doped PBI membrane.
Another object of the present invention is to provide a high temperature proton exchange membrane fuel cell comprising: the membrane electrode.
Optionally, the high temperature proton exchange membrane fuel cell operates at a temperature of 140 ℃ to 220 ℃.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects:
(1) The invention creatively pretreats the commercial catalyst, adjusts and controls the distribution state of the ionomer and the binder on the surface of the catalyst by changing the dispersion means, the sequence and the content, ensures that phosphoric acid is uniformly distributed on the cathode when the battery operates, avoids phosphoric acid poisoning, and forms a phosphoric acid film on a microscopic level, so that an active site can be simultaneously contacted with protons and oxygen to form an active three-phase interface, thereby improving the utilization rate of the catalyst and the performance and the service life of the battery.
(2) The invention limits the parameters of catalyst pretreatment materials and means, hydrophobic angle, electrochemical activity specific surface area and the like for the inner catalytic layer and the outer catalytic layer, and can achieve the optimal catalyst utilization rate.
(3) The pretreatment method of the catalyst is simple and is beneficial to realizing large-scale application.
Drawings
FIG. 1 is a schematic view of the microstructure of the catalyst pretreatment of the cathode double catalytic layer of the high temperature proton exchange membrane fuel cell of the present invention, a is a catalyst with ionomer gaps dispersed in the binder network (cathode inner layer catalyst), and b is a catalyst with binder gaps dispersed in the defects of the ionomer membrane (cathode outer layer catalyst).
FIG. 2 shows polarization curves of the membrane electrodes of example 1, example 2, comparative example 1 and comparative example 2 according to the present invention.
Fig. 3 is a graph showing the impedance of the membrane electrode of the present invention in example 1, example 2, comparative example 1 and comparative example 2.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to solve the problems of uneven phosphoric acid distribution and low catalyst utilization rate of the traditional high-temperature proton exchange membrane fuel cell catalytic layer in the operation of the cell, the invention provides a preparation method of a cathode double-catalytic layer, wherein the cathode double-catalytic layer is formed on the surface of a cathode diffusion layer and comprises a cathode outer catalytic layer and a cathode inner catalytic layer; the preparation method of the cathode double catalytic layer comprises the following steps:
s1, preparing an external cathode catalytic layer:
s1.1, uniformly dispersing a first noble metal catalyst with a carbon carrier in a solvent to obtain a first catalyst solution. The first noble metal catalyst is more than one of Pt/C, ptFe/C or PtCo/C; in Pt/C, ptFe/C or PtCo/C, the mass fraction of Pt is 5wt.% to 70wt.%.
S1.2, dropwise adding an ionomer solution, and uniformly dispersing to obtain a catalyst with an ionomer film; wherein the mass ratio of the ionomer to the carbon support in the first catalyst is 10% to 50%.
S1.3, dropwise adding a binder, uniformly dispersing, so that the binder is dispersed in a catalyst with an ionomer film in gaps, and carrying out solid-liquid separation to obtain a cathode outer layer catalyst; wherein the mass ratio of the binder to the carbon carrier in the first catalyst is 10-50%.
Specifically, a first catalyst sold in the market is firstly dispersed in water, alcohol or an organic solvent, then ionomer solution is slowly dripped into the solution, and ultrasound is carried out for 5 to 60 minutes; and further dripping the binder, fully contacting the components in each slurry through stirring and dispersing, finally carrying out suction filtration or centrifugation on the slurry, and drying the solid to obtain the catalyst powder with the binder gaps dispersed in the defects of the ionomer film, namely the cathode outer layer catalyst.
S1.4, dispersing the cathode outer catalyst in a solvent, coating the catalyst on the surface of a cathode diffusion layer, and drying to form the cathode outer catalyst layer;
s2, preparing an internal cathode catalytic layer:
s1.1, uniformly dispersing a second noble metal catalyst with a carbon carrier in a solvent to obtain a second catalyst solution, wherein the second noble metal catalyst is more than one of Pt black, ptCo/C or PtNi/C.
S1.2, dropwise adding a binder, and uniformly dispersing to obtain a catalyst with a binder network structure; the mass ratio of the binder to the carbon carrier in the second catalyst is 10-50%.
S1.3, dropwise adding an ionomer solution, uniformly dispersing, so that ionomer gaps are dispersed in the catalyst with the binder network structure, and carrying out solid-liquid separation to obtain a cathode inner layer catalyst; wherein the mass ratio of the ionomer to the carbon support in the second catalyst is 10% to 50%.
