CN117650251A - Membrane electrode coating slurry preparation method, membrane electrode and fuel cell - Google Patents
Membrane electrode coating slurry preparation method, membrane electrode and fuel cell Download PDFInfo
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- CN117650251A CN117650251A CN202311528100.7A CN202311528100A CN117650251A CN 117650251 A CN117650251 A CN 117650251A CN 202311528100 A CN202311528100 A CN 202311528100A CN 117650251 A CN117650251 A CN 117650251A
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- 239000012528 membrane Substances 0.000 title claims abstract description 124
- 239000006255 coating slurry Substances 0.000 title claims abstract description 48
- 239000000446 fuel Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 47
- 239000002245 particle Substances 0.000 abstract description 40
- 239000006185 dispersion Substances 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 4
- 239000011268 mixed slurry Substances 0.000 abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/83—Mixing plants specially adapted for mixing in combination with disintegrating operations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The application discloses a preparation method of membrane electrode coating slurry, a membrane electrode and a fuel cell, and relates to the technical field of proton exchange membrane fuel cells, wherein the preparation method of the membrane electrode coating slurry comprises the following steps: mixing and stirring a catalyst, a resin solution, deionized water and an organic solvent to obtain a first mixed solution; ball milling is carried out on the first mixed solution to obtain a second mixed solution; and homogenizing the second mixed solution to obtain a finished product of the membrane electrode coating slurry. The method sequentially carries out multistage dispersion on the mixed slurry through stirring operation, ball milling operation and homogenizing operation, overcomes the defect of insufficient dispersion in the existing single slurry dispersion mode, and ensures that the prepared membrane electrode coating slurry finished product has smaller particle size and more uniform particle size distribution, thereby improving the electrochemical performance of the membrane electrode prepared by the slurry preparation method and the stability of the finally prepared proton exchange membrane fuel cell, and better meeting the use requirement.
Description
Technical Field
The application relates to the technical field of proton exchange membrane fuel cells, in particular to a preparation method of membrane electrode coating slurry, a membrane electrode and a fuel cell.
Background
Proton exchange membrane fuel cells (PEMFCs, proton Exchange Membrane Fuel Cell) are a new type of device that can directly convert chemical energy into electrical energy. The proton exchange membrane fuel cell has no internal energy consumption of rotating parts, no combustion, and no restriction of the Kano cycle on the energy conversion efficiency, so the proton exchange membrane fuel cell has higher energy conversion efficiency. And the proton exchange membrane fuel cell adopts clean energy sources such as hydrogen, methanol and the like, has no discharge of sulfur oxides and nitrides, has little harm to the environment and has higher environmental protection. In addition, the proton exchange membrane fuel cell has the characteristics of mild working condition, small volume, light weight, safety, durability and the like, and is widely used as a mobile power supply, and is also an ideal power supply.
The membrane electrode is a core part of the proton exchange membrane fuel cell, and the preparation of the membrane electrode comprises two parts of slurry preparation and membrane electrode coating, wherein the method for preparing the slurry plays a vital role for the performance of the membrane electrode. However, the membrane electrode prepared based on the current slurry preparation method has poor electrochemical performance and poor stability, and is difficult to meet the use requirement.
Disclosure of Invention
The invention aims to provide a preparation method of a membrane electrode coating slurry, which aims to solve the technical problems that the membrane electrode prepared based on the current slurry preparation method is poor in electrochemical performance and stability and is difficult to meet the use requirement.
In order to achieve the purpose, the technical scheme adopted by the application is as follows:
a method for preparing a membrane electrode coating paste, comprising the steps of:
mixing and stirring a catalyst, a resin solution, deionized water and an organic solvent to obtain a first mixed solution;
ball milling is carried out on the first mixed solution to obtain a second mixed solution;
and homogenizing the second mixed solution to obtain a finished product of the membrane electrode coating slurry.
Further, the step of mixing the catalyst, the resin solution, the deionized water and the organic solvent and then stirring to obtain a first mixed solution comprises the following steps:
mixing the catalyst with the deionized water and stirring to obtain a first solution;
and sequentially adding the resin solution and the organic solvent into the first solution, and stirring to obtain the first mixed solution.
