CN115295816B - Anti-reversal catalyst, preparation method thereof and fuel cell - Google Patents
Anti-reversal catalyst, preparation method thereof and fuel cell Download PDFInfo
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Abstract
The invention provides an anti-reversal catalyst, a preparation method thereof and a fuel cell. The anti-reversal catalyst comprises a noble metal oxide, a first non-noble metal oxide and an optional rare earth oxide, and is of a nanocrystalline grain structure, the particle size of the anti-reversal catalyst is 1-8nm, and the specific surface area is more than or equal to 120m 2 (ii) in terms of/g. By applying the technical scheme, in the anti-reversal catalyst provided by the application, the noble metal oxide, the first non-noble metal oxide and the optional rare earth oxide are fully mixed and contacted to form a nanocrystalline grain structure with the size of 1-8nm, and the specific surface area is more than or equal to 120m 2 The electrolyte has excellent dispersibility, electrochemical activity and structural stability, and can effectively improve the anti-reversal performance and the service durability of the battery.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an anti-reversal catalyst, a preparation method thereof and a fuel cell.
Background
The fuel cell is an energy conversion device which can directly convert chemical energy into electric energy, and avoids the heat-work conversion process of heat engine power generation, so the fuel cell is not limited by Carnot cycle and has higher energy conversion efficiency. As one of the important branches of fuel cells, proton exchange membrane fuel cells have the advantages of cleanliness, no pollution, high energy conversion efficiency, high power density, low emission and heat radiation, low noise and the like, and have been widely applied in the fields of distributed power stations, electric automobiles, aerospace, aviation and the like.
In recent years, proton exchange membrane fuel cells for vehicles have been increasingly commercialized, but the problem of durability under practical operating conditions has been a problem that hinders further large-scale commercialization thereof. Wherein, the reverse pole phenomenon caused by insufficient hydrogen in the anode region affects the durability of the proton exchange membrane fuel cell for vehiclesIs one of the important factors. The reason for the occurrence of the phenomenon of the reverse polarity is that the hydrogen oxidation reaction occurring in the anode region is insufficient to provide enough electrons and protons to maintain the charge balance under the conditions of vehicle start and stop, rapid load change, gas supply failure, flooding, improper flow field design and the like, and therefore, the electrode potential of the anode region is significantly increased and exceeds the electrode potential of the cathode region, so that the phenomenon of the reverse polarity occurs. When the reverse pole phenomenon occurs, the high potential appearing at the anode causes the carbon carrier (C + 2H) 2 O→CO 2 +4H + + 4e - And C + H 2 O →CO+2H + +2e - ) And water molecule (2H) 2 O→O 2 +4H + +4e - ) Oxidation reactions occur to provide the desired electrons and protons.
When the oxidation reaction of the carbon carrier occurs, the carbon carrier can be corroded and even collapsed, so that the loaded Pt nanoparticles fall off and lose efficacy, and the high potential of the anode area can cause the Pt nanoparticles to agglomerate, so that the oxidation of the carbon carrier can seriously damage the catalyst structure, and the durability of the battery is greatly reduced. Meanwhile, a large amount of heat is easily generated due to the occurrence of the reverse polarity phenomenon, and pinholes can be generated on the proton exchange membrane due to the generated heat, so that the open-circuit voltage can be reduced, and the gases of the anode and the cathode can be mixed to cause danger. The occurrence of the oxidation reaction of water molecules as a competitive reaction of the carbon carrier reaction can effectively suppress the oxidation corrosion of the carbon carrier. Therefore, the anti-reversal catalyst is added into the anode of the proton exchange membrane fuel cell to promote the water molecule oxidation reaction, so that the anti-reversal performance of the cell can be greatly improved.
The existing anti-reverse polarization catalyst is generally synthesized by adopting a two-step method, namely, a non-noble metal oxide carrier is synthesized firstly, and then the non-noble metal oxide carrier is mixed with noble metal salt to carry out noble metal oxide loading, so that the anti-reverse polarization catalyst of the proton exchange membrane fuel cell with the non-noble metal oxide loading the noble metal oxide is formed. However, in the anti-reverse polarization catalyst synthesized by the method, the non-noble metal oxide carrier is difficult to be uniformly mixed and contacted with the noble metal salt, so that the noble metal oxide cannot be highly dispersed and supported on the surface of the non-noble metal oxide carrier, and the unsupported noble metal oxide particles are easy to agglomerate, so that the catalytic activity potential is remarkably reduced.
In view of the above, the present invention is especially proposed.
Disclosure of Invention
The invention mainly aims to provide a reverse polarization resistant catalyst, a preparation method thereof and a fuel cell, and aims to solve the problems that in the conventional reverse polarization resistant catalyst synthesized by a two-step method, precious metals cannot be highly dispersed on the surface of a non-precious metal oxide carrier, and the unsupported precious metal oxide particles are agglomerated, so that the catalytic activity potential is remarkably reduced.
