CN112340782B - Preparation method of carbon-supported metal oxide catalyst - Google Patents
Preparation method of carbon-supported metal oxide catalyst Download PDFInfo
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- H01M4/90—Selection of catalytic material
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Abstract
The invention provides a preparation method of a carbon-supported metal oxide catalyst, which comprises the following steps: s1, filtering, coating and covering the carbon material, and placing the carbon material in a metal salt solution; s2, heating the metal salt solution, and taking out after the metal salt solution is completely absorbed by the filter bag; s3, extruding the filter bag to discharge redundant solution, and completely drying to obtain a blocky carbon material; and S4, grinding the massive carbon material, and performing heat treatment to obtain the carbon-supported metal oxide catalyst. The patent discloses a preparation method of a carbon-supported metal oxide catalyst, which is different from the prior technical scheme, has the advantage of simple preparation process and can realize batch production.
Description
Technical Field
The invention relates to the technical field of metal fuel cell electrodes, in particular to a preparation method of a carbon-supported metal oxide catalyst.
Background
In the present day that 'energy and environment' become the subject of the times, finding a new energy form with high efficiency, safety and no pollution becomes the focus of general attention of the world at present, and fuel cells are generally concerned by researchers at home and abroad due to the characteristics of rich fuel storage, high energy conversion efficiency, environmental friendliness and the like. Among them, metal-air batteries represented by aluminum, zinc, magnesium, and lithium have been the focus of research in the field of fuel cells due to their distinct characteristics in many aspects, such as high theoretical energy density, abundant storage of raw materials, and high battery safety.
The metal fuel cell is a cell which takes cathode metal as fuel, the anode directly absorbs oxygen in the air to perform reaction discharge, the cathode as the fuel is continuously replaced, the anode needs to be continuously used in the reaction process, the action process needs to realize the efficient reaction of the oxygen with the content of 21 percent in the air to generate enough electric energy, and the process cannot leave the development of an efficient oxygen reduction catalyst; at present, a great deal of work in fuel cell research is used for synthesizing and regulating a catalyst, a great deal of high-efficiency oxygen reduction catalysts are developed, and good experimental performance is obtained.
Patent publication No. CN103846082B discloses a composite metal oxide catalyst supported on mesoporous carbon and its synthesis method, which is a preparation method that a nonionic surfactant and a metal salt as a precursor of the composite metal oxide are dissolved in an organic solvent, and then resol is added for curing. The organic solvent used in the preparation process of the catalyst is not beneficial to the mass preparation of the catalyst, and the problems of high cost, environmental pollution and the like exist.
Patent publication No. CN104085876B discloses a preparation method of carbon nanotube-supported bimetallic oxide hollow nanoparticles, which comprises the following steps: pretreating the surface of the carbon nano tube, taking metal nitrate as a raw material, respectively weighing different metal nitrates, and dissolving the metal nitrates in absolute ethyl alcohol; b, dispersing the carbon nano tube subjected to surface pretreatment obtained in the step A in an ethanol solution, and performing ultrasonic treatment, dispersion and stirring until the solvent is completely volatilized to obtain a dry solid; C. preheating the dried solid obtained in the step B in a nitrogen atmosphere; then heating, and switching to pure hydrogen reduction to obtain the carbon nano tube loaded bimetallic nano-particles; naturally cooling to room temperature; D. and D, oxidizing the material obtained in the step C in the air atmosphere to obtain hollow nano particles of different bimetallic oxides loaded by the carbon nano tubes. The salt solution used in the patent is organic solvent ethanol, and hydrogen is used for reduction in the later period, so that the preparation process has safety problems, and the complex preparation process is difficult to realize large-scale production.
At present, the preparation process of the catalyst in most researches can only be realized in a laboratory, the synthesis difficulty is high, the conditions are harsh, the batch synthesis is difficult to realize, and the catalyst is difficult to be practically applied to metal fuel cells; meanwhile, in the existing method capable of realizing batch synthesis, the control on the morphology, structure and distribution of the catalyst is lacked, and good performance is difficult to obtain.
