CN110745881A - Calcium-doped yttrium ruthenate, preparation method thereof and application thereof in electrochemical device - Google Patents
Calcium-doped yttrium ruthenate, preparation method thereof and application thereof in electrochemical device Download PDFInfo
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Abstract
The invention relates to the technical field of electrochemical catalysis, in particular to calcium-doped yttrium ruthenate, a preparation method thereof and application thereof in an electrochemical device. The calcium-doped yttrium ruthenate has the following molecular formula: y is2‑xCaxRu2O7Wherein, 0<x<1. The calcium-doped yttrium ruthenate provided by the invention has stable electrochemical catalytic activity under acidic and alkaline conditions, and is suitable for being used in electrochemical devices such as protonsThe oxygen reaction electrode catalyst material of the exchange membrane electrolytic cell or the zinc-air cell can greatly reduce the using amount of the oxygen reaction electrode catalyst under the same condition and reduce the cost of the electrochemical device.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalysis, and particularly relates to calcium-doped yttrium ruthenate, a preparation method thereof and application thereof in an electrochemical device.
Background
The Power to gas technology (abbreviated as P2G or PtG) is a technology for converting electric Power into gas fuel, and is a new large-scale industrial hydrogen production technology by electrolyzing water, which is closely combined with clean energy, especially intermittent renewable energy Power generation, which has been developed in recent years. The key of the electric gas conversion technology is to decompose water into oxygen and hydrogen by means of electrolysis of electricity. Hydrogen gas can be the carrier of stored energy, so this use is also referred to as hydrogen storage. Taking a solar hydrogen production and energy storage technology as an example, the core idea is as follows: when the solar power generation is sufficient but can not be completely used, the redundant electricity can be converted into hydrogen in an electrolytic water mode, and then the hydrogen is stored as an energy carrier; when electric energy is needed, the stored hydrogen is converted into electric energy through different modes (an internal combustion engine, a fuel cell or other modes) and is transmitted to the Internet. Another solution for use with renewable energy power generation is energy storage, where redundant electricity from renewable energy is stored in electrochemical cells. Common electrochemical cells include lithium batteries, flow batteries, and zinc-air batteries, among which zinc-air batteries have received much attention due to their relatively low cost, high energy density, and simple structure. There are also Proton Exchange Membrane (PEM) electrolyzers, which are energy storage devices that convert electrical energy to chemical energy and include an anode, a cathode, and a proton exchange membrane, and typically also include collector plates, field plates, and other support members. However, the oxygen reaction electrode kinetics reaction rate of the zinc-air cell and the PEM electrolytic cell is slow, which limits further application of the zinc-air cell and the PEM electrolytic cell. Therefore, it is important to develop an efficient, stable, low-cost oxygen reaction electrode catalyst.
In addition, the working environment of the zinc-air cell is generally alkaline, while the working environment of the PEM electrolytic cell is acidic, and the requirements on the characteristics of materials are greatly different. At present, no oxygen reaction electrode material which can meet the requirements of both a zinc-air cell and a PEM electrolytic cell exists.
Disclosure of Invention
Aiming at the problems that the prior oxygen reaction electrode has slow kinetic reaction rate and can not meet the requirements of use under acidic condition and alkaline condition, the invention provides calcium-doped yttrium ruthenate and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a calcium-doped yttrium ruthenate having the following formula:
Y2-xCaxRu2O7wherein, 0<x<1。
Correspondingly, the preparation method of the calcium-doped yttrium ruthenate comprises the following steps:
providing a mixed solution containing yttrium ions, calcium ions and ruthenium ions;
adding a metal ion ligand into the mixed solution to perform ligand reaction to obtain a coordination compound containing yttrium ions, calcium ions and ruthenium ions;
removing the solvent in the coordination compound to obtain a precursor of calcium-doped yttrium ruthenate;
crushing the precursor, and calcining in an oxygen-containing atmosphere to obtain calcium-doped yttrium ruthenate; the calcium-doped yttrium ruthenate has the following molecular formula: y is2-xCaxRu2O7Wherein, 0<x<1；
The molar ratio of yttrium ions, calcium ions and ruthenium ions in the mixed solution to the Y2-xCaxRu2O7The molar ratio of the element Y, Ca to Ru is the same.
Further, an oxygen reaction electrode comprising calcium-doped yttrium ruthenate as described above; or the calcium-doped yttrium ruthenate contained in the oxygen reaction electrode is prepared by the preparation method of the calcium-doped yttrium ruthenate.
A proton exchange membrane electrolytic cell comprising an anode which is an oxygen reactive electrode as described above.
A zinc-air battery comprising an air electrode which is an oxygen reactive electrode as described above.