In order to achieve the above object, according to one aspect of the present invention, there is provided a reverse-polarity-resistant catalyst, which comprises a noble metal oxide, a first non-noble metal oxide and optionally a rare earth oxide, and has a nanocrystalline structure, wherein the diameter of the reverse-polarity-resistant catalyst is 1 to 8nm, and the specific surface area is not less than 120m 2 /g。
Further, the mass content of the noble metal oxide is 50-90%, preferably 63-73%.
Further, the mass ratio of the rare earth oxide to the first non-noble metal oxide is 0.1 to 5, preferably 1.1 to 5.
Further, the noble metal oxide is iridium oxide and/or ruthenium oxide; the first non-noble metal oxide is at least one of tin oxide, tungsten oxide, antimony oxide, manganese oxide, niobium oxide or titanium oxide; the rare earth oxide is at least one of lanthanum oxide, erbium oxide, dysprosium oxide, samarium oxide or cerium oxide.
Further, the noble metal oxide is iridium oxide, the first non-noble metal oxide is tin oxide and antimony oxide, and the rare earth oxide is lanthanum oxide, more preferably, the mass content of iridium oxide is 72%, the total mass content of tin oxide and antimony oxide is 26.67%, and the mass content of lanthanum oxide is 1.33%; or the noble metal oxide is iridium oxide, the first non-noble metal oxide is titanium oxide, and the rare earth oxide is cerium oxide, more preferably, the mass content of iridium oxide is 63%, the mass content of titanium oxide is 36.1%, and the mass content of cerium oxide is 0.9%; or the noble metal oxide is iridium oxide, the first non-noble metal oxide is manganese oxide, and the rare earth oxide is erbium oxide, more preferably, the mass content of iridium oxide is 73%, the mass content of manganese oxide is 26.7%, and the mass content of erbium oxide is 0.3%; alternatively, the noble metal oxide is iridium oxide and ruthenium oxide, the first non-noble metal oxide is tin oxide and antimony oxide, and the rare earth oxide is lanthanum oxide, more preferably the mass content of iridium oxide and ruthenium oxide is 70%, the total mass content of tin oxide and antimony oxide is 28.57%, and the mass content of lanthanum oxide is 1.43%.
In order to achieve the above object, according to another aspect of the present invention, there is provided a method for preparing a reverse-polarity-resistant catalyst, the method comprising the steps of: step S1, mixing noble metal salt, first non-noble metal salt, second non-noble metal salt and optional rare earth salt to obtain mixed powder; step S2, calcining the mixed powder to obtain a calcined product; and S3, sequentially boiling, washing and drying the calcined product to obtain the anti-reaction agent catalyst.
Further, the mass ratio of the noble metal salt to the first non-noble metal salt is 1 to 3.5; and/or the mass ratio of the rare earth salt to the first non-noble metal salt is 0.1 to 3.
Further, the noble metal salt is at least one of iridium salt and/or ruthenium salt; the first non-noble metal salt is at least one of tin salt, tungsten salt, antimony salt, manganese salt, niobium salt or titanium salt; the second non-noble metal salt is at least one of lithium salt, sodium salt or potassium salt; the rare earth salt is at least one of lanthanum salt, erbium salt, dysprosium salt, samarium salt or cerium salt.
Further, in step S1, the mass ratio of the mass of the second non-noble metal salt to the mass of the noble metal salt, the first non-noble metal salt and the optional rare earth salt is 0.5 to 50, preferably 0.5 to 20;
further, in step S1, the mixing manner includes solid phase mixing or liquid phase mixing, and the liquid phase mixing includes: dispersing noble metal salt, first non-noble metal salt, second non-noble metal salt and optional rare earth salt in a dispersing agent, stirring and drying to obtain mixed powder; the solid-phase mixing comprises grinding and mixing noble metal salt, first non-noble metal salt and second non-noble metal salt; to obtain mixed powder.
Further, when the liquid phases are mixed, the dispersing agent is at least one of water, methanol, isopropanol, n-propanol or ethanol; the stirring mode is at least one of mechanical stirring, magneton stirring, shearing stirring, ball milling stirring or sand milling stirring, and the drying mode is at least one of freeze drying, vacuum drying, blast drying or spray drying; in the case of solid-phase mixing, a ball mill or a Y-type mixer is used for grinding and mixing.
Further, in the step S2, the temperature of the calcination treatment is 260-800 ℃, and the time is 0.5-10 h; and the atmosphere of the calcination treatment includes at least one of air, nitrogen, argon, or oxygen.
Further, in step S3, the boiling and washing are performed by using a detergent, wherein the detergent comprises at least one of water, hydrochloric acid, formic acid, sulfuric acid, perchloric acid or nitric acid.