Disclosure of Invention
Technical problem to be solved
Aiming at the problems, the invention provides a preparation method of a carbon-supported metal oxide catalyst, which is used for at least partially solving the technical problems that the traditional method is difficult to synthesize in large scale, difficult to realize batch synthesis, and lack of control on the morphology, structure and distribution of the catalyst.
(II) technical scheme
The invention provides a preparation method of a carbon-supported metal oxide catalyst, which comprises the following steps: s1, filtering, coating and covering the carbon material, and placing the carbon material in a metal salt solution; s2, heating the metal salt solution, and taking out after the metal salt solution is completely absorbed by the filter bag; s3, extruding the filter bag to discharge redundant solution, and completely drying to obtain a blocky carbon material; and S4, grinding the massive carbon material, and performing heat treatment to obtain the carbon-supported metal oxide catalyst.
Further, the carbon material is one or more of activated carbon, acetylene black, ketjen black, carbon nanotubes and graphene.
Further, the metal salt solution is one or more mixed solutions of transition metal soluble salt solutions, and the solvent of the metal salt solution is water.
Further, the metal salt in the metal salt solution includes nickel nitrate, cobalt nitrate, manganese nitrate, nickel oxalate, cobalt oxalate, manganese oxalate, silver nitrate.
Further, the filter bag is made of materials which are capable of passing liquid and incapable of passing carbon materials and are provided with pores.
Further, the aperture of the filter bag is smaller than 50 um; the filter bag is made of non-woven fabrics and gauze.
Further, the temperature of the heat treatment is 200-400 ℃.
Further, the heat treatment is carried out under the protection of inert atmosphere.
Further, the heat treatment time is 30-60 min.
Further, the drying temperature in S3 is 80-120 ℃.
(III) advantageous effects
According to the preparation method of the carbon-supported metal oxide catalyst provided by the embodiment of the invention, a carbon material impregnation method of filter coating is adopted, compared with the prior art, the method can effectively avoid using an organic solvent as a medium, and simultaneously, a large amount of solution existing among carbon material particles with high bulkiness can be avoided by a coating and matched extrusion process, so that the formed metal oxide with the nanoscale size is uniformly loaded on the carbon material, and excellent catalytic performance is shown.
Drawings
FIG. 1 schematically shows a flow diagram of a method for preparing a carbon-supported metal oxide catalyst according to an embodiment of the invention;
FIG. 2 schematically shows Co prepared according to an embodiment of the present invention3O4Analyzing the morphology of the carbon-supported oxide catalyst by a scanning electron microscope;
FIG. 3 schematically shows Co prepared according to an embodiment of the present invention3O4XRD component analysis of the carbon-supported oxide catalyst;
FIG. 4 schematically shows Co prepared according to an embodiment of the present invention3O4A carbon-supported oxide catalyst aluminum air cell performance test curve;
FIG. 5 schematically shows MnO prepared according to an embodiment of the present inventionXAnalyzing the appearance of the carbon-supported oxide catalyst by a transmission electron microscope;
FIG. 6 schematically shows MnO prepared according to an embodiment of the present inventionXXRD component analysis of the carbon-supported oxide catalyst;
FIG. 7 schematically shows MnO prepared according to an embodiment of the present inventionXA carbon-supported oxide catalyst aluminum air cell performance test curve;
FIG. 8 schematically shows spinel CoMn prepared under the conditions of cobalt oxalate and manganese oxalate being 1: 2 according to an embodiment of the present invention2O4Analyzing the appearance of the carbon-supported oxide catalyst by a transmission electron microscope;
FIG. 9 schematically shows spinel CoMn prepared according to an embodiment of the present invention2O4XRD component analysis of the carbon-supported oxide catalyst;
FIG. 10 schematically shows spinel CoMn prepared under conditions of cobalt oxalate and manganese oxalate of 1: 2 according to an embodiment of the present invention2O4Carbon supported oxidationTesting the performance curve of the aluminum-air battery;
FIG. 11 schematically shows MnO prepared by a conventional hybrid impregnation method in a comparative example according to the present inventionXAnd (3) carrying out shape analysis on the carbon-supported oxide catalyst by a scanning electron microscope.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
An embodiment of the present invention provides a method for preparing a carbon-supported metal oxide catalyst, referring to fig. 1, including: s1, filtering, coating and covering the carbon material, and placing the carbon material in a metal salt solution; s2, heating the metal salt solution, and taking out after the metal salt solution is completely absorbed by the filter bag; s3, extruding the filter bag to discharge redundant solution, and completely drying to obtain a blocky carbon material; and S4, grinding the massive carbon material, and performing heat treatment to obtain the carbon-supported metal oxide catalyst.