The invention has the technical effects that:
compared with the prior art, the calcium-doped yttrium ruthenate and bivalent Ca provided by the invention2+Replacing Y of pyrochlore structure2Ru2O7Partial orthotrivalent Y in (1)3+So that the calcium-doped yttrium ruthenate generates a hole doping effect in the oxygen catalysis process, the surface oxygen vacancy concentration is increased, more active sites are provided for the oxygen evolution reaction or the oxygen reduction reaction, and the positive divalent Ca2+By replacement of part of the positive trivalent Y3+Also make a single Ru4+To Ru4+And Ru5+The mixing of the components is beneficial to improving the oxidation-reduction capability of the catalyst, further promotes oxygen evolution reaction or oxygen reduction reaction, and has catalytic function under acidic and alkaline conditions.
According to the preparation method of the calcium-doped yttrium ruthenate, the precursor containing yttrium ions, calcium ions and ruthenium ions is obtained in a sol-gel mode, and then the calcium-doped yttrium ruthenate is obtained through calcination.
The oxygen reaction electrode provided by the invention has the characteristics of low content of noble metal, high electrochemical catalytic activity, good and stable oxygen reaction catalytic performance in acidic and alkaline systems and the like.
The anode of the proton exchange membrane electrolytic cell provided by the invention contains the calcium-doped yttrium ruthenate, and the proton exchange membrane electrolytic cell has good stability and catalytic characteristics under an acidic condition, so that the proton exchange membrane electrolytic cell has excellent electrochemical catalytic activity and good catalytic effect.
According to the zinc-air battery provided by the invention, the air electrode contains the calcium-doped yttrium ruthenate, and the calcium-doped yttrium ruthenate has good stability and catalytic activity under an alkaline condition, so that the zinc-air battery has a good catalytic effect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an XRD diffraction line of calcium-doped yttrium ruthenate prepared in examples 1 to 3 according to the invention and yttrium ruthenate prepared in comparative example 1;
FIG. 2 is a graph showing electrochemical oxygen evolution reaction performance of the calcium-doped yttrium ruthenate prepared in examples 1 to 3 of the present invention as an electrode and the electrodes provided in comparative examples 1 and 2 in a 0.5mol/L sulfuric acid solution system, respectively;
FIG. 3 is a graph showing that calcium-doped yttrium ruthenate prepared in example 2 according to the invention is used as an electrode and that the electrode provided in comparative example 1 is subjected to a solution of 10mA/cm in 0.5mol/L sulfuric acid2The change curve of voltage along with time when the current density and the scanning speed are 10 mV/s;
FIG. 4 is a graph comparing the electrolytic performance of a proton exchange membrane cell assembled from the electrodes of comparative example 2 and fabricated from calcium-doped yttrium ruthenate provided in example 2 of the present invention at a scan rate of 10 mV/s;
FIG. 5 is a graph showing comparison of oxygen reduction reaction performance between electrodes made of calcium-doped yttrium ruthenate according to examples 1 to 3 of the present invention and electrodes of comparative examples 1 to 3 in a 0.1mol/L potassium hydroxide solution at a scanning speed of 20 mV/s;
FIG. 6 is a graph showing comparison of oxygen evolution reaction performance between electrodes made of calcium-doped yttrium ruthenate provided in examples 1 to 3 of the present invention and electrodes provided in comparative example 1 in a 0.1mol/L potassium hydroxide solution at a scanning speed of 10 mV/s;
FIG. 7 shows that the calcium-doped yttrium ruthenate provided in example 2 of the present invention is fabricated into an electrode and assembled into a zinc-air battery and a Pt/C-IrO2A power density curve comparison graph when the zinc-air battery is assembled;
FIG. 8 shows calcium-doped ruthenic acid according to example 2 of the present inventionYttrium is made into an electrode and assembled into a zinc air battery and a Pt/C-IrO2When the zinc-air battery is assembled, the concentration is 5mA/cm2Comparative stability test chart in charge and discharge mode (1).