Further, the step of stirring the catalyst and the deionized water after mixing comprises the following steps:
mechanically stirring the catalyst and the deionized water at a rotation speed of 190-210 rad/min for 9.5-10.5 min;
the step of stirring after sequentially adding the resin solution and the organic solvent to the first solution comprises the following steps:
the first solution is mechanically stirred at a rotational speed of 190-210 rad/min for 28.5-31.5 min.
Further, the mass ratio of the catalyst, the resin solution, the deionized water and the organic solvent is 1:2.5:6:2.
further, the total time of the ball milling operation is 9.5-10.5 h, the ball milling operation comprises a rotating stage and a stopping stage, the rotating stage and the stopping stage are alternately carried out, the time of each rotating stage is 6.5-7.5 min, the time of each stopping stage is 2.8-3.2 min, and the rotating speed of the rotating stage is 285-315 rad/min.
Further, the homogenizing pressure of the homogenizing operation is 19000-21000 psi, and the cycle number of the homogenizing operation is 10.
Correspondingly, the application also provides a membrane electrode coating slurry layer, and the membrane electrode coating slurry layer is prepared by the membrane electrode coating slurry preparation method.
Correspondingly, the application also proposes a membrane electrode, comprising:
a proton exchange membrane;
the membrane electrode coating slurry layer as described above, wherein the membrane electrode coating slurry layer is coated on the proton exchange membrane.
Further, the anode of the proton exchange membrane is coated with the membrane electrode coating slurry layer with the loading capacity of 0.095-0.105 mg/cm 2 The cathode of the proton exchange membrane is coated with the membrane electrode coating slurry layer with the loading capacity of 0.38-0.42 mg/cm 2 。
Correspondingly, the application also provides a fuel cell which comprises the membrane electrode.
Compared with the prior art, the beneficial effects of this application are:
according to the preparation method of the membrane electrode coating slurry, after the catalyst, the resin solution, the deionized water and the organic solvent are mixed, the mixed slurry is subjected to multistage dispersion sequentially through stirring operation, ball milling operation and homogenizing operation, so that the defect of insufficient dispersion in the existing single slurry dispersion mode is overcome, the prepared membrane electrode coating slurry finished product is smaller in particle size and more uniform in particle size distribution, the electrochemical performance of the membrane electrode prepared by the preparation method of the slurry and the stability of the finally prepared proton exchange membrane fuel cell are improved, and the use requirement can be better met.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from the structures shown in these drawings without inventive effort to a person of ordinary skill in the art.
FIG. 1 is a schematic diagram of the steps of an exemplary method for preparing a membrane electrode coating paste according to the present disclosure;
FIG. 2 is a schematic diagram of steps of another embodiment of a method for preparing a membrane electrode coating paste according to the present application;
FIG. 3 is a schematic view of the particle size distribution of the membrane electrode coating slurry layer of the present application;
fig. 4 is a schematic diagram of the measured performance of the fuel cell of the present application.
The realization, functional characteristics and advantages of the present application will be further described with reference to the embodiments, referring to the attached drawings.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
It should be noted that, in the embodiment of the present application, directional indications (such as up, down, left, right, front, and rear … …) are referred to, and the directional indications are merely used to explain the relative positional relationship, movement conditions, and the like between the components in a specific posture, and if the specific posture is changed, the directional indications are correspondingly changed.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present application, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, if "and/or" and/or "are used throughout, the meaning includes three parallel schemes, for example," a and/or B "including a scheme, or B scheme, or a scheme where a and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present application.
After research on the existing proton exchange membrane fuel cell (PEMFC, proton Exchange Membrane Fuel Cell), the technical personnel of the application find that the slurry coated on the membrane electrode generally has the problems of large particle size and uneven particle size distribution; for this reason, the current slurry preparation method generally adopts a single slurry dispersing mode, and slurry particles are difficult to fully disperse, so that the prepared slurry has larger particle size and uneven particle size distribution.