Further, the boiling and washing temperature is 30 to 90 ℃, the filtrate after boiling and washing is neutral, and the conductivity is less than 200S/cm.
In a third aspect of the present invention, there is further provided a fuel cell using any one of the anti-reversal catalysts provided in the first aspect or the anti-reversal catalyst obtained by any one of the preparation methods provided in the second aspect.
By applying the technical scheme, in the anti-reversal catalyst provided by the application, the noble metal oxide, the first non-noble metal oxide and the optional rare earth oxide are fully mixed and contacted to form a nanocrystalline grain structure with the size of 1-8nm, and the specific surface area is more than or equal to 120m 2 The electrolyte has excellent dispersibility, electrochemical activity and structural stability, and can effectively improve the anti-reversal performance and the service durability of the battery.
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The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows examples 1 to 4Provided antipole catalyst N 2 -adsorption and desorption isotherms and pore size distribution maps;
FIG. 2 is a graph showing electrochemical oxygen evolution reaction activity curves of the anti-bipolar catalysts provided in examples 1-4 and comparative example 3.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
As analyzed by the background art of the present application, in the anti-reverse polarization catalyst synthesized by the existing two-step method, the noble metal cannot be highly dispersed on the surface of the non-noble metal oxide carrier, and the unsupported noble metal oxide particles are agglomerated, which results in the problem that the catalytic activity potential is significantly reduced. In order to solve the problem, the present application provides an anti-reversal catalyst, a method of preparing the same, and a fuel cell.
In a typical embodiment of the application, a reverse-polarity-resistant catalyst is provided, which comprises a noble metal oxide, a first non-noble metal oxide and an optional rare earth oxide, wherein the reverse-polarity-resistant catalyst has a nanocrystalline structure, the particle diameter is 1 to 8nm, and the specific surface area is larger than or equal to 120m 2 /g。
By applying the technical scheme, in the anti-reversal catalyst provided by the application, the noble metal oxide, the first non-noble metal oxide and the optional rare earth oxide are fully mixed and contacted to form a nanocrystalline grain structure with the size of 1-8nm, and the specific surface area is more than or equal to 120m 2 The electrochemical battery has excellent dispersibility, electrochemical activity and structural stability, and can effectively improve the anti-reversal performance and the service durability of the battery.
In the anti-reverse-pole catalyst, when the rare earth oxide is doped, the rare earth element is doped into the noble metal oxide, the electronic structure in the noble metal oxide is further optimized, the binding energy of the anti-reverse-pole catalyst to reaction intermediate species is optimized, the conductivity and the structural stability of the anti-reverse-pole catalyst are further improved, and the ohmic resistance of the battery is further reduced.
In order to further improve the catalytic activity of the anti-reverse-pole catalyst, the particle size of the anti-reverse-pole catalyst is 2-6 nm, so that more active site positions are exposed, and the structural stability and durability of the anti-reverse-pole catalyst are improved.
The noble metal oxide is a noble metal oxide commonly used in the field of anti-bipolar catalysts, and includes, but is not limited to, iridium oxide and/or ruthenium oxide. The first noble metal oxide is a carrier commonly used in the field of anti-reversal catalysts, and includes but is not limited to any one or more of tin oxide, tungsten oxide, antimony oxide, manganese oxide, niobium oxide or titanium oxide. The type of rare earth oxide is not limited and includes, but is not limited to, lanthanum oxide, erbium oxide, dysprosium oxide, samarium oxide, or a mixture of any one or more of cerium oxide.
In order to further improve the catalytic activity of the anti-antipole catalyst, the mass content of the noble metal oxide is preferably 50-90%, and particularly when the mass content of the noble metal oxide is 63-73%, the catalytic activity of the obtained anti-antipole catalyst is obtained.
When the anti-antipole catalyst is doped with rare earth elements for oxidation, the mass ratio of the rare earth oxide to the first non-noble metal oxide is preferably 0.1 to 5, so as to further improve the conductivity and the structural stability of the anti-antipole catalyst, and particularly when the mass ratio of the first rare earth oxide to the first non-noble metal oxide is 1.1 to 5.
Typically, but not by way of limitation, the noble metal oxide is present in the antipole catalyst in an amount, for example, in an amount ranging from 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90%, or any two of these values; the mass ratio of rare earth oxide to first non-noble metal oxide is, for example, 0.1.
In some embodiments of the present application, the noble metal oxide is iridium oxide, the first non-noble metal oxide is tin oxide and antimony oxide, and the rare earth oxide is lanthanum oxide in the anti-bipolar catalyst, especially when the anti-bipolar catalyst contains 72% by mass of iridium oxide, 26.67% by mass of tin oxide and antimony oxide, and 1.33% by mass of lanthanum oxide; or, in the anti-reversal catalyst, the noble metal oxide is iridium oxide, the first non-noble metal oxide is titanium oxide, and the rare earth oxide is cerium oxide, and especially when the mass content of iridium oxide is 63%, the total mass content of titanium oxide is 36.1%, and the mass content of cerium oxide is 0.9%, the anti-reversal catalyst has excellent catalytic activity and structural stability.
