Multi-element metal oxide catalyst for wide-temperature-range zinc-air battery and application of multi-element metal oxide catalyst

Abstract

The invention provides a multi-element metal oxide catalyst for a wide-temperature-range zinc air battery and application of the multi-element metal oxide catalyst. The multi-element metal oxide catalyst comprises an ABCD multi-element metal oxide, A is one of Al, Ga, Ge, In, Sn, Sb, Ti, Pb, Bi, Nb, Mo and Cd, B and C are respectively one of V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Zr and Y, and D is one of Pt, Ir, Ru, Pd, Au and Ag. The OER and ORR performances of the catalyst can be improved; the catalyst has ultra-long service life; the catalyst is applied to an air positive electrode of a zinc-air battery, and the battery not only has high specific capacity and high power density in a wide temperature range, but also has excellent cycle stability.

Description

Technical Field

[0001] The present invention relates to the field of battery technology, and more specifically, to a multi-metal oxide catalyst for a wide temperature range zinc-air battery and an application thereof, and more specifically, to a multi-metal oxide catalyst for a wide temperature range zinc-air battery and a preparation method thereof and a zinc-air battery. Background Art

[0002] Large-scale energy storage technology is a key core technology for building a new power system with new energy as the main body and achieving the goal of "carbon peak and carbon neutrality". Rechargeable zinc-air batteries (RZABs) have high energy density (1086Wh kg -1 ), low material cost, green and pollution-free, high safety, easy storage and operation, etc., showing great application prospects in the field of large-scale energy storage of renewable energy. However, the slow OER (oxygen evolution) and ORR (oxygen reduction) processes on the air electrode during charging and discharging seriously limit the energy efficiency of RZABs and reduce the cycle life of the battery.

[0003] At present, a series of bifunctional oxygen catalysts have been developed, including single-atom catalysts and multiphase coupled catalysis based on metal oxides / sulfides / phosphides / hydroxides, etc. However, there are few reports on bifunctional oxygen catalysts for alkaline aqueous RZABs with wide temperature range. Working at both low and high temperatures has high requirements for catalysts, especially at low temperatures, the slower electrochemical kinetics are not conducive to the reaction of oxygen-containing species on the active sites. Therefore, the catalysts for alkaline aqueous RZABs with wide temperature range need to be further studied. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems in the related art to a certain extent. To this end, one object of the present invention is to provide a multi-metal oxide catalyst for a wide temperature range zinc-air battery, the multi-metal oxide catalyst having very excellent electrocatalytic oxygen reduction (ORR) and oxygen evolution (OER) performance, and the zinc-air battery using the multi-metal oxide catalyst as the positive electrode exhibits good performance in a wide temperature range.

[0005] In the aspect of the present invention, the present invention provides a multi-metal oxide catalyst for a wide temperature range zinc-air battery. According to an embodiment of the present invention, the multi-metal oxide catalyst includes an ABCD multi-metal oxide, wherein A is one of Al, Ga, Ge, In, Sn, Sb, Ti, Pb, Bi, Nb, Mo and Cd, B and C are one of V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Zr and Y, respectively, and D is one of Pt, Ir, Ru, Pd, Au and Ag. Thus, in the multi-metal oxide catalyst, by changing the content of different metals in the ABCD multi-metal oxide, the regulation of the electronic structure of the catalyst can be achieved, so that the adsorption energy of oxygen-containing intermediate species (OOH*, O* and OH*) on the OER and ORR sites is optimized, and the OER and ORR performance of the multi-metal oxide catalyst is improved, and the obtained catalyst has an ultra-long life; moreover, the multi-metal oxide catalyst is applied to the air positive electrode of the zinc-air battery, and the assembled zinc-air battery has not only high specific capacity and large power density in a wide temperature range, but also excellent cycle stability performance.

[0006] According to an embodiment of the present invention, in the ABCD multi-metal oxide, the atomic percentage content of A is 0.001-99.9at%, the atomic percentage content of B is 0.001-99.9at%, the atomic percentage content of C is 0.01-99.9at%, and the atomic percentage content of D is 0.01-99.9at%.

[0007] According to an embodiment of the present invention, in the ABCD multi-metal oxide, the atomic percentage content of A is 1-10 at %, the sum of the atomic percentage contents of B and C is 10-25 at %, and the atomic percentage content of D is 50-70 at %.