The working principle of the proton exchange membrane fuel cell is essentially a process that ions repeatedly circulate between positive and negative electrode materials of a membrane electrode, in the process, the ions are continuously embedded into the electrode materials and are continuously de-embedded from the electrode materials, and the swing type embedding and de-embedding process only enables the proton exchange membrane fuel cell to be repeatedly charged and discharged. The intercalation and deintercalation of ions is affected by many factors, wherein the spatial effect generated when the particle size of the slurry is too large directly adversely affects the intercalation and deintercalation of ions, thereby causing the charge-discharge performance of the battery to be degraded. In addition, when the particle size of the slurry is too large, active substances, conductive agents and the like in the slurry cannot be stably connected, so that the slurry does not have a good ion channel and a conductive network, and the electrochemical performance of the membrane electrode is reduced; in addition, when the particle size of the slurry is too large, the stability of the slurry is affected, the slurry may have problems of sedimentation, poor consistency and the like, and the conditions of blocking, pitting, cracking and the like occur in the process of coating the slurry on the proton exchange membrane, so that the quality of the proton exchange membrane is adversely affected, and the cycle performance and the rate performance of the battery are seriously reduced.
On the other hand, when slurry is unevenly dispersed and has serious agglomeration phenomenon, the electrochemical performance of the membrane electrode is adversely affected; if the conductive agent is unevenly distributed, the conductivity of each part of the membrane electrode is different in the charge and discharge process, and different electrochemical reactions can occur, so that the reversible capacity is reduced, and a local overcharge and overdischarge phenomenon is accompanied, so that certain potential safety hazard exists; if the binder is unevenly distributed, the adhesion between the particles and the current collector is too large or too small, so that the internal resistance of the electrode is unstable, and the capacity of the battery is finally affected.
In summary, the size and the uniformity of dispersion of the slurry particles are critical factors affecting the electrochemical performance of the membrane electrode in the proton exchange membrane fuel cell and the overall charge-discharge stability of the cell. Based on the findings, the application correspondingly provides a preparation method of the membrane electrode coating slurry, which aims at reducing the particle size of slurry particles and improving the dispersion uniformity of the slurry particles.
Referring to fig. 1, the preparation method of the membrane electrode coating slurry provided in the embodiment of the application includes the following steps:
s1, mixing a catalyst, a resin solution, deionized water and an organic solvent, and stirring to obtain a first mixed solution; the function of this step is to pre-mix the catalyst, resin solution, deionized water and organic solvent.
Specifically, the catalyst, the resin solution, the deionized water and the organic solvent with preset amounts can be weighed by an electronic balance and uniformly stirred in a reaction container, so that the proportion of the resin solution, the deionized water and the organic solvent is strictly controlled, and the proportion of the prepared first mixed solution is more accurate. Wherein the stirring operation can be performed by a mechanical stirrer, and the first mixed liquid in the reaction vessel can be more uniformly mixed by the mechanical stirrer than by manual stirring.
And S2, performing ball milling operation on the first mixed solution to obtain a second mixed solution.
And S3, homogenizing the second mixed solution to obtain a finished product of the membrane electrode coating slurry.
Specifically, the ball milling operation may be performed at a preset rotational speed and time by the ball mill, and the ball milling operation may grind the particle size of the catalyst and the resin to a smaller level. The homogenizing operation can be performed by a homogenizer according to preset pressure and cycle times, and the homogenizing operation can break up the granularity of the catalyst and the resin to below 1 um. Through the cooperation between stirring operation, ball-milling operation and the homogeneity operation, can realize the multistage dispersion of thick liquids, overcome the insufficient drawback of dispersion that current single thick liquids dispersion mode exists for the finished product particle diameter of membrane electrode coating thick liquids that prepares is little, particle diameter distribution is even and stability is high.
The particle size distribution of the finished product of the membrane electrode coating slurry prepared by the preparation method of the membrane electrode coating slurry provided by the embodiment of the application is shown in a figure 3, and the particle size of the slurry is about 700nm, so that the particle size of the slurry is smaller, the particle size distribution basically accords with normal distribution, and the particle size distribution of the slurry is more uniform.