The method comprises the following specific steps: preparing metal salt solution with corresponding concentration and placing the metal salt solution in a container; putting the carbon material into a filter bag, sealing the filter bag, and putting the filter bag into the container filled with the solution; the container is heated to reduce the hydrophobicity of the carbon material, so that the salt solution completely immerses the carbon material, the filter bag is taken out when the solution is completely absorbed and sinks to the bottom of the container, and redundant solution is removed in an extruding mode; placing the filter bag obtained in the step (a) in an oven for completely drying, and fully grinding; and (3) placing the ground material in a muffle furnace or other equipment for heat treatment.
According to the method, the carbon material can be bound in the filter bag in a filter bag coating mode, so that the complex operations of dispersion, stirring, filtering, cleaning and the like in the traditional preparation process are directly avoided, and the preparation process is more efficient; and meanwhile, the environmental problem of floating of the carbon material in the preparation process is effectively avoided. On the other hand, compared with the existing direct impregnation method, the filter coating method obtains smaller metal oxide particles which are nano-scale particles. Therefore, the specific surface area is larger, more active sites capable of catalytic reaction are available, and the catalytic activity is higher.
On the basis of the above embodiments, the carbon material is one or more of activated carbon, acetylene black, ketjen black, carbon nanotubes, and graphene.
The carbon material is a common carbon material and is not limited to the above 5 types, the adsorption characteristic of the carbon material is utilized in a manner of coating and soaking the carbon material, redundant metal salt solution is removed through simple extrusion at the later stage, only the part of the carbon material in the pore channel is remained, the oxide load distribution obtained in the state is more uniform, the combination degree with the carbon material is higher, and the catalytic effect and the stability are more advantageous.
On the basis of the above embodiment, the metal salt solution is one or more mixed solutions of transition metal soluble salt solutions, and the solvent of the metal salt solution is water.
Compared with the organic solvent used in the prior art, the metal salt solution is one or more mixed solutions of transition metal soluble salt solutions such as Ni, Co, Mn, Ag and the like, and the solvent is water, so that the method has the advantages of safety, low cost, contribution to large-scale production and the like.
On the basis of the above embodiment, the metal salt in the metal salt solution includes nickel nitrate, cobalt nitrate, manganese nitrate, nickel oxalate, cobalt oxalate, manganese oxalate, silver nitrate.
By controlling the concentration of the metal salt solution, metal oxide catalysts with different loading contents can be obtained, so that the metal fuel cell catalyst with optimized performance is obtained. In order to ensure that all carbon material is fully contacted with the solution for sufficient adsorption, it is therefore necessary to immerse for a certain time, and continuing the immersion does not cause increased adsorption, and therefore concentration control is primarily used. Under solutions with different concentrations, the salt amount obtained by adsorbing the same solution by the carbon material is different, so that the loading amount after decomposition is different, and the regulation and control are realized.
On the basis of the embodiment, the filter bag is made of a material which can pass liquid and can not pass carbon materials and is provided with a pore passage.