Specifically, a commercial catalyst (second catalyst) is firstly dispersed in water, alcohol or an organic solvent, then a binder is slowly dripped into the catalyst, the binder is dispersed by stirring, an ionomer solution is further dripped into the catalyst, each component in each slurry is fully contacted by ultrasonic treatment for 5 to 20min, finally the slurry is subjected to suction filtration or centrifugation, and the solid is dried to obtain catalyst powder with ionomer gaps dispersed in a binder network, and the catalyst powder is used as a cathode inner layer catalyst.
S1.4, dispersing the cathode inner layer catalyst in a solvent, coating the catalyst on the surface of the cathode outer catalytic layer, and drying to form the cathode inner catalytic layer.
The binder is a hydrophobic binder and comprises at least one of PTFE, polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ECTFE (ethylene chlorotrifluoroethylene copolymer), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) and Polydimethylsiloxane (PDMS).
The ionomer is an ionic polymer capable of adsorbing phosphoric acid or conducting protons, such as mPBI (meta-wholly aromatic polybenzimidazole), oPBI (arylene ether type polybenzimidazole), F x PBI (fluoropolymer)Benzimidazole, x represents the atomic proportion of F), PWN (2, 3,5, 6-tetrafluorostyrene-4-phosphonic acid).
In the cathode double-catalytic layer, the regulation and control of the distribution of the inside and outside catalytic layers on the phosphoric acid is realized mainly by the distribution of an ionomer absorbing the phosphoric acid and an acid-repellent binder on the surface of the catalyst, and for the outside catalytic layer which needs more gas channels, catalyst powder which is pertinently dispersed on the defect of an ionomer film by using a binder gap has weaker hydrophobicity and a hydrophobic angle of 75-95 degrees (more preferably 80-90 degrees); for the inner catalytic layer near one side of the membrane, the catalyst powder dispersed in the binder network with ionomer interstices is purposefully more hydrophobic with a hydrophobic angle of 45 ° -65 ° (more preferably 50 ° -60 °). Further, the noble metal loading in the cathode outer catalytic layer and the cathode inner catalytic layer is 0.05-2.0mg cm -2 And the noble metal loading in the cathode inner catalytic layer is higher than the noble metal loading in the cathode outer catalytic layer. The reason is that the inner layer is close to the proton exchange membrane, the phosphoric acid content is higher, and proton channels are more, so that the utilization rate of the catalyst is higher.
The invention also provides a membrane electrode which is formed by sequentially arranging a cathode diffusion layer, a cathode outer catalytic layer, a cathode inner catalytic layer, a proton exchange membrane, an anode catalytic layer and an anode diffusion layer, wherein the proton exchange membrane is a phosphoric acid doped PBI membrane.
The invention also provides a high temperature proton exchange membrane fuel cell comprising: the membrane electrode. The working temperature of the high-temperature proton exchange membrane fuel cell is 140-220 DEG C
The following description is made with reference to examples and comparative examples. The raw materials or reagents used in the examples and comparative examples are commercially available.
Example 1
The preparation method of the high-temperature proton exchange membrane fuel cell cathode ionomer-binder differential distribution membrane electrode comprises the following steps:
preparation of a gas diffusion layer: firstly mixing VulcannXC-72 carbon powder and PTFE emulsion, adding a proper amount of ethanol, carrying out ultrasonic stirring to prepare slurry, coating the slurry on the surface of commercial Toray carbon paper, and then determining the carbon powder loading and PTFE content by a weighing method. Finally, the mixture is placed in a muffle furnace, heat treated for 25 minutes at 340 ℃, and cooled to room temperature to obtain the gas diffusion layer, wherein the gas diffusion layer is used as an anode diffusion layer and a cathode diffusion layer in the subsequent steps.
Preparation of anode GDE (anode catalytic layer+anode diffusion layer): the desired Pt/C catalyst (0.5 mg was weighed out Pt cm -2 ) Adding a small amount of deionized water, stirring and wetting, adding a certain amount of PTFE aqueous alcohol solution, and uniformly dispersing by ultrasonic to obtain anode catalyst slurry; and uniformly coating the slurry on the surface of the microporous layer of the anode diffusion layer by adopting an ultrasonic spraying method to obtain the anode GDE.