In this example, the catalyst comprises 10 to 80% wt of any one or more of Pt/C, ptCo/C, ptRu/C, ptIr/C; the resin solution can be perfluorinated sulfonic acid resin solution, and the resin solution has the function of bonding catalyst particles and providing a proton transmission channel in the operation process of the subsequent proton exchange membrane fuel cell; the organic solvent is one or more of ethanol, isopropanol, N-propanol, ethylene glycol and N-methylpyrrolidone, preferably isopropanol.
Since the line of the homogenizer is narrow and the primary particle diameter of the slurry particles is large, if the first mixed liquid is directly homogenized, the homogenizer is likely to be clogged. Based on this consideration, in this embodiment, the first mixed solution is initially dispersed by the ball mill to control the particle size of the slurry to a smaller level, and then the homogenizing operation is performed by the homogenizer, so that the slurry is ensured to be progressively dispersed, and meanwhile, the problem of blockage of the homogenizer can be effectively avoided.
Therefore, the preparation method of the membrane electrode coating slurry provided by the embodiment mixes the catalyst, the resin solution, the deionized water and the organic solvent, and sequentially carries out multistage dispersion on the mixed slurry through stirring operation, ball milling operation and homogenizing operation, so that the defect of insufficient dispersion in the existing single slurry dispersion mode is overcome, the prepared membrane electrode coating slurry finished product has smaller particle size and more uniform particle size distribution, the electrochemical performance of the membrane electrode prepared by the slurry preparation method and the stability of the finally prepared proton exchange membrane fuel cell are improved, and the use requirement can be better met.
Further, referring to fig. 2, in another alternative embodiment, step S1 includes:
s11, mixing a catalyst with deionized water and stirring to obtain a first solution;
and S12, sequentially adding the resin solution and the organic solvent into the first solution, and stirring to obtain a first mixed solution.
In the embodiment, the catalyst is firstly mixed with deionized water, and then the resin solution and the organic solvent are added, so that the organic solvent and the catalyst can be prevented from being directly contacted in the air to oxidize and burn; specifically, deionized water is added first to prevent combustion.
Alternatively, referring to fig. 1 and 2, the mass ratio of the catalyst, the resin solution, deionized water, and the organic solvent is 1:2.5:6:2.
optionally, referring to fig. 1 and 2, step S11 includes:
s111, mechanically stirring the catalyst and deionized water for 9.5-10.5 min at a rotating speed of 190-210 rad/min;
step S12 includes:
s121, mechanically stirring the first solution for 28.5-31.5 min at a rotating speed of 190-210 rad/min.
Alternatively, referring to fig. 1 and 2, the total time of the ball milling operation is 9.5 to 10.5 hours, the ball milling operation includes a rotation stage and a stop stage, the rotation stage and the stop stage are alternately performed, the time of each rotation stage is 6.5 to 7.5 minutes, the time of each stop stage is 2.8 to 3.2 minutes, and the rotation speed of the rotation stage is 285 to 315rad/min.
Alternatively, referring to FIGS. 1 and 2, the homogenization pressure of the homogenization operation is 19000-21000 psi and the number of cycles of the homogenization operation is 10.
In one embodiment, 10g of catalyst, 25g of resin solution, 60g of deionized water and 20g of isopropyl alcohol may be weighed using an electronic balance and mixed and dispersed as in the examples above. Specifically, during the dispersion, the mechanical stirrer preferably mechanically agitates the catalyst and deionized water at a speed of 200rad/min for 10 minutes to obtain a first solution; then mechanically stirring the first solution for 30min at a rotating speed of 200rad/min to obtain a first mixed solution; performing ball milling operation on the first mixed liquid by using a ball mill at a rotating speed of 300rad/min, stopping the ball mill for 3min when the ball mill rotates for 7min, namely performing ball milling operation on the first mixed liquid by taking 10min as one period, and continuously performing the ball milling operation for 10h in total, so that the damage to equipment caused by continuous operation of the ball mill at a higher rotating speed can be avoided; after the ball milling operation is finished, a second mixed solution can be obtained, the second mixed solution can be subjected to homogenizing operation by using a homogenizer under the pressure of 20000psi and is circulated for 10 times, so that the slurry is further dispersed, and finally, a finished product of the membrane electrode coating slurry can be obtained.