The filter bag mainly plays a role in coating the carbon material, so that the carbon material is prevented from being completely dispersed in the solution, and the using amount of the solution is reduced; the solution is absorbed by the carbon material in the filter bag in the dipping process, and the solution is not absorbed after the material is adsorbed to saturation, so that the complicated operations of dispersion, stirring, filtering, cleaning and the like are avoided; meanwhile, redundant solution can be removed in an extrusion mode only in the later stage of a coating mode, and extrusion is the simplest and most effective mode, and the redundant solution in the extrusion die can be removed more by external pressure.
On the basis of the embodiment, the pore diameter of the filter bag is less than 50 um; the filter bag is made of non-woven fabrics and gauze.
The aperture of the filter bag cannot be too large and is generally smaller than 50 um; the filter bag is one of the modes, and the filter bag can be made into a bag with proper pore size by flexible cloth or directly wrapped (such as non-woven fabrics).
In the above embodiment, the heat treatment temperature is 200 to 400 ℃.
The heat treatment functions to convert metal salts (nitrates, oxalates, etc.) previously adsorbed into the carbon material into oxides by means of thermal decomposition. The metal salt has a decomposition temperature that is sufficient to decompose the salt to an oxide (e.g., cobalt nitrate decomposes to produce cobalt oxide under heating). The heat treatment temperature is 200-400 ℃, not only the decomposition temperature of oxidation is reached, but also the carbon material ablation cannot be caused due to overhigh temperature.
On the basis of the above examples, the heat treatment was carried out under inert atmosphere conditions.
The heat treatment is carried out in an inert atmosphere, so that the ablation problem of the carbon material can be effectively avoided, and the stability of the carbon carrier, the combination distribution uniformity of the catalyst and the carbon carrier and the catalytic activity are ensured.
In addition to the above embodiments, the heat treatment time is 30 to 60 min.
The time for the heat treatment cannot be too short, the time is required for complete decomposition of the metal salt, and the too short time may cause incomplete conversion of the metal salt into an oxide, resulting in changes in the catalyst composition and properties.
In addition to the above embodiments, the drying temperature in S3 is 80-120 ℃.
The standard of complete drying is that the weight loss is required to be less than 5%, the drying process mainly removes water, metal is left in the material, and residual water can influence the later grinding effect of the catalyst, so that the catalyst cannot be ground to a dispersed state, and the problem of catalyst particle agglomeration is easily generated in the later heat treatment process, thereby influencing the performance of the catalyst.
The preparation method of the carbon-supported metal oxide catalyst comprises the processes of preparation of metal salt solution, coating of carbon material, impregnation, drying, grinding, heat treatment and the like, and has the advantages of simple preparation process, easy control of the process and capability of realizing batch high-efficiency synthesis. The catalyst has universality for the synthesis of a class of catalysts with metal oxides loaded on carbon materials.
The invention is described in detail below with 3 specific examples.
Example 1
Weighing about 4g of cobalt nitrate, putting the cobalt nitrate into 1L of pure water, fully stirring to form a cobalt salt solution, weighing 6g of Ketjen black, putting the Ketjen black into a filter bag, sealing the upper end of the Ketjen black, putting the filter bag and the solution into the salt solution, putting the container containing the solution and the filter bag into a water bath, heating for 10min to completely immerse the filter bag into the salt solution, taking out the container, and naturally cooling to room temperature.
And after the solution is completely cooled, taking out the filter bag, squeezing out the redundant solution inside in a wringing or squeezing mode to obtain the molded carbon material, wherein the redundant solution can be recycled for secondary use. And (3) drying the filter bag in an oven at the temperature of 80-120 ℃ to obtain a blocky carbon material after complete drying.
And (3) fully grinding the blocky carbon material, and then placing the material in a muffle furnace to carry out heat treatment on the material at 200-400 ℃ under the condition of oxygen or nitrogen, wherein the heat treatment time is 30-60 min, so as to obtain the catalyst material.