Preparing a catalyst with binder gaps dispersed in defects of the ionomer film (i.e., cathode outer layer catalyst): commercial catalyst 30% PtCo/C was first dispersed in organic solvent NMP (N-methylpyrrolidone), then ionomer solution F6PBI (1 wt.%) was slowly dropped into ultrasound for 40min, further binder PTFE was dropped into and dispersed by stirring (500 r.min) -1 30 min) to allow the components in each slurry to fully contact, and centrifuging the slurry (8000 r.min) -1 ) And drying the solid to obtain a catalyst powder with binder gaps dispersed in the defects of the ionomer film, the catalyst powder has a structure shown as b in figure 1, the catalyst particles macroscopically show weaker hydrophobicity on the outer surface, the hydrophobic angle is 80-90 degrees, and the electrochemical activity specific surface area is 72.061m 2 ·g -1 Microscopic appearance is that the binder interstices are dispersed in the defects of the ionomer film, both of which cover the catalyst surface. Wherein the mass ratio of the ionomer to the carbon support in the catalyst is 30% and the mass ratio of the binder to the carbon support in the catalyst is 10%.
Preparation of catalyst with ionomer interstices dispersed in the binder network (i.e., cathode inner layer catalyst): dispersing a commercial catalyst PtCo/C (Pt content is 30 wt.%) in an organic solvent NMP, slowly dripping a bonding agent PTFE, stirring and dispersing, further dripping an ionomer solution F6PBI (1 wt.%) for ultrasonic treatment for 5min to enable components in each slurry to fully contact, and finally centrifuging the slurry (8000 r.min) -1 ) And drying the solid to obtain catalyst powder with ionomer gaps dispersed in binder network, its structure is as followsThe macro structure of a in FIG. 1 shows that the outer surface has strong hydrophobicity, the hydrophobic angle is 50-60 degrees, and the electrochemical activity specific surface area is 50.582m 2 ·g -1 Microscopic appearance is that the ionomer interstices are dispersed in the binder network, both of which cover the catalyst surface. Wherein the mass ratio of the ionomer to the carbon support in the catalyst is 10%, and the mass ratio of the binder to the carbon support in the catalyst is 30%.
Preparation of cathode GDE (cathode double catalytic layer+cathode diffusion layer):
dispersing a catalyst (cathode outer catalyst) with binder gaps dispersed in defects of an ionomer film in NMP, coating the catalyst on a cathode diffusion layer, and evaporating the solvent at 120 ℃ to form an outer catalyst layer; the catalyst with ionomer gaps dispersed in the binder network (cathode inner layer catalyst) was dispersed in NMP and coated on the outer catalytic layer, and the solvent was evaporated at 120 ℃ to form the inner catalytic layer.
Preparation of PBI/H by impregnation 3 PO 4 Composite film: s1, cutting a PBI film into a certain size according to the requirement; s2, soaking the cut film in 85wt.% phosphoric acid at 120 ℃ for a corresponding time; s3, sucking the excessive phosphoric acid on the surface of the membrane by using filter paper, and rapidly weighing to obtain the phosphoric acid adsorption amount of the membrane. Investigation of the Membrane phosphate adsorption amount m Using the phosphoric acid to PBI Mass ratio PA /m PBI . The cycle was repeated S2-S3 until the phosphoric acid adsorption reached 400wt.%.
Mixing the prepared electrode with PBI/H 3 PO 4 The composite membranes are stacked in a mould in the order of anode GDE and cathode GDE are respectively positioned in the PBI/H 3 PO 4 Two sides of the composite membrane, the catalytic layer in the cathode is adjacent to the PBI/H 3 PO 4 And (3) a composite membrane. Then, the membrane electrode is placed in a hot press for hot pressing and forming, so as to obtain the membrane electrode of the fuel cell, and then the membrane electrode is placed in a sealing bag for standby.
