CN113394438A - Preparation and loading integrated process of catalyst layer in oxygen cathode membrane electrode - Google Patents
Preparation and loading integrated process of catalyst layer in oxygen cathode membrane electrode Download PDFInfo
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a process for integrating preparation and loading of a catalyst layer in an oxygen cathode membrane electrode, which comprises the steps of placing uniformly mixed raw materials of the catalyst layer in an electrostatic spinning device, fixing a gas diffusion layer on a receiving body, setting corresponding operation parameters, carrying out electrostatic spinning for a certain time, separating the gas diffusion layer and the catalyst layer loaded on the gas diffusion layer from the receiving body after the spinning is finished, carrying out heat treatment on the gas diffusion layer and the catalyst layer loaded on the gas diffusion layer, and cooling to obtain the oxygen cathode membrane electrode integrating preparation and loading of the catalyst layer. The invention utilizes the characteristics of the electrostatic spinning technical device to fix the conductive gas diffusion layer on the receiving body, can receive and thermally treat the precursor of the catalyst layer under the condition of not influencing the high-voltage electrostatic field, realizes the integrated process from preparation to loading of the catalyst layer, and simplifies the process flow. The low Pt or non-noble metal catalyst is selected to ensure the performance of the membrane electrode and greatly reduce the manufacturing cost of the membrane electrode, and the process has an industrialization prospect by utilizing the characteristic of electrostatic spinning batch manufacturing.
Description
Technical Field
The invention belongs to the field of electrostatic spinning and new energy battery membrane electrode manufacturing, and particularly relates to a process for realizing integration of preparation and loading of a catalyst layer in an oxygen cathode membrane electrode by an electrostatic spinning method.
Background
Proton exchange membrane fuel cells and metal air cells are used as representatives of new energy batteries and have the advantages of high power density, environmental friendliness, wide application field and the like. The oxygen cathode membrane electrode which is a common core component of the two is mainly composed of a gas diffusion layer and a catalytic layer. Wherein, the catalytic layer is a structure with certain activity of catalyzing oxygen molecules to carry out four-electron reduction reaction. The gas diffusion layer is used for buffering oxygen with higher flow rate to ensure that the oxygen is uniformly and fully contacted with the catalyst layer, and simultaneously, the gas diffusion layer is used for blocking electrolyte to prevent the electrolyte from permeating into a gas flow passage and ensuring that water vapor generated by the fuel cell is smoothly led out.
Currently, the catalyst layer in the commercial oxygen cathode membrane electrode is used for promoting the inert oxygen reduction reaction to efficiently perform by adding four times of noble metal platinum (Pt) loaded on the anode. The high cost associated with too high a noble metal Pt loading is the largest barrier that has hindered large-scale commercial applications of proton exchange membrane fuel cells and metal air cells. In addition, the Pt catalyst has weak methanol toxicity resistance, which requires a great increase in the purity of hydrogen in industrial processes of methanol hydrogen production and the like, and at the same time, limits the development of such membrane electrodes in other new energy batteries such as methanol fuel cells and the like.
The conventional mature method for manufacturing the oxygen cathode membrane electrode double-layer assembly is to uniformly coat the prepared catalyst slurry on the gas diffusion layer. And after the solvent is volatilized, carrying out hot pressing on the solvent and other structures such as a battery anode to finish assembly. Although the traditional mode of respectively preparing and reloading the catalyst layer and the gas diffusion layer can refine the product performance control of the two structures, the traditional mode undoubtedly brings too many process flows to the production and processing of the oxygen cathode membrane electrode. Therefore, on the premise of ensuring the performance of the battery, reducing the load of the noble metal catalyst as much as possible or replacing the noble metal catalyst with a non-noble transition metal nitrogen-carbon material with methanol toxicity resistance is one of important means for reducing the production cost of the oxygen cathode membrane electrode. In addition, the process for realizing integration of the double-layer assembly from preparation to loading can greatly simplify the process route.
The electrostatic spinning technology has excellent advantages in preparing large batches of non-noble metal nitrogen-carbon catalyst precursors with uniform appearance and size. And (3) the precursor fiber is electrospun on the gas diffusion layer, and then heat treatment is carried out, so that the process of integrating the preparation of the catalyst layer and the loading of the double-layer assembly can be realized. Different from mechanical hot pressing loading, the electrostatic spinning loading method can greatly reduce the interval resistance between the catalyst layer and the gas diffusion layer, reduce energy loss and enhance the material transportation and electronic conduction in the battery.