In other embodiments of the present application, the noble metal oxide is iridium oxide, the first non-noble metal oxide is manganese oxide, and the rare earth oxide is erbium oxide in the anti-reverse catalyst, particularly when the anti-reverse catalyst has an iridium oxide mass content of 73%, a manganese oxide mass content of 26.7%, and an erbium oxide mass content of 0.3%; or, in the anti-reversal catalyst, the noble metal oxide is iridium oxide and ruthenium oxide (the molar ratio of the two is 1.
In another exemplary embodiment of the present application, there is also provided a method of preparing a counter-electrode-resistant catalyst, the method comprising the steps of: step S1, mixing noble metal salt, first non-noble metal salt, second non-noble metal salt and optional rare earth salt to obtain mixed powder; step S2, calcining the mixed powder to obtain a calcined product; and S3, sequentially boiling, washing and drying the calcined product to obtain the anti-reversal catalyst.
By applying the technical scheme, the catalyst is prepared by adopting a one-step method, the noble metal salt, the first non-noble metal salt, the second non-noble metal salt and the optional rare earth salt are mixed and calcined, the second non-noble metal salt is molten, and the advantage of high solubility of the second non-noble metal salt is utilized, so that the noble metal salt, the first non-noble metal salt and the optional rare earth salt are fully oxidized, and further, the noble metal oxide and the optional rare earth oxide are generatedUniformly loaded on a first non-noble metal oxide to form a powder with the particle diameter of 1 to 8nm and the specific surface area of more than or equal to 120m 2 The anti-reversal catalyst per gram not only has simple process and easy mass production, but also obviously improves the anti-reversal agent activity and durability of the anti-reversal catalyst.
The types of the noble metal salts are not limited, and include, but are not limited to, noble metal nitrates, noble metal chlorides, noble metal sulfates, or the like. Specific noble metals include, but are not limited to, iridium or a mixed salt of either or both. Also, the type of the first non-metal salt is not limited, and includes, but is not limited to, a first non-noble metal nitrate, a first non-noble metal carbonate, a first non-noble metal chloride or sulfate, and the like, and the first non-noble metal includes, but is not limited to, a composite non-noble metal formed from any one or more of tin, tungsten, antimony, manganese, niobium, or titanium. The type of such second non-metal salts are also not limiting and include, but are not limited to, second non-noble metal nitrates, carbonates, chlorides or sulfates of the second non-noble metal, and the like, and second non-noble metals include, but are not limited to, lithium, sodium, potassium, and the like. The type of rare earth salt is also not limited, and includes, but is not limited to, rare earth nitrate, rare earth chloride, and the like, and the type of rare earth includes, but is not limited to, lanthanum, erbium, dysprosium, samarium, cerium, or the like.
In order to further improve the anti-bipolar activity of the prepared anti-bipolar catalyst, the mass of the noble metal salt and the mass of the first non-noble metal salt are preferably 1 to 3.5, so that the mass content of the noble metal oxide prepared by the method is 50 to 90 percent.
In order to further improve the conductivity and structural stability of the prepared anti-bipolar catalyst, the mass ratio of the rare earth salt to the first non-noble metal salt is preferably 0.1-3 to 100, so that the anti-bipolar catalyst with the rare earth element doping content of 0.01-2.5% can be prepared conveniently.
In order to further promote more sufficient contact between the noble metal oxide and the first non-noble metal oxide and the optional rare earth oxide in the antipole catalyst, preferably, in step S1, the mass ratio of the mass of the second non-noble metal salt to the sum of the noble metal salt, the first non-noble metal salt and the optional rare earth salt is 0.5 to 50, so that the second non-noble metal salt forms a uniform melting environment during the subsequent calcination process, and the noble metal, the first non-noble metal and the optional rare earth are sufficiently contacted during the oxidation process to form a nanocrystalline structure. If the sum of the mass of the second non-noble metal salt and the mass of the noble metal salt, the first non-noble metal salt and the optional rare earth salt is less than 0.5, an insufficient melting environment is not provided, resulting in insufficient mixed contact of the noble metal oxide, the first non-noble metal oxide and the optional rare earth oxide, resulting in poor catalytic activity, and if the ratio of the mass of the second non-noble metal salt to the sum of the mass of the noble metal salt, the first non-noble metal salt and the optional rare earth salt is more than 50, resulting in waste of the second non-noble metal salt. Particularly, when the mass ratio of the mass of the second non-metal salt to the sum of the noble metal salt, the first non-noble metal salt and the optional rare earth salt is 0.5 to 20, the waste of the second non-noble metal salt is further reduced while the antipole catalyst with higher catalytic activity is prepared.