[0008] According to an embodiment of the present invention, the multi-metal oxide catalyst has a porous structure.

[0009] In another aspect of the present invention, the present invention provides a method for preparing the multi-metal oxide catalyst described above. According to an embodiment of the present invention, the method for preparing the multi-metal oxide catalyst comprises: adding a carbon source and a decomposing agent to a metal precursor salt solution, and stirring evenly to obtain a mixed solution; freeze-drying the mixed solution to obtain a frozen intermediate product; calcining the frozen intermediate product to obtain the multi-metal oxide catalyst, wherein the decomposing agent decomposes and produces gas during the calcination process. Thus, the multi-metal oxide catalyst can be prepared by the above method, and the preparation method is simple, low-cost, environmentally friendly and easy to scale production; by changing the content of different metals in the ABCD multi-metal oxide, the electronic structure of the multi-metal oxide catalyst can be regulated, so that it optimizes the adsorption energy of oxygen-containing intermediate species (OOH*, O* and OH*) on the OER and ORR sites, and improves the OER and ORR performance of the multi-metal oxide catalyst, and the obtained catalyst has an ultra-long life; and the multi-metal oxide catalyst is applied to the air positive electrode of the zinc-air battery, and the assembled zinc-air battery has not only high specific capacity and large power density in a wide temperature range, but also excellent cycle stability.

[0010] According to an embodiment of the present invention, the concentration of the metal precursor salt in the metal precursor salt solution is 0.001-100 mg / mL.

[0011] According to an embodiment of the present invention, the mass ratio of the carbon source to the decomposing agent is 1:100-1:1.

[0012] According to an embodiment of the present invention, the carbon source includes at least one of galactose, sucrose, fructose, glucose and maltose, and the decomposing agent includes at least one of thiourea, ammonium chloride, urea and ammonium sulfate.

[0013] According to an embodiment of the present invention, the temperature of the freeze-drying treatment is -50-0°C, and the time is 0.1-200h; and / or the temperature of the calcination treatment is 200-1500°C, and the time is 0.1-1800h.

[0014] In another aspect of the present invention, the present invention provides a zinc-air battery. According to an embodiment of the present invention, the zinc-air battery comprises the multi-metal oxide catalyst described above. Thus, the zinc-air battery has high specific capacity, high power density, and excellent cycle stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0016] Figure 1 is a scanning electron microscope image of the multi-metal oxide catalyst in Example 9 of the present invention;

[0017] Figure 2 is a curve chart of the stability test of the multi-metal oxide catalyst in Example 9 of the present invention;

[0018] Figure 3 a in the figure is a schematic diagram of a zinc-air battery module in Example 9 of the present invention;

[0019] Figure 3 b is an open circuit voltage curve of the zinc-air battery in Example 9 of the present invention;

[0020] Figure 3 c is a power density curve of the zinc-air battery in Example 9 of the present invention;

[0021] Figure 3 d in is the specific capacity curve of the zinc-air battery in Example 9 of the present invention;

[0022] Figure 4 This is a test chart of the constant current charge and discharge stability of the zinc-air battery in Example 9 of the present invention under a wide temperature range (room temperature, low temperature and high temperature). DETAILED DESCRIPTION

[0023] The scheme of the present invention will be explained below in conjunction with the embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Where specific techniques or conditions are not indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used are not indicated by the manufacturer and are all conventional products that can be obtained commercially.

[0024] The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0025] In an aspect of the present invention, the present invention provides a multi-metal oxide catalyst for a wide-temperature-range zinc-air battery. According to an embodiment of the present invention, the multi-metal oxide catalyst comprises an ABCD multi-metal oxide, wherein A is one of Al, Ga, Ge, In, Sn, Sb, Ti, Pb, Bi, Nb, Mo, and Cd, B and C are each one of V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Zr, and Y, and D is one of Pt, Ir, Ru, Pd, Au, and Ag, where 0≤x<1, 0≤y<1, 0<z<1, and 0<x + y + z<1, and x and y are not both 0 at the same time. Thus, in this multi-metal oxide catalyst, by changing the contents of different metals in the ABCD multi-metal oxide, the electronic structure of the catalyst can be regulated to optimize the adsorption energies of oxygen-containing intermediate species (OOH*, O*, and OH*) on the OER and ORR sites, improving the OER and ORR performances of the multi-metal oxide catalyst, and at the same time, the obtained catalyst has an extremely long lifespan; moreover, when this multi-metal oxide catalyst is applied to the air cathode of a zinc-air battery, the assembled zinc-air battery not only has a high specific capacity and a large power density in a wide temperature range, but also has excellent cycle stability performance.