Disclosure of Invention
The invention relates to a process for integrating preparation and loading of a catalyst layer in an oxygen cathode membrane electrode, wherein the core technology used is electrostatic spinning, and the main process flow comprises mixing of the raw materials of the catalyst layer, electrospinning of a precursor and heat treatment. The uniform mixing of the raw materials of the catalyst layer is realized by a solvent dispersion method, a crushing and stirring method and the like, the gas diffusion layer is used as a receiving body, the precursor fiber is loaded on the gas diffusion layer by utilizing an electrostatic spinning technology, and the heat treatment process needs to carry out corresponding parameter setting such as a calcining atmosphere, a heating rate, a heat preservation platform and the like according to the used polymer material. Compared with the mature preparation process and the disclosed invention process, the invention provides an innovative modification idea: 1. and (3) directly carrying out electrostatic spinning on the gas diffusion layer to prepare and load a precursor. 2. And carrying out heat treatment on the precursor and the gas diffusion layer together to realize an integrated process of preparing the catalyst layer and loading the catalyst layer on the gas diffusion layer.
For the current membrane electrode manufacturing process, the preparation and loading of the catalyst layer are generally to disperse and coat the nano-catalyst obtained by a water bath method, a crystal growth method and the like on the gas diffusion layer in the form of ink, and obtain a double-layer component after the solvent is volatilized. The traditional method for controlling the growth of the nano structure has great difficulty in controlling the conditions in large scale in industry. The process adopts the electrostatic spinning technology to realize the large-scale production of the catalyst nanofiber, and utilizes the characteristics of a receiving device thereof to convert precursor into active catalyst through heat treatment and load the active catalyst on a gas diffusion layer, thereby finally forming the oxygen cathode membrane electrode.
The manufacturing process of the novel oxygen cathode membrane electrode is different from the prior process in that: firstly, the selection surface of the catalytic layer material is widened, and all oxygen reduction catalysts prepared based on the electrostatic spinning technology can be applied to the process; secondly, the process flow is simplified, and the loading of the catalyst layer on the gas diffusion layer is realized in the preparation process of the catalyst layer structure; thirdly, the industrial production scale is conveniently amplified, the nano-fiber catalyst layer with uniform and controllable appearance, good performance and low cost can be produced on a large scale by utilizing the electrostatic spinning technology based on the preparation raw material of the non-noble transition metal oxygen reduction catalyst, and the nano-fiber catalyst layer has the prospect of industrial manufacturing.
The catalyst layer raw materials in the novel oxygen cathode membrane electrode manufacturing process are raw materials for preparing the oxygen reduction catalyst by an electrostatic spinning method, and include but are not limited to high molecular polymers such as polyacrylonitrile, polystyrene, polyvinylpyrrolidone, polymethyl methacrylate and the like which can be subjected to electrostatic spinning, and the molecular weight of the polymers is usually between 1 million and 1 million; metal components providing catalytic activity for oxygen reduction reaction, such as compounds and derivatives containing noble metals of Pt, Pd, Au, etc., and non-noble metals of compounds and derivatives containing Fe, Co, Ni, Cu, Zn, etc.; raw materials such as glucose, urea, thiourea, dicyandiamide, melamine and the like which can provide oxygen reduction reaction catalyst with certain performance improvement help; additives with certain oxygen reduction reaction catalytic activity such as carbon nanotubes, graphene, graphite type carbon nitride and the like.
The gas diffusion layer in the novel oxygen cathode membrane electrode manufacturing process is all applied gas diffusion layer types in the membrane electrode, including but not limited to carbon paper, carbon cloth, carbon felt and the like.
The catalyst layer raw material is loaded on the gas diffusion layer by using an electrostatic spinning method in the novel oxygen cathode membrane electrode manufacturing process, and the electrostatic spinning method is all electrostatic spinning technologies which follow the electrostatic spinning principle, including but not limited to solution electrostatic spinning, melt electrostatic spinning, needle-free and other special electrostatic spinning technologies.
The method used in the heat treatment in the novel oxygen cathode membrane electrode manufacturing process is a heat treatment method used in all preparation of oxygen reduction reaction catalysts, the used atmosphere is optimally protective gas such as nitrogen, argon and the like, corresponding atmospheres are adopted for different raw materials, for example, polyacrylonitrile adopts oxygen-containing atmosphere at the pre-oxidation stage between 100 ℃ and 300 ℃ at lower temperature, reducing gas such as hydrogen, carbon monoxide and the like is adopted for reducing operation, and gas capable of introducing heteroatom doping is adopted such as hydrogen fluoride, ammonia and the like for etching and compensating operation, and the used atmosphere comprises but is not limited to the atmosphere.