The smaller the particle size of the active material in the slurry, the larger the viscosity, the weaker the slurry layering phenomenon caused by gravity, and the better the stability of the suspension system; however, when the particle size of the active material is reduced to a certain small size, the binding force between the particles becomes a main effect, and agglomeration phenomenon occurs between the particles, which is not favorable for the stability of the system. Therefore, in the slurry dispersing process, the particle size is not finer and better, but is distributed in a narrower size range, so that the mutual balance of suction force and repulsive force is achieved, the stability of a slurry system is ensured, the problems that the slurry viscosity is too high and is not easy to precipitate, the subsequent coating is unfavorable, the drying difficulty caused by the too low slurry viscosity is avoided, and the problems of coating cracks, slurry particle aggregation, poor surface density consistency and the like are also avoided. Based on the specific parameter settings in the above embodiments, the particle size of the slurry may be limited within a suitable size range, so that the slurry has stable and proper viscosity, thereby being more beneficial to subsequent slurry coating and further improving the stability of the finally manufactured proton exchange membrane fuel cell.
Specifically, the finished product of the membrane electrode coating slurry prepared by the preparation method of the membrane electrode coating slurry has the measured viscosity of 225 mPa.s after the slurry is dispersed, and the measured viscosity after the slurry is left for 24 hours of 220 mPa.s, and the viscosity is basically unchanged, so that the stability is better.
Correspondingly, the embodiment of the application also provides a membrane electrode coating slurry layer, which is prepared by the membrane electrode coating slurry preparation method in any embodiment.
In the present embodiment, the related contents concerning the membrane electrode coating paste layer have been described in detail in the embodiments of the above-described membrane electrode coating paste preparation method, and specific reference is made to the above-described embodiments. The membrane electrode coating slurry layer adopts all the technical schemes of all the embodiments, so that the membrane electrode coating slurry layer has at least all the beneficial effects brought by the technical schemes of the embodiments, and is not described in detail herein.
Correspondingly, the embodiment of the application also provides a membrane electrode, which comprises:
a proton exchange membrane;
the membrane electrode coating slurry layer of any one of the above embodiments, wherein the membrane electrode coating slurry layer is coated on the proton exchange membrane.
Optionally, the anode coating film electrode coating slurry layer of the proton exchange film has the loading of 0.095-0.105 mg/cm 2 The carrying capacity of the cathode coating film electrode coating slurry layer of the proton exchange film is 0.38-0.42 mg/cm 2 。
In this embodiment, after the membrane electrode coating slurry layer is coated on the proton exchange membrane, ions can be continuously embedded into the electrode material based on the transmission channel provided by the membrane electrode coating slurry layer, and simultaneously, the ions can be continuously released from the electrode material, so that the proton exchange membrane fuel cell can be repeatedly charged and discharged for use. Wherein, the loading of the anode coating film electrode coating slurry layer of the proton exchange film is preferably 0.1mg/cm 2 The loading of the cathode coating film electrode coating slurry layer of the proton exchange film is preferably 0.4mg/cm 2 Thus, the durability of the membrane electrode can be optimized on the premise of ensuring the performance of the membrane electrode.
The membrane electrode provided in this embodiment adopts all the technical solutions of all the embodiments, so at least the beneficial effects brought by the technical solutions of the embodiments are not described in detail herein.
Correspondingly, the embodiment of the application also provides a fuel cell, which comprises the membrane electrode in any embodiment.