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 the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides calcium-doped yttrium ruthenate, which has the following molecular formula:
Y2-xCaxRu2O7wherein, 0<x<1。
Y2Ru2O7(abbreviated as: YRO) is an oxide having a pyrochlore structure which has been found to have certain oxygen evolution and oxygen reduction activities. Relative to RuO2YRO has a Ru noble metal content of 76.5% (RuO)2) Reduced to 41%, however, YRO required further increases in electrochemical catalytic activity to meet the needs of proton exchange membrane electrolytic cells and zinc air cells. By at the A position (A)2B2O7) Doping is carried out, and Ca is partially introduced2+The catalyst generates a hole doping effect, so that the surface oxygen vacancy concentration is further improved relative to YRO, and more active sites are provided for oxygen evolution and oxygen reduction reactions; at the same time, Ca is introduced2+Partially substituted Y3+The valence state of B-position Ru can be increased to make the material have single Ru4+To Ru4+And Ru5+The average valence of Ru is increased, the redox capability of Ru is enhanced, the electrochemical activity of Ru is further improved, and the Ru can stably exist in acidic oxygen evolution reaction and alkaline oxygen evolution reaction and shows good catalytic effect. Compared with other catalysts, the amount of the oxygen evolution reaction catalyst can be greatly reduced under the same performance. In particular, the calcium-doped yttrium ruthenate may be Y1.95Ca0.05Ru2O7、Y1.9Ca0.1Ru2O7、Y1.85Ca0.15Ru2O7、Y1.8Ca0.2Ru2O7、Y1.75Ca0.25Ru2O7、Y1.7Ca0.3Ru2O7、Y1.65Ca0.35Ru2O7、Y1.6Ca0.4Ru2O7、Y1.55Ca0.45Ru2O7、Y1.5Ca0.5Ru2O7、Y1.45Ca0.55Ru2O7、Y1.4Ca0.6Ru2O7、Y1.35Ca0.65Ru2O7、Y1.3Ca0.7Ru2O7、Y1.25Ca0.75Ru2O7、Y1.2Ca0.8Ru2O7、Y1.15Ca0.85Ru2O7、Y1.1Ca0.9Ru2O7、Y1.05Ca0.95Ru2O7And the like.
Preferably, the particle size of the calcium-doped yttrium ruthenate is (100-2000) nm. For example, the particle diameter may be 100nm, 150nm, 180nm, 200nm, 210nm, 250nm, 260nm, 280nm, 300nm, 350nm, 380nm, 400nm, 450nm, 500nm, 550nm, 580nm, 600nm, 620nm, 650nm, 680nm, 780nm, 800nm, 960nm, 980nm, 1200nm, 1300nm, 1400nm, 1500nm, 1550nm, 1600nm, 1700nm, 1800nm, 1900nm, 2000nm, etc. The grain diameter is in the range, so that the calcium-doped yttrium ruthenate has higher specific surface area and shows better oxygen evolution catalytic activity.
Further preferably, the calcium-doped yttrium ruthenate has the formula 0.15. ltoreq. x.ltoreq.0.4, e.g. the calcium-doped yttrium ruthenate may be Y1.85Ca0.15Ru2O7、Y1.8Ca0.2Ru2O7、Y1.75Ca0.25Ru2O7、Y1.7Ca0.3Ru2O7、Y1.65Ca0.35Ru2O7、Y1.6Ca0.4Ru2O7And the like.
More preferably, the calcium-doped yttrium ruthenate is Y1.85Ca0.15Ru2O7、Y1.75Ca0.25Ru2O7、Y1.6Ca0.4Ru2O7Any one of the above.
Any of the calcium-doped yttrium ruthenates described above can be prepared by:
step S01, providing a mixed solution containing yttrium ions, calcium ions and ruthenium ions, wherein the molar ratio of the yttrium ions, the calcium ions and the ruthenium ions in the mixed solution is ensured to be equal to that of a target product Y2-xCaxRu2O7The molar ratio of the element Y, Ca to Ru is the same;
step S02, adding a metal ion ligand into the mixed solution obtained in the step S01 to enable ligand reaction to occur, and obtaining a coordination compound containing yttrium ions, calcium ions and ruthenium ions;
s03, removing the solvent in the coordination compound obtained in the step S02 to obtain a precursor of calcium-doped yttrium ruthenate;
and S04, crushing the precursor, and calcining in an oxygen-containing atmosphere to obtain the calcium-doped yttrium ruthenate.
In step S01, yttrium salt, calcium salt, and ruthenium salt may be mixed together, and then a solvent such as deionized water is added to prepare a mixed solution; or respectively preparing yttrium salt solution, calcium salt solution and ruthenium salt solution, and mixing the three solutions. Yttrium salt used is selected from Y (NO)3)3·6H2O、YCl3、YCl3·6H2At least one of O; the calcium salt is at least one selected from calcium nitrate, calcium acetate monohydrate, calcium chloride and calcium sulfate; the ruthenium salt is selected from RuCl3、(NH4)2RuCl6、K2RuCl5(H2O). The yttrium salt, calcium salt and ruthenium salt have good solubility, and can be prepared into stableThe solution of (1); in addition, the yttrium salt, the calcium salt and the ruthenium salt have high purity and less impurities, so that the finally prepared oxygen reaction catalyst has high purity, and the catalytic activity and the stability of the oxygen reaction catalyst are effectively improved.
Preferably, in the mixed solution, the concentration of yttrium ions is (0.001-0.1) mol/L, the concentration of ruthenium ions is (0.001-0.1) mol/L, and the concentration of calcium ions is (0.001-0.1) mol/L; the concentrations of yttrium ions, ruthenium ions and calcium ions can be adjusted according to the final required calcium-doped yttrium ruthenate molecular formula.