[0026] In a zinc-air battery, the oxygen reduction (ORR) reaction is that in an alkaline environment, oxygen undergoes a 4-electron reaction to generate OH - , and the ORR active sites of the multi-metal oxide catalyst of the present invention are conducive to O 2 to obtain electrons and be reduced to OH−, reducing the reaction energy barrier. The oxygen evolution (OER) reaction is theoretically the opposite reaction of ORR. In an alkaline environment, OH in the solution - , loses electrons and becomes oxygen, and the OER active sites in the multi-metal oxide catalyst of the present invention are conducive to the progress of this reaction. That is to say, the multi-metal oxide catalyst of the present invention has excellent OER and ORR performances, which is conducive to improving the reaction activities of the zinc-air battery at low and high temperatures in a wide temperature range.

[0027] In some embodiments, the temperature range of the wide temperature range can be -20 - 60 degrees Celsius.

[0028] It should be noted that ABCD is not the chemical formula of the multi-metal oxide, but only represents the metal elements contained in the multi-metal oxide, that is, it means that the multi-metal oxide contains four metal elements A, B, C, and D, and all four metal elements exist in the form of metal oxides. In some embodiments of the present invention, in the ABCD multi-metal oxide, the metal element B and the metal element C can be the same metal element or two different metal elements. Therefore, the ABCD multi-metal oxide of the present invention is a ternary metal oxide or a quaternary metal oxide.

[0029] According to some embodiments of the present invention, in the ABCD multi-metal oxide, the sum of the atomic percentage contents of A, B, C, D and oxygen atoms is 100at%, wherein the atomic percentage content of A is 0.001-99.9at% (for example, 0.001at%, 0.01at%, 0.1at%, 1at%, 10at%, 20at%, 30at%, 40at%, 50at%, 60at%, 70at%, 80at%, 90at%, 95at%, 99.9at%, etc.), and the atomic percentage content of B is 0.001-99.9at% (for example, 0.001at%, 0.01at%, 0.1at%, 1at%, 10at%, 20at%, 30at%, 40at%, 50at%, 60at%, 70at%, 80at%, 90at%, 95at%, 99.9at%, etc.). 0at%, 70at%, 80at%, 90at%, 95at%, 99.9at%, etc.), the atomic percentage content of C is 0.01-99.9at% (for example, 0.01at%, 0.1at%, 1at%, 10at%, 20at%, 30at%, 40at%, 50at%, 60at%, 70at%, 80at%, 90at%, 95at%, 99.9at%, etc.), and the atomic percentage content of D is 0.01-99.9at% (for example, 0.01at%, 0.1at%, 1at%, 10at%, 20at%, 30at%, 40at%, 50at%, 60at%, 70at%, 80at%, 90at%, 95at%, 99.9at%, etc.).

[0030] In some specific embodiments, in the ABCD multi-metal oxide, the atomic percentage content of A is 1-10 at %, the sum of the atomic percentage contents of B and C is 10-25 at %, and the atomic percentage content of D is 50-70 at %.

[0031] According to an embodiment of the present invention, the multi-metal oxide catalyst is a porous structure. As such, the porous structure has a relatively large specific surface area, which can help to further improve the catalytic efficiency.

[0032] In some embodiments, the multi-metal oxide catalyst is in a foamy form and is formed by accumulation of nano-sized metal oxide particles.

[0033] In another aspect of the present invention, the present invention provides a method for preparing the multi-metal oxide catalyst described above. According to an embodiment of the present invention, the method for preparing the multi-metal oxide catalyst comprises:

[0034] S100: adding a carbon source and a decomposing agent into a metal precursor salt solution and stirring the mixture evenly to obtain a mixed solution.