Typically but not limitatively, the mass of the second non-metallic salt and the mass of the sum of the noble metal salt, the first non-noble metal salt and the optional rare earth salt are such as from 0.5.
In order to further increase the loading of the noble metal oxide and optionally the rare earth oxide on the first non-noble metal oxide in the antipole catalyst, the preferred manner of mixing comprises solid phase mixing or liquid phase mixing.
In some embodiments of the present application, the solid phase mixing comprises the steps of: and mixing noble metal salt, first non-noble metal salt, second non-noble metal salt and optional rare earth salt, and grinding to obtain the mixed powder. The above grinding is carried out in a ball mill or a Y-type compounding.
In some embodiments of the present application, the liquid phase mixing comprises the steps of: and dispersing noble metal salt, first non-noble metal salt, second non-noble metal salt and optional rare earth salt in a dispersing agent, and drying to obtain mixed powder.
In order to further improve the calcination efficiency and enable the second non-noble metal salt to be more fully melted, in the step S2, the calcination temperature is preferably 260 to 800 ℃ and the calcination time is preferably 0.5 to 10 hours.
The type of the above-mentioned dispersant is not limited, and any substance capable of dispersing the noble metal salt, the first non-noble metal salt, the second non-noble metal salt, and optionally the rare earth salt may be used, including but not limited to a mixed solution formed by any one or more of water, methanol, isopropanol, n-propanol, or ethanol.
The above drying method is not limited, and includes, but is not limited to, freeze drying, vacuum drying, air drying, spray drying, etc. In order to further avoid the phenomenon of nonuniform mixing such as demixing and the like in a liquid phase mixing mode, the preferred drying mode is spray drying.
In order to further improve the calcination efficiency, in the step S2, the temperature of the calcination treatment is preferably 260 to 800 ℃ and the time is preferably 0.5 to 10h, so as to facilitate the second non-noble metal salt to be fully melted, so that the noble metal salt, the first non-noble metal salt and the optional rare earth salt are fully mixed, contacted and oxidized, and further the specific surface area is formed to be more than or equal to 120m 2 A nanocrystalline structure with a particle diameter of 1 to 8 nm. The calcination temperature is too low, which is not beneficial to the insufficient oxidation of the noble metal salt, the first non-noble metal salt and the optional rare earth salt, and the complete transformation of the second non-noble metal salt into a molten state cannot be promoted, so that the formed antipole catalyst has larger particles and is agglomerated, and the catalytic activity of the catalyst cannot be effectively improved; a calcination temperature higher than 800 c causes the grain structure to grow excessively large to be significantly large and the agglomeration to be severe.
Typically, but not by way of limitation, in step S2, the temperature of the calcination process is, for example, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ or a range of any two values; the time is 0.5h, 0.8h, 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or a range value consisting of any two numerical values.
In order to avoid introducing impurities during the calcination, the atmosphere of the calcination treatment is preferably a mixed gas formed by any one or more of air, nitrogen, argon, or oxygen.
In order to further reduce the influence of impurity ions in the anti-reversal catalyst on the catalytic activity, such as the second non-noble metal oxide, it is preferable that in step S3, scouring is performed using a detergent, the type of the detergent is not particularly limited, and the detergent can remove impurity ions and unstable substances in the calcined product, including but not limited to a mixed solution formed by any one or more of water, hydrochloric acid, formic acid, sulfuric acid, perchloric acid and nitric acid. Preferably, the detergent used in the boiling is an acidic detergent to further improve the boiling efficiency and the purity of the product, and the washing is performed with water after acid washing until the filtrate is neutral, so as to further improve the stability and durability of the antipolarity catalyst. In order to further improve the pickling efficiency, the pH of the acidic detergent is preferably 0.1 to 4.
In order to further improve the boiling efficiency, the boiling temperature is preferably 30 to 90 ℃, so that the influence of impurities on the durability of the catalyst activity is further eliminated by the second non-noble metal salt, the second non-noble metal oxide, the possible transition metals such as Fe, co, ni and the like and some unstable active components in the calcined product.
In a third exemplary embodiment of the present application, there is also provided a use of any one of the anti-bipolar catalysts provided in the first exemplary embodiment described above or the anti-bipolar catalyst obtained according to any one of the preparation methods provided in the second exemplary embodiment described above in a fuel cell.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
This example provides a catalyst with anti-reversal polarity, which is prepared according to the following steps:
(1) Dispersing 1g of chloroiridic acid, 0.173g of tin chloride, 0.11g of antimony chloride and 0.008g of lanthanum chloride (accounting for 2.83 percent of the total mass of the tin chloride and the antimony chloride) in a mixed solution of water and ethanol, adding 25.82g of sodium nitrate (the mass of the sodium nitrate is 20 times of the total mass of the chloroiridic acid, the tin chloride, the antimony chloride and the lanthanum chloride), uniformly stirring and mixing, and then carrying out spray drying to obtain mixed powder;
(2) Calcining the mixed powder in an air atmosphere at 500 ℃ for 4h to obtain a calcined product;
(3) And (3) placing the calcined product in a nitric acid aqueous solution (pH = 2) at 60 ℃ for boiling and washing, then washing with deionized water until the pH of the filtrate is 6.9 and the conductivity is less than 160S/cm, and drying to obtain the anti-bipolar catalyst, wherein the iridium oxide accounts for 72% by mass.