In step S02, the metal ion ligand used is at least one of citric acid, citric acid monohydrate, and ethylenediaminetetraacetic acid.
The molar ratio of the metal ion ligand to the total amount of the yttrium ions, the ruthenium ions and the calcium ions in the mixed solution is (1-10): 1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 10:1 and the like. Adding excessive metal ion ligand to make yttrium ion, ruthenium ion and calcium ion generate sufficient coordination reaction, thereby making the molecular formula Y2-xCaxRu2O7The metered addition of yttrium ions, ruthenium ions and calcium ions can be completely finished into the final product. After the metal ion ligand is mixed with the mixed solution, ligand reaction occurs, and yttrium ions, calcium ions and ruthenium ions form stable coordination compounds with the ligand, so that the coordination compounds simultaneously containing yttrium ions, calcium ions and ruthenium ions appear in a liquid phase system of the reaction.
Preferably, after the mixed solution is mixed with the metal ion ligand, the pH of the mixed solution containing the metal ion ligand is adjusted to be alkaline, so as to improve the stability of the ligand, thereby forming a stable sol. Further preferably, the pH value of the solution system after the ligand reaction is finished is 8.5-9. If the pH value is too high, metal ions can be precipitated to generate corresponding metal oxide byproducts; if the pH is too low, the stability of the coordination compound is not good, and the purity of the product is influenced.
When the pH is adjusted, the adjusting agent used is an alkaline agent such as ammonia water, preferably ammonia water, which does not introduce impurities.
In step S03, drying the mixture for 6 to 24 hours at 100 to 150 ℃ under vacuum condition to remove the solvent in the liquid phase system, thereby obtaining a gel-state coordination compound, namely the precursor of the calcium-doped yttrium ruthenate.
Before drying, the solvent may be volatilized by heating in a water bath or the like. The mixed solution containing the coordination compound obtained in step S02 may be subjected to a standing aging treatment to precipitate the coordination compound, and finally the solvent may be removed by solid-liquid separation to obtain a solid mixture, which is then dried.
In step S04, the pulverization may be ball milling or other pulverization methods. Through crushing treatment, the particle size of the calcined product is 100 nm-2000 nm, so that on one hand, the particle size of the calcined product can be effectively controlled, and the specific surface area of the calcined product is improved, thereby being beneficial to improving the catalytic activity of the calcined product; on the other hand, the pulverization treatment enables the solid mixture to be sufficiently calcined.
Calcining the precursor subjected to pulverization treatment in an oxygen-containing atmosphere to cause the components to undergo lattice migration to generate Y2-xCaxRu2O7. Wherein, the oxygen-containing atmosphere in the calcination can lead the precursor to be fully oxidized to form the corresponding oxide, and the organic components in the metal complex are removed.
Preferably, the temperature of the calcination treatment is 600 ℃ to 1200 ℃. For example, the temperature is raised to 600-800 ℃ for calcination (6-12) h, and then raised to 800-1200 ℃ for constant temperature (6-12) h.
According to the preparation method, the calcium-doped yttrium ruthenate is obtained. The preparation method has the characteristics of easily controlled process conditions, good repeatability and the like.
The calcium-doped yttrium ruthenate described above can be used in electrochemical devices. Specifically, it can be used as an oxygen reaction electrode of an electrochemical device.
Specifically, the calcium-doped yttrium ruthenate contained in the oxygen reaction electrode may be of formula Y2-xCaxRu2O7(0<x<1) At least one of them, e.g. Y1.95Ca0.05Ru2O7、Y1.9Ca0.1Ru2O7、Y1.85Ca0.15Ru2O7、Y1.8Ca0.2Ru2O7、Y1.75Ca0.25Ru2O7、Y1.7Ca0.3Ru2O7、Y1.65Ca0.35Ru2O7、Y1.6Ca0.4Ru2O7、Y1.55Ca0.45Ru2O7、Y1.5Ca0.5Ru2O7、Y1.45Ca0.55Ru2O7、Y1.4Ca0.6Ru2O7、Y1.35Ca0.65Ru2O7、Y1.3Ca0.7Ru2O7、Y1.25Ca0.75Ru2O7、Y1.2Ca0.8Ru2O7、Y1.15Ca0.85Ru2O7、Y1.1Ca0.9Ru2O7、Y1.05Ca0.95Ru2O7And the like, or a mixture of several of them.