FIGS. 2, 3 and 4 are tables of the structure, composition and catalyst performance carried out in example 1 of the inventionThe figure 2 is a feature of a morphological structure, and the size of the material is dozens of nanometers and the uniformity is good as can be seen from the figure (combined with a scale); the compositional analysis of FIG. 3 revealed that the oxide obtained by the thermal decomposition was Co3O4The feasibility of synthesizing the oxide is verified; FIG. 4 is a graph of performance of the catalyst of example 1 in a metal fuel cell test at 150mA/cm2The average voltage under the current density of the high-voltage power supply can reach 1.2V, and the high-voltage power supply has good performance.
Example 2
Weighing about 10mL of manganese nitrate solution (50%) and adding the manganese nitrate solution into 1L of pure water, fully stirring to form manganese salt solution, weighing 6g of Keqin black and placing the Keqin black into a filter bag, sealing the upper end of the Keqin black and placing the Keqin black into the salt solution, placing the container filled with the solution and the filter bag into a water bath for heating for 10min to completely immerse the filter bag into the salt solution, taking out the container and naturally cooling to room temperature.
And after the solution is completely cooled, taking out the filter bag, squeezing out the redundant solution inside in a wringing or squeezing mode, and recycling the redundant solution of the formed carbon material. And (3) drying the filter bag in an oven at the temperature of 80-120 ℃ to obtain a blocky carbon material after complete drying.
And (3) fully grinding the blocky carbon material, and then placing the material in a muffle furnace to carry out heat treatment on the material at 200-400 ℃ under the condition of oxygen or nitrogen, wherein the heat treatment time is 30-60 min, so as to obtain the catalyst material.
FIGS. 5, 6, and 7 are representations of the structure, composition, and catalyst performance of example 2 of the present invention, wherein FIG. 5 is a topographical feature of the catalyst, and the dimensions of the material can be seen as tens of nanometers with reference to the scale in the figures; from the brightness contrast, the particles with high brightness are carbon materials, the particles with low brightness are metal oxides, and the distribution of the oxides in the interior is relatively uniform; FIG. 6 is a test of the composition of the material, and it is confirmed that Mn is obtained by thermal decomposition of manganese nitrate in example 23O4And Mn5O8Mixed oxides of (4); FIG. 7 shows the performance of the catalyst in a 150mA/cm metal fuel cell test2The average voltage under the current density of the high-voltage power supply can also reach 1.2V, and the high-voltage power supply has good performance.
Example 3
Weighing 4g of mixed salt of cobalt oxalate and manganese oxalate according to the ratio of 1: 2, 1: 1 and 2: 1 respectively, adding the mixed salt into 1L of pure water, fully stirring to form a mixed salt solution of cobalt and manganese, weighing 6g of acetylene black, placing the acetylene black into a filter bag, sealing the upper end of the acetylene black into the salt solution, placing the container filled with the solution and the filter bag into a water bath, heating for 10min to completely immerse the filter bag into the salt solution, taking out the container, and naturally cooling to room temperature.
And after the solution is completely cooled, taking out the filter bag, squeezing out the redundant solution inside in a wringing or squeezing mode, and recycling the redundant solution of the formed carbon material. And (3) drying the filter bag in an oven at the temperature of 80-120 ℃ to obtain a blocky carbon material after complete drying.
And (3) fully grinding the blocky carbon material, and then placing the material in a muffle furnace to carry out heat treatment on the material at 200-400 ℃ under the condition of oxygen or nitrogen, wherein the heat treatment time is 30-60 min, so as to obtain the catalyst material.
FIGS. 8, 9 and 10 are representations of the structure, composition and catalyst performance of example 3 of the present invention, which differs from examples 1 and 2 in that example 3 employs two metal salts in combination for catalyst synthesis; wherein, fig. 8 shows the morphology structure of the catalyst prepared under the condition that the ratio of cobalt oxalate to manganese oxalate is 1: 2 in example 3, the distribution size is also tens of nanometers, and the uniformity is better; as shown in FIG. 9, the composition analysis shows that CoMn having a spinel structure as an oxide is obtained by 1: 2 cobalt oxalate and manganese oxalate2O4(ii) a FIG. 10 is a graph of the performance of the catalysts prepared in example 3 at different ratios of cobalt oxalate and manganese oxalate for metal fuel cell testing at 150mA/cm2Under the current density of the three groups of catalysts, the average voltage of the three groups of catalysts can reach 1.2V, and the three groups of catalysts have good performance.