Example 2
This example provides a catalyst with anti-reversal polarity, which is prepared according to the following steps:
(1) Dispersing 1g of iridium chloride, 0.83g of titanium chloride and 0.015g of cerium chloride (accounting for 1.8% of the mass of the titanium chloride) in water, adding 92g of lithium nitrate (the mass of the lithium nitrate is 50 times of the total mass of the iridium chloride, the titanium chloride and the cerium chloride), stirring and mixing uniformly, and then carrying out spray drying to obtain mixed powder;
(2) Calcining the mixed powder in a mixed atmosphere of oxygen and nitrogen at 260 ℃ for 10h to obtain a calcined product;
(3) And (3) placing the calcined product into a sulfuric acid aqueous solution (pH = 4) at 90 ℃ for boiling and washing, then washing with deionized water until the pH of the filtrate is 6.8 and the conductivity is less than 150S/cm, and drying to obtain the anti-reversal catalyst, wherein the iridium oxide accounts for 63% by mass.
Example 3
This example provides a counter-electrode resistant catalyst prepared as follows:
(1) Putting 1g of potassium chloroiridate, 0.35g of manganese nitrate and 0.003g of erbium chloride (accounting for 0.9 percent of the mass of the manganese nitrate) into a ball milling tank, adding 0.7g of lithium carbonate (the mass of the lithium carbonate is 0.5 time of the total mass of the potassium chloroiridate, the manganese nitrate and the erbium chloride), and carrying out ball milling and uniform mixing to obtain mixed powder;
(2) Calcining the mixed powder in a mixed atmosphere of oxygen and nitrogen at 800 ℃ for 0.5h to obtain a calcined product;
(3) And (3) putting the calcined product into a formic acid aqueous solution (pH = 0.1) at 30 ℃ for boiling and washing, then washing with deionized water until the pH of the filtrate is 6.8 and the conductivity is less than 200S/cm, and drying to obtain the anti-reversal catalyst, wherein the iridium oxide accounts for 73% by mass.
Example 4
The present example differs from example 1 in that in step (1), chloroiridic acid was replaced with a mixture of equal mass of chloroiridic acid and ruthenium chloride (and the molar ratio of iridium to ruthenium in both was 1), and the mass ratio of the sum of the masses of iridium oxide and ruthenium oxide in the anti-reversal catalyst was 70%.
Example 5
The difference from example 3 is that in step (1), the mass of erbium chloride was adjusted to 0.00035g, which was 0.1% of the mass of manganese nitrate, and the mass content of iridium oxide in the anti-reverse catalyst was 70%.
Example 6
This example is different from example 3 in that, in step (1), the amount of potassium chloroiridate was 0.685g, and the iridium oxide content by mass in the anti-reversal catalyst was 50%.
Example 7
This example is different from example 3 in that the amount of potassium chloroiridate used in step (1) was adjusted to 1.23g and the iridium oxide content in the anti-reversal catalyst was 90% by mass.
Example 8
This example is different from example 3 in that in step (1), potassium chloroiridate was used in an amount of 0.55g, and the iridium oxide content in the anti-reverse catalyst was 40% by mass.
Example 9
This example is different from example 3 in that, in step (1), potassium chloroiridate was used in an amount of 1.27g, and the iridium oxide content in the anti-reversal catalyst was 93% by mass.
Example 10
This example is different from example 2 in that in step (2), the calcination temperature was changed to 230 ℃, and the content of iridium oxide by mass in the anti-reversal catalyst was 60%.
Example 11
This example is different from example 2 in that in step (2), the calcination temperature was changed to 1200 ℃, and the iridium oxide content in the anti-reversal catalyst was 61% by mass.
Example 12
This example is different from example 3 in that in step (1), the mass of erbium chloride was adjusted to 0.021g, which accounts for 6% of the mass of manganese nitrate, and the mass content of iridium oxide in the anti-reverse catalyst was 69%.
Comparative example 1
This comparative example is different from example 1 in that in step (1), sodium nitrate was not added.
Comparative example 2
This comparative example differs from example 1 in that tin chloride and antimony chloride were replaced with equal mass of tin antimony oxide (ATO).
Comparative example 3
This comparative example provides a counter-electrode resistant catalyst that is commercially available iridium oxide.