The oxygen reaction electrode comprises a carrier and calcium-doped yttrium ruthenate attached to the surface of the carrier. Specifically, the support may be a carbon support such as graphite, acetylene black, glassy carbon, or the like. The calcium-doped yttrium ruthenate can be attached to the surface of the carrier by means of a binder or the like. The binder used may be a binder conventionally used for oxygen-reactive electrodes, and may be, for example, teflon, perfluorosulfonic acid (Nafion), or the like. The oxygen reaction electrode can be used for Oxygen Evolution Reaction (OER) and Oxygen Reduction Reaction (ORR). Because the calcium is doped, on one hand, the content of noble metal is reduced, the cost of the oxygen reaction electrode is reduced, and on the other hand, the electrochemical catalytic activity is excellent, and the catalytic stability in an acidic environment and an alkaline environment is good.
The electrochemical device comprising the oxygen-reactive electrode described above may be a proton exchange membrane electrolytic cell (PEM electrolytic cell) or a zinc-air cell.
The PEM electrolytic cell comprises an anode and a cathode which are oppositely arranged, a proton exchange membrane, a collector plate, a field flow plate and other supporting components. The anode in the PEM electrolytic cell is the oxygen reaction electrode provided by the invention, the oxygen reaction electrode plays a role in acidic oxygen evolution in the PEM electrolytic cell reaction, has the characteristics of stable performance, high oxygen evolution rate and the like in the reaction environment of the PEM electrolytic cell, and can also reduce the economic cost of the PEM electrolytic cell.
The zinc-air battery comprises a zinc electrode and an air electrode which are oppositely arranged, the air electrode is the oxygen reaction electrode provided by the invention, the alkaline oxygen evolution and oxygen reduction reaction effects are realized in the zinc-air battery reaction, the electrochemical activity is good, and meanwhile, the cost of the zinc-air battery can be reduced due to the fact that the zinc-air battery contains less noble metals.
In order to more effectively explain the technical solution of the present invention, a plurality of specific examples are described below.
Example 1
A calcium-doped yttrium ruthenate and a preparation method thereof. The calcium-doped yttrium ruthenate has the molecular formula of Y1.75Ca0.25Ru2O7(YCRO-0.25 for short) has pyrochlore structure, and the particle diameter of 90% or more is 200-800 nm.
The preparation method of the calcium-doped yttrium ruthenate comprises the following steps:
s11, mixing Y (NO)3)3·6H2Dissolving O in 50mL of deionized water to obtain a first solution, wherein the concentration of yttrium ions is 0.04375mol L-1(ii) a Mixing Ca (NO)3)2Dissolving in the first solution to obtain a second solution with calcium ion concentration of 0.00625mol L-1(ii) a Adding RuCl3Adding into the second solution to make the concentration of ruthenium ion be 0.05mol L-1Stirring for 10 minutes to obtain a mixed solution;
s12, dissolving citric acid in the mixed solution obtained in the step S11, wherein the concentration of the citric acid is 0.20mol L-1Stirring for 30 minutes to allow ligand reaction to occur, and adding ammonia water to adjust the pH to 8.5 to obtain a complex.
S13, placing the coordination compound obtained in the step S12 in a water bath at 80 ℃, heating, evaporating the solvent to dryness, and placing the obtained product in a vacuum drying oven, and drying for 10 hours at 120 ℃.
S14, grinding the dry powder obtained in the step S13 for 20 minutes, putting the powder into a crucible, calcining the powder in air at the temperature of 600 ℃ for 6 hours, then continuously heating the powder to 1050 ℃, keeping the temperature for 12 hours, and then naturally cooling the powder to obtain the calcium-doped yttrium ruthenate.
Example 2
A calcium-doped yttrium ruthenate and a preparation method thereof. The calcium-doped yttrium ruthenate has the molecular formula of Y1.6Ca0.4Ru2O7(YCRO-0.4 for short) has pyrochlore structure, and the particle diameter of 90% or more is 200-800 nm.
The preparation method of the calcium-doped yttrium ruthenate comprises the following steps:
s21, mixing Y (NO)3)3·6H2Dissolving O in 50mL of deionized water to obtain a first solution, wherein the concentration of yttrium ions is 0.04mol L-1(ii) a Mixing Ca (NO)3)2Dissolving in the first solution to obtain a second solution with calcium ion concentration of 0.01mol L-1(ii) a Adding RuCl3Adding into the second solution to make the concentration of ruthenium ion be 0.05mol L-1Stirring for 10 minutes to obtain a mixed solution;
s22, dissolving citric acid in the mixed solution obtained in the step S21, wherein the concentration of the citric acid is 0.20mol L-1Stirring for 30 minutes to allow ligand reaction to occur, and adding ammonia water to adjust the pH to 9.0 to obtain a complex.
S23, placing the coordination compound obtained in the step S22 in a water bath at 80 ℃, heating, evaporating the solvent to dryness, and placing the obtained product in a vacuum drying oven, and drying for 10 hours at 120 ℃.