Comparative example
Weighing 4g of manganese oxalate, adding the manganese oxalate into 1L of pure water, fully stirring to form a manganese salt solution, and further adding a certain amount of ethanol into the solution to reduce the surface tension of the carbon material. And weighing 6g of Ketjen black, directly adding into the salt solution, slowly stirring to avoid flying carbon material, heating the container in water bath for 30min, continuously stirring to completely impregnate the carbon material, and taking out the container to naturally cool to room temperature.
And after the solution is completely cooled, separating the carbon material from the solution in a filtering mode, collecting the obtained carbon material, putting the carbon material obtained by filtering into a container, drying the carbon material in an oven at the temperature of 80-120 ℃, and completely drying to obtain the blocky carbon material.
And (3) fully grinding the blocky carbon material, and then placing the material in a muffle furnace to carry out heat treatment on the material at 200-400 ℃ under the condition of oxygen or nitrogen, wherein the heat treatment time is 30-60 min, so as to obtain the catalyst material.
FIG. 11 is a catalyst prepared by the process of directly adding carbon material into metal salt solution, stirring and filtering in example 4 of the present invention, which shows that a large amount of blocky, granular, linear and other structural materials are distributed in the catalyst, and the distribution uniformity is poor. In scale, the size of part of materials reaches more than micron level, and the size difference is obvious, which is not beneficial to the efficient utilization and performance of the catalyst.
It should be noted that all the above catalysts were used in the same manner for the preparation of air electrode of metal fuel cell, the air electrode for the catalyst was the cathode of metal air, and the experimental aluminum cathode (Vs Al) was 150mA/cm2(6A) The air electrode has an active area of 40cm when tested under current2The electrolyte was 6M KOH aqueous solution.
Comparing the examples with the comparative examples, it can be seen that the scale distribution of the metal oxide obtained by coating the carbon material with the filter bag and the matched treatment method is tens of nanometers, and the metal oxide has larger specific surface area and distribution uniformity. In the comparative example, in the prior art, an organic solvent is required to be used for promoting the carbon material to be impregnated in the preparation process so as to prevent the carbon material loss and the environmental problem caused by flying and floating of the material in the stirring process. Meanwhile, in the state of the obtained material, the catalyst oxide prepared by the prior art has larger scale, and part of the material reaches the micron level and cannot be combined with the carbon material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method of preparing a carbon-supported metal oxide catalyst, comprising:
s1, filtering, coating and covering the carbon material, and placing the carbon material in a metal salt solution; the pore diameter of the filter bag is less than 50 um; the filter bag is made of at least one of non-woven fabrics and gauze;
s2, heating the metal salt solution, and taking out the filter bag after the filter bag completely absorbs the metal salt solution; the metal salt in the metal salt solution comprises at least one of nickel nitrate, cobalt nitrate, manganese nitrate, nickel oxalate, cobalt oxalate, manganese oxalate and silver nitrate;
s3, squeezing the filter bag to discharge redundant solution, and completely drying to obtain a massive carbon material;
s4, grinding the massive carbon material, and performing heat treatment at 200-400 ℃ to obtain the carbon-supported metal oxide catalyst.
2. The method for preparing a carbon-supported metal oxide catalyst according to claim 1, wherein the carbon material is one or more of activated carbon, acetylene black, ketjen black, carbon nanotubes, and graphene.
3. The method of preparing a carbon-supported metal oxide catalyst according to claim 1, wherein the heat treatment is performed under an inert atmosphere.
4. The method for preparing a carbon-supported metal oxide catalyst according to claim 3, wherein the heat treatment time is 30 to 60 min.
5. The method for preparing a carbon-supported metal oxide catalyst according to claim 1, wherein the drying temperature in S3 is 80 to 120 ℃.
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