The active area of the membrane electrode prepared in this example was 50cm 2 . The cathode and anode gas diffusion layers have the same composition and structure, and are composed of a supporting layer and a microporous layer, wherein the supporting layer is mainly made of Torray carbon paper, and the thickness of the supporting layer is 140 micrometers. The microporous layer is mainly composed of carbon powderIs composed of PTFE, the type of carbon powder is Vulcan XC-72, and the loading capacity of the carbon powder in the microporous layer is 4mg cm -2 The PTFE content was 25wt.% and the thickness was 40. Mu.m. The anode catalyst layer consisted of 40wt.% Pt/C catalyst (40 wt.% Pt/C catalyst is the percentage of Pt mass in the catalyst to total mass of catalyst) and PTFE, with a platinum loading of 0.5mg cm -2 . The PTFE content in the anode catalytic layer was 20wt.%. The cathode catalytic layer consists of 30% PtCo/C, PTFE and F6PBI, and the Pt loading is 0.5mg cm -2 The cathode catalytic layer comprises a cathode inner catalytic layer and a cathode outer catalytic layer, wherein the cathode inner catalytic layer is close to the proton exchange membrane, F 6 The mass ratio of PBI and the carbon carrier in the catalyst is 10 percent, and the mass ratio of PTFE and the carbon carrier in the catalyst is 30 percent; the cathode outer catalytic layer is adjacent to the microporous layer, F 6 The mass ratio of PBI and the carbon carrier in the catalyst is 30%, and the mass ratio of PTFE and the carbon carrier in the catalyst is 10%.
Example 2
The difference from example 1 is that: f of cathode inner/outer catalytic layer in example 2 6 The mass ratio of PBI and the carbon carrier in the catalyst is 20%, and the mass ratio of PTFE and the carbon carrier in the catalyst is 20%. That is, in example 2, there was no F between the cathode inner/outer catalytic layers 6 The difference in the PBI and PTFE contents is only the distribution of the PBI and PTFE on the catalyst surface.
Comparative example 1
The difference from example 1 is that: the cathode catalytic layer of the high temperature proton exchange membrane fuel cell membrane electrode assembly in comparative example 1 adopts F-free catalyst 6 The pretreated catalyst of PBI, namely PtCo/C and PTFE only in the catalytic layer, has a mass ratio of PTFE to carbon support of 40%.
Comparative example 2
The difference from example 1 is that: the cathode catalyst layer of the high temperature proton exchange membrane fuel cell membrane electrode assembly of comparative example 2 uses a pretreatment catalyst without PTFE, i.e. PtCo/C and F are only contained in the catalyst layer 6 PBI，F 6 The ratio of PBI mass to carbon support mass was 40%.
Performance detection
Referring to GB/T20042.5-2009, the obtained high temperature proton exchange membrane fuel cell membrane electrode is subjected to polarization curve test, and specific operation conditions are as follows: the working temperature of the single cell is 160 ℃, the anode is fed with pure hydrogen, the cathode is fed with normal pressure air, and the cathode/anode feeding is respectively 3/1.5 times of the metering ratio.
According to GB/T20042.5-2009, the impedance detection of the membrane electrode of the high-temperature proton exchange membrane fuel cell is carried out, and specific operation conditions are as follows: the working temperature of the single cell is 160 ℃, the anode is pure hydrogen feeding, the cathode is normal pressure air feeding, the cathode/anode feeding is 3/1.5 times of the metering ratio, and the discharge current density is 0.5A cm -2 。
Referring to GB/T20042.5-2009, the membrane electrode cyclic voltammetry detection of the high-temperature proton exchange membrane fuel cell is carried out under the following specific operation conditions: the working temperature of the single cell is 160 ℃, and the cathode is introduced with dry N 2 The flow rate was 4.6 ml.min -1 ·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Anode is led into dry H 2 The flow rate was 6.9 ml.min -1 ·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The voltage range is 0.05V-1.2V, and the sweeping speed is 0.05 V.s -1 。
The test results are shown in the accompanying drawings 2-3 of the specification, wherein example 1 is a membrane electrode using a cathode double catalytic layer with ionomer-binder differential distribution, comparative example 1 is a membrane electrode with a cathode catalytic layer containing PtCo/C and PTFE only, and comparative example 2 is a membrane electrode with a cathode catalytic layer containing PtCo/C and F only 6 Membrane electrode of PBI.