S24, grinding the dry powder obtained in the step S23 for 20 minutes, putting the powder into a crucible, calcining the powder in air at the temperature of 600 ℃ for 6 hours, then continuously heating the powder to 1050 ℃, keeping the temperature for 12 hours, and then naturally cooling the powder to obtain the calcium-doped yttrium ruthenate.
Example 3
A calcium-doped yttrium ruthenate and a preparation method thereof. The calcium-doped yttrium ruthenate has the molecular formula of Y1.85Ca0.15Ru2O7(YCRO-0.15 for short) has pyrochlore structure, and the particle diameter of 90% or more is 200-800 nm.
The preparation method of the calcium-doped yttrium ruthenate comprises the following steps:
s31, mixing Y (NO)3)3·6H2Dissolving O in 50mL of deionized water to obtain a first solution, wherein the concentration of yttrium ions is 0.04625mol L-1(ii) a Mixing Ca (NO)3)2Dissolving in the first solution to obtain a second solution with calcium ion concentration of 0.00375mol L-1(ii) a Adding RuCl3Adding into the second solution to make the concentration of ruthenium ion be 0.05mol L-1Stirring for 10 minutes to obtain a mixed solution;
s32, dissolving citric acid in the mixed solution obtained in S31, wherein the concentration of the citric acid is 0.20mol L-1And stirred for 10 minutes to allow ligand reaction to occur, and ammonia water was added to adjust the pH to 8.8, to obtain a complex.
S33, placing the coordination compound obtained in the step S32 in a water bath at 80 ℃, heating, evaporating the solvent to dryness, and placing the obtained product in a vacuum drying oven, and drying for 10 hours at 120 ℃.
S34, grinding the dry powder obtained in the step S33 for 20 minutes, putting the powder into a crucible, calcining the powder in air at the temperature of 600 ℃ for 6 hours, then continuously heating the powder to 1050 ℃, keeping the temperature for 12 hours, and then naturally cooling the powder to obtain the calcium-doped yttrium ruthenate.
Comparative example 1
An oxygen evolution reaction catalyst and a preparation method thereof. The molecular formula of the oxygen evolution reaction catalyst is Y2Ru2O7(YRO for short) has pyrochlore structure, and 90% or more of the particles have a diameter of 200 to 800 nm.
The YRO is prepared by the following steps:
D11. mixing Y (NO)3)3·6H2Dissolving O in deionized water to obtain a first solution with yttrium ion concentration of 0.005mol L-1；
D12. Adding RuCl3Adding into the first solution obtained from D11, and stirring for 10min to obtain a second solution with ruthenium ion concentration of 0.005mol L-1；
D13. Dissolving citric acid in a second solution of D12, wherein the concentration of citric acid is 0.022mol L-1Stirring for 30 minutes;
D14. heating the solvent D13 in 80 ℃ water bath, evaporating the solvent to dryness, putting the obtained product into a vacuum drying oven, and drying for 10h at 120 ℃;
D15. the dried powder obtained from D14 was ground for 20 minutes, placed in a crucible and calcined in air for 12 hours at 1000 ℃.
Comparative example 2
Commercialized IrO2A catalyst.
Comparative example 3
A commercial Pt/C catalyst.
To better illustrate the properties of the resulting materials, the materials of examples 1-3 and comparative examples 1-3 were subjected to the corresponding performance tests:
(1) characterization of XRD
The X-ray powder diffraction results of the materials prepared in examples 1 to 3 and comparative example 1 are shown in FIG. 1.
As can be seen from fig. 1, the catalyst (YCRO) in which Y is partially replaced by Ca and the catalyst YRO in which Y is not doped have similar characteristic peaks, but there is a shift of the characteristic peaks, which is caused by the partial replacement of Y by Ca.
(2) Three electrode test in acidic solution
Taking 6mg of the materials obtained in the embodiments 1-3 respectively, taking 1mg of acetylene black as a carrier, dissolving the materials in the embodiments 1-3 in 0.7mL of isopropanol, dissolving the acetylene black in 0.3mL of deionized water, carrying out ultrasonic treatment for 10min respectively, taking 30 mu L of 5 wt% Nafion solution by using a liquid transfer gun, continuing to disperse for 1h in an ice bath, taking 10 mu L of the Nafion solution, coating the Nafion a glassy carbon electrode with the diameter of 5mm, and naturally airing. The electrode YCRO-0.25 of example 1, the electrode YCRO-0.4 of example 2, and the electrode YCRO-0.15 of example 3 were prepared.
Electrode YRO of comparative example 1 and electrode IrO of comparative example 2 were prepared in the same manner2And Pt/C electrode of comparative example 3.