[0035] According to some embodiments of the present invention, the carbon source includes at least one of galactose, sucrose, fructose, glucose and maltose. Thus, the carbon source is carbonized in the subsequent calcination process, which is conducive to the uniform dispersion of metal ions, and has a wide source, is easy to purchase, and has a low cost.

[0036] According to some embodiments of the present invention, the decomposition agent includes at least one of thiourea, ammonium chloride, urea, ammonium bicarbonate and ammonium sulfate. Thus, the above decomposition agent decomposes and generates gas during the heating process (such as the subsequent calcination process), which is conducive to forming a loose and porous multi-metal oxide catalyst structure. In some embodiments, a porous foam catalyst can be formed, and the foam multi-metal oxide catalyst is formed by the accumulation of nano-scale metal oxide particles.

[0037] According to some embodiments of the present invention, there is no special requirement for the specific type of the metal precursor salt in the above-mentioned metal precursor salt solution. Those skilled in the art can flexibly select its soluble salt according to the specific type of metal selected, for example, metal halide salt, metal ammonium salt, etc.

[0038] According to some embodiments of the present invention, the mass ratio of the carbon source to the decomposer is 1:100-1:1, such as 1:100, 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:5, 1:1, etc. The above mass ratio is conducive to the formation of a good multi-metal oxide catalyst with stable structure; if the proportion of the carbon source is large, that is, the proportion of the decomposer is relatively small, the amount of gas generated by its decomposition is insufficient, that is, it is relatively unfavorable for the formation of a porous structure of the multi-metal oxide catalyst; if the proportion of the carbon source is relatively small, that is, the proportion of the decomposer is relatively large, then the gas generated is excessive, so that the porous structure size of the multi-metal oxide catalyst is relatively large, which still leads to a relative decrease in the specific surface area of ​​the multi-metal oxide catalyst, which is not conducive to the improvement of the catalytic effect, and may also lead to insufficient structural stability of the multi-metal oxide catalyst.

[0039] According to some embodiments of the present invention, the concentration of the metal precursor salt in the metal precursor salt solution is 0.001-100 mg / mL, such as 0.001 mg / mL, 0.01 mg / mL, 0.1 mg / mL, 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL, 100 mg / mL, etc. The above concentration refers to the total concentration of multiple metal precursor salts.

[0040] In some embodiments of the present invention, the specific method of the above stirring may include but is not limited to magnetic stirring, mechanical stirring, ultrasonic stirring and the like.

[0041] S200: freeze-drying the mixed solution to obtain a frozen intermediate product, namely a freeze-dried mixed metal precursor salt.

[0042] According to some embodiments of the present invention, the freeze drying process can be carried out in a freeze dryer. In some embodiments, the temperature of the freeze drying process is -50-0°C, such as -50°C, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, etc., and the time is 0.1-200h, such as 0.1h, 1h, 10h, 20h, 50h, 75h, 100h, 120h, 150h, 170h, 200h, etc. Under the above conditions, the mixed solution can be frozen quickly and effectively.

[0043] In some embodiments, the frozen intermediate product may be a brown material.

[0044] S300: calcining the frozen intermediate product to obtain a multi-metal oxide catalyst. In this process, the decomposition agent decomposes to generate gas, the carbon source is carbonized, the metal precursor salt begins to decompose to generate metal oxides, and a multi-metal oxide catalyst with a porous structure is formed under the action of the gas.

[0045] According to some embodiments of the present invention, the temperature of the calcination treatment is 200-1500°C, such as 200°C, 500°C, 700°C, 900°C, 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, etc., and the time is 0.1-1800h, such as 0.1h, 1h, 10h, 20h, 50h, 75h, 100h, 120h, 150h, 170h, 200h, 500h, 800h, 1000h, 1200h, 1500h, 1800h, etc.

[0046] According to some embodiments of the present invention, the calcination process may be performed in an oxygen-containing atmosphere, for example, in an air or oxygen atmosphere, in which the carbon source and the metal salt decompose to generate gas and generate metal oxides.