Test example 1
The particle size, conductivity, specific surface area, activity of oxidation reaction of electrolyzed water, and anti-reversal performance of the anti-reversal catalysts provided in the above examples and comparative examples were respectively tested, and the results are shown in table 1 below.
Wherein, (1) the particle size is determined by an X-ray diffractometer;
(2) The conductivity is measured by a powder conductivity tester;
(3) The BET specific surface area is measured by a specific surface area and micropore analyzer;
(4) The activity of the oxidation reaction of the electrolyzed water is measured by a three-electrode system by adopting a rotating disc electrode and an electrochemical workstation, and the specific measurement conditions are as follows: the electrolyte is 0.1M HClO saturated with oxygen 4 Aqueous solution with noble metal loading of 20 mug/cm 2 The test temperature is 25 ℃, the rotating speed is 1600 rpm, and the scanning speed is 5 mV/s;
(5) The antipole time is measured by a fuel cell test system; the specific measurement conditions are as follows: introducing nitrogen into the anode side of the fuel cell, wherein the test temperature is 80 ℃, and the set current density is 0.2A/cm 2 ；
TABLE 1
| Catalyst and process for preparing same | Crystallite diameter (nm) | Conductivity (S/cm @5 MPa) | BET specific surface area (m) 2 /g） | RHE (@ 10 mA/cm) potential V vs 2 ) | Time of reversal resistance (min) |
| Example 1 | 2.5 | 6.1 | 186 | 1.48 | 368 |
| Example 2 | 2.0 | 3.9 | 209 | 1.52 | 355 |
| Example 3 | 6.0 | 2.0 | 160 | 1.56 | 286 |
| Example 4 | 2.2 | 5.3 | 176 | 1.47 | 280 |
| Example 5 | 6.3 | 1.1 | 158 | 1.60 | 228 |
| Example 6 | 4.9 | 1.4 | 171 | 1.60 | 274 |
| Example 7 | 7.4 | 6.5 | 154 | 1.59 | 281 |
| Example 8 | 6.2 | 0.3 | 158 | 1.66 | 69 |
| Example 9 | 9.8 | 7.1 | 120 | 1.65 | 91 |
| Example 10 | 3.2 | 0.02 | 86 | 1.75 | 12 |
| Example 11 | 16.1 | 1.6 | 11 | 1.69 | 36 |
| Example 12 | 7.3 | 1.0 | 109 | 1.64 | 78 |
| Comparative example 1 | 15.1 | 4.3 | 30 | 1.69 | 25 |
| Comparative example-2 | 8.2 | 3.6 | 106 | 1.63 | 102 |
| Comparative example-3 | 7.4 | 5.3 | 38 | 1.65 | 43 |
FIG. 1 shows the antipole catalyst N provided in examples 1 to 4 2 Adsorption and desorption isotherms and pore size distribution diagrams, fig. 2 is an electrochemical oxygen evolution reaction activity curve of the anti-bipolar catalysts provided in examples 1-4 and comparative example 3, and it can be seen from fig. 1 that example 1 and comparative example 1 have significantly superior pore distribution compared to comparative example 2 and example 11, indicating that the addition of the second non-noble metal salt and a suitable calcination temperature are beneficial for preparing the anti-bipolar catalyst having a superior pore structure; it can be seen from fig. 2 that the catalysts prepared in examples 1 to 4 are capable of producing higher current density at the same potential and lower potential at the same current density as compared to comparative example 3, demonstrating the excellent catalytic performance of the anti-antipole catalysts prepared in examples 1 to 4.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: .
(1) The catalysts of examples 1-7 all had smaller crystallite size, larger BET specific surface area, better performance in the oxidation reaction of electrolyzed water, and longer resistance to the reversal time than the commercial iridium oxide catalyst of comparative example 3.
(2) Comparing example 1 with example 4, it can be seen that the introduction of ruthenium atoms can improve the oxidation activity of electrolyzed water, and the anti-reversal time can be shortened, because in the strong acid and high potential environment, the oxidation reaction of electrolyzed water by ruthenium oxide is carried out by a lattice oxygen participation mechanism, which follows the mechanism to obviously improve the reaction rate, but the lattice oxygen participates in the reaction process, so that the structure is easy to collapse, and the ruthenium atoms are excessively oxidized and dissolved, thereby shortening the anti-reversal time.