The electrodes of examples 1 to 3 and comparative examples 1 to 2 were used as working electrodes, a standard hydrogen electrode as a reference electrode, and a platinum mesh as a counter electrode, respectivelyElectrodes, constituting a three-electrode electrochemical system, at 0.5M H2SO4And (5) carrying out electrochemical performance test under the conditions of solution and nitrogen introduction. Wherein the voltage scanning interval of the polarization curve is (1.1-1.7) V, the scanning rate is 10mV/s, the rotating speed is 1600 revolutions, and the working electrode is at 10mA/cm2The current density of (2) was continuously operated in a three-electrode cell, and the voltage was recorded as a function of time, as shown in FIG. 2.
As can be seen from FIG. 2, the electrode current densities of examples 1-3 are due to the electrode current densities of comparative examples 1-2 at the same applied potential; and the current density of the electrode of example 2(YCRO-0.25) was significantly better than that of the electrode of example 2 (YCRO-0.4) and that of the electrode of example 3 (YCRO-0.15), indicating that partial substitution of Y with Ca did improve the acidic oxygen evolution reaction performance.
And 10mA cm was applied to each of the electrodes of example 2 and comparative example 1-2The test voltage versus time.
As can be seen from FIG. 3, the electrode made of the material of example 2 did not significantly change in voltage over 8h of constant current electrolysis, while the electrode of comparative example 1(YRO) had significantly deteriorated performance by 6h of electrolysis, indicating that the Ca-doped Y proposed by the present invention was doped with Ca2Ru2O7The catalyst can improve the intrinsic stability in the acidic oxygen evolution reaction. Therefore, the oxygen evolution reaction catalyst provided by the embodiment of the invention has the advantages of high catalytic activity, good stability, high purity and good repeatability of the preparation method.
(3) Testing of proton exchange membrane electrolytic cells
According to the test result at the point (2), the material of the example 2(YCRO-0.25) and the catalyst of the comparative example 2 are selected to be subjected to the performance characterization test of the proton exchange membrane electrolytic cell, the material obtained in the example 2 is coated on the proton exchange membrane to be used as the anode of the electrolytic cell, and the loading amount of YCRO-0.25 is 4mg/cm2The other side of the proton exchange membrane is sprayed with Pt/C as the cathode of the electrolytic cell, and the Pt loading capacity is 1.5mg/cm2. Meanwhile, IrO commercialized as comparative example 22The catalyst is anode, Pt/C is cathode, which are respectively sprayed on the proton exchange membrane, IrO2The loading amount of (A) is 4mg/cm2Pt loading of 1.5mg/cm2。
And respectively assembling the components into PEM electrolytic cells, and performing performance test, wherein the test temperature is 60 ℃, the loading electrolysis voltage interval is (0.8-1.8) V, the scanning rate is 20mV/s, and the result is shown in figure 4.
As can be seen from FIG. 4, the performance of the proton exchange membrane electrolyzer using the material obtained in example 2 as the anode significantly exceeds that of IrO2A commercial catalyst.
(4) Three-electrode test in alkaline solution
The electrodes prepared in the example 1-3 and the electrodes provided in the comparative examples 1-2 in the point (2) were subjected to an alkaline oxygen evolution reaction performance test, and the concentration of the potassium hydroxide solution was 0.1mol/L, the voltage scan interval of the polarization curve was (1.1-1.7) V, the scan rate was 10mV/s, and the rotation speed was 1600 revolutions. In the performance test of the alkaline oxygen reduction reaction, high-purity oxygen (99.999%) is firstly introduced for half an hour to ensure that the solution is saturated with oxygen, oxygen is continuously introduced in the test process, the rotating speed of the rotating disc electrode is 1600, the voltage scanning interval is (1.1-0.1) V (relative to the potential of a standard hydrogen electrode), the voltage scanning rate is 20mV/s, and the test result is shown in figure 5.
As can be seen from FIG. 5, the oxygen reduction reaction performance of examples 1 to 3 is significantly better than that of comparative examples 2 to 3, and the oxygen reduction performance of the material prepared in example 1(YCRO-0.25) is significantly better than that of example 1(YRO catalyst without Ca doping). Description of the Ca-doped Y proposed by the present invention2Ru2O7The catalyst can improve the oxygen reduction performance in alkaline solution.
According to the test results of FIG. 5, the oxygen evolution reaction test was performed on examples 1 to 3 and comparative example 1 under the specific conditions of 0.1mol/L potassium hydroxide solution, and the results are shown in FIG. 6.
As can be seen from FIG. 6, the oxygen evolution activities of examples 1 to 3 significantly exceeded the oxygen evolution activity of comparative example 1(YRO), and the oxygen evolution activity of example 1 was optimized.