[0047] According to the embodiments of the invention, a multinary metal oxide catalyst can be prepared by the above method, and the preparation method is simple, low-cost, environmentally friendly and easy to mass-produce; the electronic structure of the multinary metal oxide catalyst can be regulated by changing the content of different metals in the ABCD multinary metal oxide, so that the adsorption energy of oxygen-containing intermediate species (OOH*, O* and OH*) at the OER and ORR sites is optimized, and the OER and ORR performance of the multinary metal oxide catalyst is improved, and the obtained catalyst has an ultra-long life; moreover, the multinary metal oxide catalyst is applied to the air positive electrode of a zinc-air battery, and the assembled zinc-air battery has not only a high specific capacity and a large power density in a wide temperature range, but also excellent cycle stability performance.

[0048] In another aspect of the present invention, the present invention provides a zinc-air battery. According to an embodiment of the present invention, the zinc-air battery comprises the above-mentioned multi-metal oxide catalyst. Thus, the zinc-air battery has high specific capacity, high power density, and excellent cycle stability.

[0049] In an embodiment of the present invention, the zinc air electrode comprises a zinc electrode, a diaphragm, an air electrode and an electrolyte, wherein the air electrode comprises a current collector, a multi-metal oxide catalyst and a hydrophobic gas collecting layer stacked in sequence, and when the battery is discharged, the air electrode serves as the positive electrode of the battery.

[0050] Example

[0051] Example 1

[0052] The method for preparing a multi-metal oxide catalyst comprises:

[0053] (1) Weigh a certain amount of (NH 4 ) 6 Mo 7 O 24 ·4H 2 O、SnCl 2 、IrCl 3 and MnCl 3 Dissolve in deionized water to make the total concentration of metal precursor salt 10 mg / mL;

[0054] (2) Then, ammonium bicarbonate and sucrose (mass ratio of 1:6, unit: mg) were added, and a clear mixed solution was obtained by continuous stirring.

[0055] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -50°C for 48 hours to obtain a brown substance loaded with a metal salt.

[0056] (4) Finally, the obtained brown substance is placed in a muffle furnace and calcined at 600°C for 18 hours in an air atmosphere to obtain a SnMoMnIr quaternary metal oxide catalyst (wherein the atomic percentage contents of Sn, Mo, Mn and Ir are 1at%, 2at%, 12at% and 60at%, respectively), and the quaternary metal oxide catalyst is attached to the porous carbon skeleton, that is, a multi-metal oxide catalyst is obtained.

[0057] Example 2

[0058] The method for preparing a multi-metal oxide catalyst comprises:

[0059] (1) Weigh a certain amount of BiCl 3 、IrCl 3 and CoCl 2 6H 2 O was dissolved in deionized water to make the total concentration of metal precursor salt 8 mg / mL;

[0060] (2) Urea and galactose (mass ratio of 1:10, unit: mg) were then added, and a clear mixed solution was obtained by continuous stirring.

[0061] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -40°C for 28 hours to obtain a brown substance loaded with a metal salt.

[0062] (4) Finally, the obtained brown substance is placed in a tubular furnace and calcined at 300°C for 12 hours in an oxygen atmosphere to obtain a BiCoIr ternary metal oxide catalyst (wherein the atomic percentage contents of Bi, Co and Ir are 2at%, 15at% and 55at%, respectively), and the ternary metal oxide catalyst is attached to the porous carbon skeleton, that is, a multi-metal oxide catalyst is obtained.

[0063] Example 3

[0064] The method for preparing a multi-metal oxide catalyst comprises:

[0065] (1) Weigh a certain amount of SbCl 5 、IrCl 3 and MnCl 2 Dissolve in deionized water to make the total concentration of metal precursor salt 10 mg / mL;

[0066] (2) Thiourea and glucose (mass ratio of 1:30, unit: mg) were then added, and a clear mixed solution was obtained by continuous stirring.

[0067] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -50°C for 24 hours to obtain a brown substance loaded with a metal salt.

[0068] (4) Finally, the obtained brown substance was placed in a muffle furnace and calcined at 550°C for 14 hours in an air atmosphere to obtain a SbMnIr ternary metal oxide catalyst (wherein the atomic percentage contents of Sn, Mn and Ir are 5at%, 23at% and 54at%, respectively), and the quaternary metal oxide catalyst was attached to the porous carbon skeleton, thus obtaining a multi-metal oxide catalyst.