Referring to fig. 2, the polarization characteristics of the membrane electrode of the cathode structure of example 1 and the cathode structures of comparative examples 1 and 2 according to the present invention were measured. As can be seen from the graph, the concentration of the fluorescent dye is 0.1 A.cm -2 Next (a of fig. 3), the voltages of the cathode structures prepared in examples 1 and 2 according to the present invention and the corresponding membrane electrodes of the cathode structures prepared in comparative examples 1 and 2 were measured to be 0.710V, 0.688V, 0.684V, and 0.668V, respectively; at 0.5 A.cm -2 Next (b of fig. 3), the voltages of the cathode structures prepared in examples 1 and 2 according to the present invention and the corresponding membrane electrodes of the cathode structures prepared in comparative examples 1 and 2 were measured to be 0.589V, 0.552V, 0.555V, and 0.527V, respectively; at 1.0 A.cm -2 The voltages of the cathode structures prepared in examples 1 and 2 of the present invention and the cathode structures prepared in comparative examples 1 and 2, respectively, were measured0.490V, 0.450V, 0.446V, 0.419V; the maximum power densities of the cathode structures prepared in examples 1 and 2 of the present invention and the corresponding membrane electrodes of the cathode structures prepared in comparative examples 1 and 2 were respectively 0.619 W.cm -2 、0.580W·cm -2 、0.520W·cm -2 、0.483W·cm -2 . As described above, the membrane electrode of the cathode double catalytic layer having ionomer-binder differential distribution in examples 1 and 2 of the present invention has smaller polarization loss and larger maximum power density than the membrane electrode of the cathode structure prepared in comparative examples 1 and 2.
Referring to the impedance spectra of fig. 3, it can be seen that the internal resistance at high frequency and the cathode charge transfer resistance at intermediate frequency of example 1 are smaller compared to comparative examples 1, 2, mainly because the catalyst surface binder gap of the cathode outer catalyst layer is dispersed in the defect of the ionomer film, and the structure is easier to form a phosphoric acid liquid film on the catalyst surface; the ionomer gaps on the catalyst surface of the catalytic layer in the cathode are dispersed on a binder network, and the structure further limits the aggregation of phosphoric acid while the phosphoric acid is adsorbed on the catalyst surface, so that the excessive phosphoric acid is prevented from poisoning the catalyst active site, and an oxygen transmission channel is constructed. Proton and oxygen transmission channels are reasonably regulated and controlled under the cooperation of the inner catalytic layer and the outer catalytic layer of the cathode, so that cathode polarization and ohmic polarization are reduced, and the performance of the battery is improved. The cathode double catalytic layer of example 2 only had a difference in the coating state of the binder, ionomer on the catalyst surface, and no change in ionomer and binder content, so the effect of improving cathode polarization was not great, but there was a significant polarization reduction compared to comparative examples 1, 2. In contrast, in comparative example 1, the PTFE with a single cathode catalyst layer used as a binder protected the active sites from poisoning by phosphoric acid, but the constructed hydrophobic network prevented diffusion of phosphoric acid, resulting in insufficient contact of the catalyst in the catalyst layer farther from the membrane with sufficient phosphoric acid, and insufficient utilization of a portion of the catalyst due to insufficient proton transport channels. In comparative example 2, F was used for the cathode catalyst layer 6 PBI is used as ionomer, and a continuous film is formed on the surface of the catalyst, so that phosphoric acid is excessively diffused in the cathode catalytic layer to block the transmission channel of oxygen, and the oxygen at the active site is formedThe concentration decreases, resulting in an increase in cathodic polarization, while the phosphoric acid content in the membrane decreases due to the attraction of the ionomer in the catalytic layer to the phosphoric acid, and the proton conductivity of the membrane decreases resulting in a greater ohmic resistance.