(5) Testing of zinc-air cells
The material prepared in example 1(YCRO-0.25) was sprayed on carbon paper with a loading of 4.5mg/cm2Foamed nickel as a collectionAnd fluid is tightly attached to carbon paper coated with YCRO-0.25, the whole body is used as an air electrode of a zinc-air battery, the zinc electrode is a zinc sheet, the thickness of the zinc sheet is 0.2mm, the electrolyte solution is 6mol/L potassium hydroxide and 0.2mol/L zinc acetate, the zinc-air battery is assembled according to the sequence of the zinc-air battery, a discharge curve test is carried out on the zinc-air battery, the voltage scanning interval is (1.6-0.6) V, and the voltage scanning speed is 1 mV/s. Then, a charging curve test was performed, the voltage sweep interval was (1.4-2.5) V, and the voltage sweep rate was 5mV/s, the results are shown in FIG. 7.
Further testing the stability and durability of the zinc-air battery, wherein the current density of charging and discharging is 5mA/cm2The charging and discharging time in one cycle was 10 minutes, and the results are shown in FIG. 8.
As comparative examples, commercial Pt/C and IrO were used2(mass ratio is 1:1) is an air electrode, and the loading capacity is 4.5mg/cm2And assembling the zinc-air battery device into a zinc-air battery device and testing the performance of the zinc-air battery device.
As can be seen from FIG. 7, the discharge capacity and Pt/C-IrO of the zinc-air battery assembled from the electrode of example 1(YCRO-0.25)2Similarly, the charging performance of the zinc-air battery assembled by the electrode of example 1(YCRO-0.25) significantly surpassed that of Pt/C-IrO2。
As can be seen from FIG. 8, the zinc air battery assembled with the electrode of example 1(YCRO-0.25) did not undergo significant deterioration even after more than 320 charge-discharge cycles (6400min), while the comparative example Pt/C-IrO2The catalyst started to fade after 50 charge cycles (1000min), thus demonstrating the Ca doping Y proposed by the present invention2Ru2O7The catalyst has excellent stability when being applied to the zinc-air battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A calcium-doped yttrium ruthenate having the formula:
Y2-xCaxRu2O7wherein, 0<x<1。
2. The calcium-doped yttrium ruthenate according to claim 1, wherein the particle size of said calcium-doped yttrium ruthenate is (100 to 2000) nm.
3. The calcium-doped yttrium ruthenate according to claim 1, wherein in the formula 0.15. ltoreq. x.ltoreq.0.4.
4. The calcium-doped yttrium ruthenate according to claim 1, wherein said calcium-doped yttrium ruthenate is Y1.85Ca0.15Ru2O7、Y1.75Ca0.25Ru2O7、Y1.6Ca0.4Ru2O7At least one of (1).
5. A preparation method of calcium-doped yttrium ruthenate is characterized by comprising the following steps:
providing a mixed solution containing yttrium ions, calcium ions and ruthenium ions;
adding a metal ion ligand into the mixed solution to perform ligand reaction to obtain a coordination compound containing yttrium ions, calcium ions and ruthenium ions;
removing the solvent in the coordination compound to obtain a precursor of calcium-doped yttrium ruthenate;
crushing the precursor, and calcining in an oxygen-containing atmosphere to obtain calcium-doped yttrium ruthenate; the calcium-doped yttrium ruthenate has the following molecular formula: y is2-xCaxRu2O7Wherein, 0<x<1；
The molar ratio of yttrium ions, calcium ions and ruthenium ions in the mixed solution to the Y2-xCaxRu2O7The molar ratio of the element Y, Ca to Ru is the same.
6. The method of preparing calcium-doped yttrium ruthenate according to claim 5, wherein the mixed solution has a concentration of yttrium ions of (0.001-0.1) mol/L, a concentration of ruthenium ions of (0.001-0.1) mol/L and a concentration of calcium ions of (0.001-0.1) mol/L.
7. The method of preparing calcium-doped yttrium ruthenate according to claim 5, wherein said metal ion ligand is at least one of citric acid, citric acid monohydrate, ethylenediaminetetraacetic acid;
the molar ratio of the metal ion ligand to the total amount of the yttrium ions, the ruthenium ions and the calcium ions in the mixed solution is (1-10) to 1;
and/or the temperature of the calcination treatment is (600-1200) DEG C.
8. An oxygen-reactive electrode comprising the calcium-doped yttrium ruthenate according to any one of claims 1 to 4; or the calcium-doped yttrium ruthenate contained in the oxygen reaction electrode is prepared by the method for preparing calcium-doped yttrium ruthenate according to any one of claims 5 to 7.
9. A proton exchange membrane electrolytic cell comprising an anode, wherein the anode is the oxygen reactive electrode of claim 8.
10. A zinc-air battery comprising an air electrode, wherein the air electrode is the oxygen reaction electrode of claim 8.
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