The technological process of the novel oxygen cathode membrane electrode manufacturing process comprises the steps of uniformly mixing the raw materials of the catalyst layer, dissolving or dispersing by using a solvent dispersion method for preparing solution electrostatic spinning, and refining and uniformly mixing particles of solid components by using a crushing stirrer for preparing melt electrostatic spinning. The uniform catalyst layer raw material is placed in an electrostatic spinning device, a gas diffusion layer is fixed on a receiving body, corresponding operation parameters such as injection speed, screw rotating speed, needle type and inner diameter, distance from a needle to the receiving body, type of the receiving body, rotating speed of a rotary receiving drum and the like are set, and certain working temperature and environment humidity are controlled. And setting the voltage of an electrostatic generator, and carrying out electrostatic spinning for a certain time, wherein the load of the catalytic layer on the gas diffusion layer is determined by the spinning time. After spinning, the gas diffusion layer and the catalytic layer mounted thereon are separated from the receiving body and subjected to heat treatment. Setting parameters such as heating rate, heat preservation platform, calcining atmosphere and flow of heat treatment, and cooling to obtain the oxygen cathode membrane electrode integrating catalyst layer preparation and loading.
The novel oxygen cathode membrane electrode manufacturing process has the advantages that the characteristics of an electrostatic spinning technical device are utilized, the conductive gas diffusion layer is fixed on the receiving body, the catalyst layer precursor can be received under the condition that the high-voltage electrostatic field is not influenced, heat treatment is carried out after the precursor is received, the integrated process from preparation to loading of the catalyst layer is realized, and the process flow is simplified. The process is suitable for preparing the catalyst for the oxygen reduction reaction based on the electrostatic spinning technology, can select the low-Pt or non-noble metal catalyst, greatly reduces the manufacturing cost of the membrane electrode while ensuring the performance of the membrane electrode, combines the advantages of uniform and controllable fiber appearance and size and large-batch manufacturing of electrostatic spinning, and has the value of industrial application.
Drawings
FIG. 1 is a schematic view of the process;
FIG. 2 is an SEM topography of carbon fibers in the catalytic layer;
FIG. 3 is a statistical fit of the average diameter of carbon fibers to a normal distribution curve;
FIG. 4 is a polarization curve of a catalytic layer at 1600rpm in an oxygen saturated alkaline solution compared to commercial electrode performance;
FIG. 5 is a comparison of the four electron reaction selectivity of catalytic layers versus commercial electrodes;
FIG. 6 is a resistance test of a catalytic layer in a system without added methanol;
FIG. 7 is a catalytic layer resistance test in a system with added methanol;
FIG. 8 is a comparison of the open circuit voltage provided by the bi-layer assembly produced by the present process and a single Gas Diffusion Layer (GDL) loaded in a metal zinc-air cell;
FIG. 9 is a comparison of the constant current step wave generated by loading a single GDL into a metal-zinc-air cell;
fig. 10 is a comparison of the sustained discharge 6h performance of the dual layer assembly produced by the process compared to a single GDL loaded in a metal zinc-air cell.
Detailed Description
The preparation of the bilayer assembly was carried out according to the process flow shown in figure 1. 0.80mmol of Fe (NO3) 3.9H 2O, 0.30g of glucose and 1.00g of polyacrylonitrile were weighed, dissolved and dispersed in 9.00g N, N-dimethylformamide solvent, and vigorously stirred magnetically at room temperature for 12 hours to form a uniform solution.
Placing the solution in a solution electrostatic spinning device for electrostatic spinning, adopting a stainless steel needle with 18 calibers and the inner diameter of 0.86mm, fixing hydrophilic carbon paper on a roller receiver, setting the injection rate to be 0.30mL/h, setting the distance from the outlet of the needle to the roller to be 20.00cm, setting the rotating speed of the roller to be 600rpm, and setting the positive high voltage to be 24.00 kV.
And (3) carrying out heat treatment on the carbon paper loaded with the precursor, keeping the temperature for 1h when the temperature rise rate is up to 250 ℃ at 1 ℃/min under the air atmosphere, keeping the temperature for 1h when the temperature rise rate is up to 450 ℃ at 5 ℃/min under the argon atmosphere, and keeping the temperature for 2h when the temperature rise rate is up to 800 ℃ at 5 ℃/min.
The morphology of the fibres in the catalytic layer supported on the carbon paper was well maintained after heat treatment (figure 2), the mean diameter of the fibres being about 225.78nm (figure 3). The fiber surface generates a multi-stage structure of nano spider webs, becomes rough, increases the active specific surface area of the catalytic layer and exposes more active sites. A double-layer assembly with the area of 9.00cm2 square is selected and loaded in a metal zinc air cell testing device for testing the cell operation performance, and meanwhile, a part of catalytic layers are selected and ground into powder to be placed in a rotating ring disc electrode for testing the basic electrochemical performance.