The fuel cell provided by the embodiment adopts all the technical schemes of all the embodiments, so that the fuel cell at least has all the beneficial effects brought by the technical schemes of the embodiments, namely, after the catalyst, the resin solution, the deionized water and the organic solvent are mixed, the mixed slurry is subjected to multistage dispersion sequentially through stirring operation, ball milling operation and homogenizing operation, the defect of insufficient dispersion in the existing single slurry dispersion mode is overcome, the particle size of the prepared membrane electrode coating slurry finished product is smaller, the particle size distribution is more uniform, and the electrochemical performance of the membrane electrode prepared by the slurry preparation method and the stability of the finally prepared proton exchange membrane fuel cell are improved, so that the use requirement can be better met.
Specifically, referring to fig. 4, the fuel cell according to the present embodiment, when the current density is 2.1A/cm 2 When the average voltage is 0.656V, the rated power density reaches 1.3776W/cm 2 This can demonstrate that the fuel cell performs well.
It should be noted that, the preparation method of the membrane electrode coating slurry, the membrane electrode and other contents of the fuel cell disclosed in the present application may refer to the prior art, and are not described herein again.
The foregoing is merely an alternative embodiment of the present application, and is not intended to limit the scope of the patent application, and all equivalent structural changes made by the specification and drawings of the present application or direct/indirect application in other related technical fields are included in the scope of the patent protection of the present application.
Claims (10)
1. The preparation method of the membrane electrode coating slurry is characterized by comprising the following steps of:
mixing and stirring a catalyst, a resin solution, deionized water and an organic solvent to obtain a first mixed solution;
ball milling is carried out on the first mixed solution to obtain a second mixed solution;
and homogenizing the second mixed solution to obtain a finished product of the membrane electrode coating slurry.
2. The method for preparing a membrane electrode coating paste according to claim 1, wherein the step of mixing the catalyst, the resin solution, the deionized water and the organic solvent and then stirring to obtain a first mixed solution comprises:
mixing the catalyst with the deionized water and stirring to obtain a first solution;
and sequentially adding the resin solution and the organic solvent into the first solution, and stirring to obtain the first mixed solution.
3. The method for preparing a membrane electrode coating paste according to claim 2, wherein the step of stirring after mixing the catalyst with the deionized water comprises:
mechanically stirring the catalyst and the deionized water at a rotation speed of 190-210 rad/min for 9.5-10.5 min;
the step of stirring after sequentially adding the resin solution and the organic solvent to the first solution comprises the following steps:
the first solution is mechanically stirred at a rotational speed of 190-210 rad/min for 28.5-31.5 min.
4. The method for preparing a membrane electrode coating paste according to claim 1, wherein the mass ratio of the catalyst, the resin solution, the deionized water and the organic solvent is 1:2.5:6:2.
5. the method of preparing a membrane electrode coating paste according to claim 1, wherein the total time of the ball milling operation is 9.5 to 10.5 hours, the ball milling operation includes a rotation stage and a stop stage, the rotation stage and the stop stage are alternately performed, the time of each rotation stage is 6.5 to 7.5 minutes, the time of each stop stage is 2.8 to 3.2 minutes, and the rotation speed of the rotation stage is 285 to 315rad/min.
6. The method for producing a membrane electrode coating paste according to claim 1, wherein the homogenizing pressure of the homogenizing operation is 19000 to 21000psi, and the number of cycles of the homogenizing operation is 10.
7. A membrane electrode coating paste layer, characterized in that the membrane electrode coating paste layer is prepared by the membrane electrode coating paste preparation method according to any one of claims 1 to 6.
8. A membrane electrode, characterized in that the membrane electrode comprises:
a proton exchange membrane;
the membrane electrode coating slurry layer according to claim 7, which is coated on the proton exchange membrane.
9. The membrane electrode according to claim 8, wherein the anode of the proton exchange membrane coats the membrane electrode coating slurry layer with a loading of 0.095-0.105 mg/cm 2 The cathode of the proton exchange membrane is coated with the membrane electrode coating slurry layer with the loading capacity of 0.38-0.42 mg/cm 2 。
10. A fuel cell comprising the membrane electrode according to any one of claims 8 to 9.
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