In summary, the present invention prepares a catalyst in which ionomer gaps are dispersed in a binder network (cathode inner layer catalyst) and a catalyst in which binder gaps are dispersed in an ionomer film (cathode outer layer catalyst) by changing a catalyst pretreatment means and reconstructing a catalyst surface ionomer and binder distribution manner, respectively. For the inner catalytic layer close to the proton exchange membrane, a catalyst with ionomer interstices dispersed in the binder network is used, and for the outer catalytic layer far from the proton exchange membrane, a catalyst with binder interstices dispersed at the ionomer membrane defects is used. The catalyst with ionomer gaps dispersed in the binder network has strong hydrophobicity, and the surface has less phosphoric acid adsorption capacity, so that the mass transfer channel can be opened; the catalyst with the binder gaps dispersed on the defects of the ionomer film has weaker hydrophobicity of catalyst particles, and the surface of the catalyst is easier to form a phosphoric acid liquid film to assist the diffusion of phosphoric acid to the external catalytic layer. According to the invention, different distribution modes of the ionomer and the binder on the surface of the catalyst are constructed on the inner catalytic layer and the outer catalytic layer, so that the distribution of phosphoric acid and oxygen on the cathode is more reasonable when the battery is in operation, and the effects of improving the battery performance and the catalyst utilization rate are achieved.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. The preparation method of the cathode double-catalysis layer is characterized in that the cathode double-catalysis layer is formed on the surface of a cathode diffusion layer and comprises a cathode outer catalysis layer and a cathode inner catalysis layer; the preparation method of the cathode double catalytic layer comprises the following steps:
s1, preparing an external cathode catalytic layer:
s1.1, uniformly dispersing a first noble metal catalyst with a carbon carrier in a solvent to obtain a first catalyst solution;
s1.2, dropwise adding an ionomer solution, and uniformly dispersing to obtain a first catalyst with an ionomer film;
s1.3, dropwise adding a binder, uniformly dispersing, so that the binder is dispersed in the first catalyst with the ionomer film in gaps, and carrying out solid-liquid separation to obtain a cathode outer layer catalyst;
s1.4, dispersing the cathode outer catalyst in a solvent, coating the catalyst on the surface of the cathode diffusion layer, and drying to form the cathode outer catalyst layer;
s2, preparing an internal cathode catalytic layer:
s1.1, uniformly dispersing a second noble metal catalyst with a carbon carrier in a solvent to obtain a second catalyst solution;
s1.2, dropwise adding a binder, and uniformly dispersing to obtain a second catalyst with a binder network structure;
s1.3, dropwise adding an ionomer solution, uniformly dispersing, so that ionomer gaps are dispersed in the second catalyst with the binder network structure, and carrying out solid-liquid separation to obtain a cathode inner layer catalyst;
s1.4, dispersing the cathode inner layer catalyst in a solvent, coating the catalyst on the surface of the cathode outer catalytic layer, and drying to form the cathode inner catalytic layer.
2. The method for preparing a cathode double catalytic layer according to claim 1, wherein the mass ratio of ionomer to carbon support in the first catalyst in the cathode outer catalytic layer is 10% -50% and the mass ratio of binder to carbon support in the first catalyst is 10% -50%.
3. The method of preparing a cathode bi-catalytic layer according to claim 1, wherein the mass ratio of ionomer to carbon support in the second catalyst in the cathode internal catalytic layer is 10% to 50% and the mass ratio of binder to carbon support in the second catalyst is 10% to 50%.
4. The method of preparing a cathode bi-catalytic layer according to claim 1, wherein the binder is a hydrophobic binder comprising at least one of PTFE, PVDF, FEP, ECTE, ETFE, PFA or PDMS.
5. The method for preparing a cathode double catalytic layer according to claim 1, wherein the ionomer is an ionic polymer capable of adsorbing phosphoric acid or conducting protons, and is mPBI, oPBI, F x At least one of PBI and PWN, wherein x represents the atomic proportion of F.
6. The method of preparing a cathode double catalytic layer according to claim 1, wherein the first catalyst is at least one of Pt/C, ptFe/C or PtCo/C; in the first catalyst, the mass fraction of Pt is 5wt.% to 70wt.%; the second catalyst is at least one of Pt black, ptCo/C or PtNi/C.
7. A membrane electrode, characterized in that it comprises: a cathode, a proton exchange membrane, and an anode, the cathode comprising: the cathode bi-catalytic layer of any one of claims 1-6; wherein the hydrophobic angle of the cathode outer catalytic layer is 75-95 degrees; the hydrophobic angle of the catalytic layer in the cathode is 45-65 degrees;
the loading of noble metal in the outer and inner catalytic layers is 0.05-2.0mg cm -2 And the noble metal loading in the cathode inner catalytic layer is higher than the noble metal loading in the cathode outer catalytic layer.
8. The membrane electrode according to claim 7, wherein the membrane electrode is formed by sequentially arranging a cathode diffusion layer, a cathode outer catalytic layer, a cathode inner catalytic layer, a proton exchange membrane, an anode catalytic layer and an anode diffusion layer, and the proton exchange membrane is a phosphoric acid doped PBI membrane.
9. A high temperature proton exchange membrane fuel cell comprising: the membrane electrode of claim 6.
10. The high temperature proton exchange membrane fuel cell as claimed in claim 9, wherein the high temperature proton exchange membrane fuel cell operates at a temperature of 140 ℃ to 220 ℃.
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