[0069] Example 4

[0070] The method for preparing a multi-metal oxide catalyst comprises:

[0071] (1) Weigh a certain amount of AlCl 3 、IrCl 3 and CoCl 2 6H 2 O was dissolved in deionized water to make the total concentration of metal precursor salt 10 mg / mL;

[0072] (2) Then, ammonium chloride and sucrose (mass ratio of 1:8, unit: mg) were added, and a clear mixed solution was obtained by continuous stirring.

[0073] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -45°C for 48 hours to obtain a brown substance loaded with a metal salt.

[0074] (4) Finally, the obtained brown substance is placed in a tubular furnace and calcined at 600°C for 18 hours in an oxygen atmosphere to obtain an AlCoIr ternary metal oxide catalyst (wherein the atomic percentage contents of Al, Co and Ir are 3at%, 12at% and 58at%, respectively), and the ternary metal oxide catalyst is attached to the porous carbon skeleton, that is, a multi-metal oxide catalyst is obtained.

[0075] Example 5

[0076] The method for preparing a multi-metal oxide catalyst comprises:

[0077] (1) Weigh a certain amount of CoCl 2 6H 2 O、SbCl 5 , PdCl 2 and (NH 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in deionized water to make the total concentration of metal precursor salt 10 mg / mL;

[0078] (2) Urea and fructose (mass ratio of 1:10, unit: mg) were then added, and a clear mixed solution was obtained by continuous stirring.

[0079] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -50°C for 24 hours to obtain a brown substance loaded with a metal salt.

[0080] (4) Finally, the obtained brown substance is placed in a muffle furnace and calcined at 550°C for 12 hours in an air atmosphere to obtain a SbCoMoPd quaternary metal oxide catalyst (wherein the atomic percentage contents of Sb, Co, Mo and Pd are 1at%, 10at%, 3at% and 62at%, respectively), and the quaternary metal oxide catalyst is attached to the porous carbon skeleton, that is, a multi-metal oxide catalyst is obtained.

[0081] Example 6

[0082] The method for preparing a multi-metal oxide catalyst comprises:

[0083] (1) Weigh a certain amount of CoCl 2 6H 2 O, GaCl 3 , PdCl 2 and FeCl 3 Dissolve in deionized water to make the total concentration of metal precursor salt 5 mg / mL;

[0084] (2) Urea and sucrose (mass ratio of 1:25, unit: mg) were then added, and a clear mixed solution was obtained by continuous stirring.

[0085] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -45°C for 48 hours to obtain a brown substance loaded with a metal salt.

[0086] (4) Finally, the obtained brown substance is placed in a muffle furnace and calcined at 600°C for 10 hours in an air atmosphere to obtain a GaCoFePd quaternary metal oxide catalyst (wherein the atomic percentage contents of Ga, Co, Fe and Pd are 2at%, 15at%, 1at% and 52at%, respectively), and the quaternary metal oxide catalyst is attached to the porous carbon skeleton, that is, a multi-metal oxide catalyst is obtained.

[0087] Example 7

[0088] (1) Weigh a certain amount of FeCl 3 、GaCl 3 , K 2 PtCl 6 and CoCl 2 6H 2O was dissolved in ionized water to make the total concentration of metal precursor salt 8 mg / mL.

[0089] (2) Then, ammonium bicarbonate and fructose (mass ratio of 1:35, unit: mg) were added, and a clear mixed solution was obtained by continuous stirring.

[0090] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -30°C for 50 h to obtain a metal salt-loaded brown substance.

[0091] (4) Finally, the obtained brown substance is placed in a muffle furnace and calcined at 400°C for 24 hours in an air atmosphere to obtain a GaCoFePt quaternary metal oxide catalyst (wherein the atomic percentages of Ga, Co, and Fe mixed into Pt are 1.5 at%, 12 at%, 1 at%, and 56 at%, respectively), and the quaternary metal oxide catalyst is attached to the porous carbon skeleton, thus obtaining a multi-metal oxide catalyst.

[0092] Example 8

[0093] (1) Weigh a certain amount of SnCl 2 、CoCl 2 6H 2 O、PdCl 2 and Cu(NO 3 ) 2 6H 2 O was dissolved in ionized water to make the total concentration of metal precursor salt 8 mg / mL.

[0094] (2) Then, ammonium sulfate and glucose (mass ratio of 1:5, unit: mg) were added, and a clear mixed solution was obtained by continuous stirring.