Oxygen was introduced into the 0.10M KOH electrolyte to a saturated state, and the rotation speed of the rotating ring disk electrode was set to 1600rpm, to obtain a polarization curve in FIG. 4 showing an initial potential of 1.07V which is 1.05V superior to that of the commercial noble metal electrode, and a half-wave potential of 0.86V, differing by only 10 mV. The four-electron transfer number of fig. 5 after treatment is close to 4.00, which shows that the catalytic layer has good selectivity of four-electron oxygen reduction reaction. FIG. 6A tolerance test of 2000s on the catalytic layer shows that the catalytic layer consistently provided a current density of-4.72 mA cm-2. In fig. 7, methanol is added at 300s to form a tolerance test of 1.00M methanol concentration, and the current provided by the catalytic layer is not significantly reduced or fluctuated due to the introduction of methanol, which proves the excellent methanol resistance of the catalytic layer.
The electrolyte was 6.00M KOH and the bi-layer assembly produced by the process provided a stable open circuit voltage of 1.42V in a metal zinc air cell of 300s in a metal zinc air cell with a square electrode effective contact area of 4.00cm2 (figure 8). 4 different current densities at 1, 10, 50 and 100mA cm-2 are set for transient polarization test to obtain a constant current step wave pattern 9. After two cycles, the response speed of the battery when the battery recovers to the steady state and the stability of maintaining the steady state are good, and the platform voltages of 0.67V, 0.94V, 1.21V and 1.36V are provided respectively. In fig. 10, the continuous operation of the battery for 6h maintains the good operation discharge voltage of 1.18V, and the discharge voltage loss rate is 2.50%.
The above presents a detailed example of the implementation possibilities of the process of the invention. The invention is not limited to the above-mentioned processes, and any modification of the components and local adjustment of the processes based on the above-mentioned processes are within the scope of the invention.
Claims (5)
1. A process for integrating preparation and loading of a catalyst layer in an oxygen cathode membrane electrode is characterized in that: firstly, uniformly mixing raw materials of a catalyst layer, dissolving or dispersing by using a solvent dispersion method for solution electrostatic spinning, or refining and uniformly mixing particles of solid components by using a crushing stirrer for melt electrostatic spinning; secondly, placing uniform raw materials of the catalyst layer on an electrostatic spinning device, fixing a gas diffusion layer on a receiving body, setting corresponding operating parameters, controlling certain working temperature and environmental humidity, setting voltage of an electrostatic generator, and carrying out electrostatic spinning for a certain time, wherein the load of the catalyst layer on the gas diffusion layer is determined by the spinning time; and finally, after spinning is finished, separating the gas diffusion layer and the catalyst layer loaded on the gas diffusion layer from the receiving body, carrying out heat treatment on the gas diffusion layer and the catalyst layer, setting the temperature rise rate, the heat preservation platform, the calcining atmosphere and the flow parameters of the heat treatment, and cooling to obtain the oxygen cathode membrane electrode integrating preparation and loading of the catalyst layer.
2. The process of claim 1 for integrating the preparation and loading of the catalyst layer in the oxygen cathode membrane electrode, which is characterized in that: the catalyst layer raw material is the raw material for preparing the oxygen reduction catalyst by all electrostatic spinning methods, and comprises polyacrylonitrile, polystyrene, polyvinylpyrrolidone or polymethyl methacrylate, the molecular weight is between 1 million and 1 million, and the metal component providing the catalytic activity of the oxygen reduction reaction is a compound and a derivative containing noble metals of Pt, Pd and Au, or a compound and a derivative of non-noble metals of Fe, Co, Ni, Cu and Zn; glucose, urea, thiourea, dicyandiamide or melamine and the like which can provide oxygen reduction reaction catalyst with certain performance improvement help; carbon nano-tube, graphene or graphite type carbon nitride as additives with certain catalytic activity of oxygen reduction reaction.
3. The process of claim 1 for integrating the preparation and loading of the catalyst layer in the oxygen cathode membrane electrode, which is characterized in that: the gas diffusion layer is all the types of gas diffusion layers applied in the membrane electrode, including carbon paper, carbon cloth, or carbon felt.
4. The process of claim 1 for integrating the preparation and loading of the catalyst layer in the oxygen cathode membrane electrode, which is characterized in that: the heat treatment method used in the heat treatment is all heat treatment methods used in the preparation of the oxygen reduction reaction catalyst, and the atmosphere used is nitrogen or argon.
5. The process of claim 4 for integrating the preparation and loading of the catalyst layer in the oxygen cathode membrane electrode, which is characterized in that: the polyacrylonitrile adopts oxygen-containing atmosphere at the pre-oxidation stage between 100 ℃ and 300 ℃ at a lower temperature, adopts reducing gases such as hydrogen, carbon monoxide and the like which need reducing operation, and adopts gases capable of introducing heteroatom doping such as hydrogen fluoride, ammonia and the like which need etching and compensating operation.
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