(3) Example 5 the amount of erbium chloride doped is reduced to 0.1% with respect to 0.9% of the first non-noble metal salt, resulting in a reduction in the conductivity and thus in the anti-antipole performance;
(4) The lower amount of iridium oxide in example 8 resulted in a substantial decrease in conductivity, and the higher amount of iridium oxide in example 9 resulted in an increase in crystallite particle size and a decrease in specific surface area;
(5) In the embodiment 10, the calcination temperature is changed to 230 ℃, iridium oxide cannot be effectively generated at the temperature, the conductivity is greatly reduced, and the oxidation reaction performance and the anti-reversal time of electrolytic water are greatly reduced, in the embodiment 11, the calcination temperature is changed to 1200 ℃, and catalyst particles are grown and agglomerated due to high temperature, so that the crystallite particle size is remarkably increased, the BET specific surface area is remarkably reduced, and the oxidation reaction performance and the anti-reversal time of hydrolytic water are reduced;
(6) In example 12, the content of erbium chloride in the first non-noble metal salt is changed to 6 percent, and the introduction of excessive rare earth elements can cause the reduction of the electrical conductivity, the reduction of the specific surface area, the reduction of the carrier and the IrO 2 And/or RuO 2 The interaction between the two components is weakened, and the oxidation reaction performance and the anti-reversal time of the electrolytic water are reduced;
(4) In comparative example 1, the second non-noble gold salt was not added, the crystallite size was significantly increased, the BET specific surface area was significantly reduced, and the oxidation reaction performance and the anti-reversal time of the electrolyzed water were significantly reduced.
(5) In the comparative example 2, a two-step method is adopted, namely tin chloride and antimony chloride are replaced by ATO with equal mass, the dispersion of ATO is poor, so that the iridium oxide load is uneven, therefore, the crystallite grain size is increased, the BET specific surface area is reduced, the conductivity is slightly reduced, the electrolytic water oxidation reaction performance and the anti-reversal time are reduced due to the weak interaction between the iridium oxide and the ATO, in addition, the structure of the ATO is unstable under high potential and acidic environment, the separation of antimony element is easy to cause, the structure collapses, and lanthanum ions are difficult to be doped into the ATO, so that the structure stability and the conductivity are difficult to be improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The anti-reversal catalyst is characterized by comprising a noble metal oxide, a first non-noble metal oxide and a rare earth oxide, wherein the anti-reversal catalyst is of a nanocrystalline grain structure, the particle size of the anti-reversal catalyst is 1-8nm, and the specific surface area of the anti-reversal catalyst is more than or equal to 120m 2 /g；
The mass content of the noble metal oxide is 50% -90%;
the mass ratio of the rare earth oxide to the first non-noble metal oxide is 0.1 to 5;
the noble metal oxide is at least one of iridium oxide or ruthenium oxide;
the first non-noble metal oxide is at least one of tin oxide, tungsten oxide, antimony oxide, manganese oxide, niobium oxide or titanium oxide;
the rare earth oxide is at least one of lanthanum oxide, erbium oxide, dysprosium oxide, samarium oxide or cerium oxide.
2. The method for preparing a catalyst according to claim 1, comprising the steps of:
step S1, mixing noble metal salt, first non-noble metal salt, second non-noble metal salt and rare earth salt to obtain mixed powder;
s2, calcining the mixed powder to obtain a calcined product;
s3, sequentially boiling, washing and drying the calcined product to obtain the anti-reversal catalyst;
the mass ratio of the rare earth salt to the first non-noble metal salt is 0.1 to 3;
the mass ratio of the noble metal salt to the first non-noble metal salt is 1 to 3.5; the noble metal salt is at least one of iridium salt and/or ruthenium salt;
the first non-noble metal salt is at least one of tin salt, tungsten salt, antimony salt, manganese salt, niobium salt or titanium salt; the second non-noble metal salt is at least one of lithium salt, sodium salt or potassium salt;
the rare earth salt is at least one of lanthanum salt, erbium salt, dysprosium salt, samarium salt or cerium salt;
in the step S1, the mass ratio of the mass of the second non-noble metal salt to the total mass of the noble metal salt, the first non-noble metal salt and the rare earth salt is 0.5 to 50;
in the step S2, the temperature of the calcination treatment is 260-800 ℃, the time is 0.5-10 h, and the atmosphere of the calcination treatment comprises at least one of air, nitrogen, argon or oxygen.
3. The production method according to claim 2,
the mixing mode comprises solid phase mixing or liquid phase mixing, and the liquid phase mixing comprises the following steps: dispersing the noble metal salt, the first non-noble metal salt, the second non-noble metal salt and the rare earth salt in a dispersing agent, stirring and drying to obtain the mixed powder;
the solid phase mixing comprises: and grinding and mixing the noble metal salt, the first non-noble metal salt, the second non-noble metal salt and the rare earth salt to obtain the mixed powder.
4. The method according to claim 2, wherein the boiling washing is performed with a detergent including at least one of water, hydrochloric acid, formic acid, sulfuric acid, perchloric acid, or nitric acid at step S3;
the boiling and washing temperature is 30-90 ℃, the filtrate after boiling and washing is neutral, and the conductivity is less than 200S/cm.
5. Use of the anti-reversal catalyst according to claim 1 or obtained by the preparation method according to any one of claims 2 to 4 in a fuel cell.
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