[0095] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -50°C for 24 h to obtain a metal salt-loaded brown substance.

[0096] (4) Finally, the obtained brown substance is placed in a muffle furnace and calcined at 450°C for 28 hours in an air atmosphere to obtain a SnCoCuPd quaternary metal oxide catalyst (wherein the atomic percentage contents of Sn, Co, Cu and Pd are 2at%, 15at%, 3at% and 53at%, respectively), and the quaternary metal oxide catalyst is attached to the porous carbon skeleton, that is, a multi-metal oxide catalyst is obtained.

[0097] Example 9

[0098] (1) Weigh a certain amount of GaCl 3 、MnSO 4 and RuCl 3Dissolve in ionized water to make the total concentration of metal precursor salt 8 mg / mL.

[0099] (2) Then, ammonium sulfate and glucose (mass ratio of 1:5, unit: mg) were added, and a clear mixed solution was obtained by continuous stirring.

[0100] (3) The beaker containing the mixed solution was then placed in a freeze dryer and dried at -50°C for 24 h to obtain a metal salt-loaded brown substance.

[0101] (4) Finally, the obtained brown substance was placed in a muffle furnace and calcined at 450°C in an air atmosphere for 28 hours and 8 hours to obtain a GaMnRu ternary metal oxide catalyst (wherein the atomic percentages of Ga, Mn and Ru are 2at%, 12at% and 57at%), and the ternary metal oxide catalyst was attached to the porous carbon skeleton, thus obtaining a multi-metal oxide catalyst.

[0102] Morphological characterization of multi-metal oxide catalysts:

[0103] The multi-metal oxide catalyst obtained in Example 9 was subjected to electron microscopy to observe its morphological characteristics. Figure 1 As shown in the SEM image ( Figure 1 In a), the multi-metal oxide catalyst is in the form of porous foam sheets. Figure 1 In b), it can be seen that the foam sheet-like multi-metal oxide catalyst is composed of accumulation of tiny nanoparticles of a few nanometers.

[0104] ORR and OER performance characterization of multi-metal oxide catalysts:

[0105] The multi-metal oxide catalyst obtained in Example 9, ethanol and Nafion solution were prepared into a mixed slurry in a certain ratio (the content of the multi-metal oxide catalyst was 5 mg / ml). The mixed slurry was then coated on a rotating ring disk electrode and a linear sweep voltammetry test was performed in a three-electrode system (where the rotating ring disk electrode was the working electrode, the Ag / AgCl electrode was the reference electrode, and the Pt wire was the counter electrode) to obtain an LSV curve, as shown in FIG. Figure 2 Then, Pt / C and IrO 2 For the combined catalyst, a linear sweep voltammetry test was performed in a three-electrode system according to the above method to obtain an LSV curve, such as Figure 2 As shown in a in .

[0106] From the LSV curve, it can be seen that the ORR and OER performances of the multi-metal oxide catalyst are better than those of commercial Pt / C and IrO 2 The oxygen potential difference is 0.605V, which is much better than commercial Pt / C and IrO2 The combined catalyst showed excellent bifunctionality.

[0107] Stability test:

[0108] The stability of the multi-metal oxide catalyst obtained in Example 9 was subjected to an accelerated test (after a certain number of cycles of the accelerated test, an LSV test was performed). The test results can be found in Figure 2 b and Figure 2 The catalyst also has good ORR stability after 300,000 CV cycles ( Figure 2 b), the half-wave potential changes little. The OER stability of the catalyst is also good. After 30,000 CV cycles, the overpotential remains basically unchanged ( Figure 2 c) in.

[0109] Performance characterization of zinc-air batteries at room temperature and low temperature when multi-metal oxide catalysts are used as air electrode materials:

[0110] The multi-metal oxide catalyst obtained in Example 9, ethanol and Nafion solution were mixed into a slurry in a certain ratio. The slurry was coated on the composite electrode substrate (the multi-metal oxide catalyst content was 1 mg cm -2 ) and assembled into the zinc-air battery module (such as Figure 3 a), test the open circuit voltage of the zinc-air battery (such as Figure 3 b) Power density (such as Figure 3 c) and specific capacity (such as Figure 3 d). For the zinc-air battery containing multi-metal oxide catalysts, its open circuit voltage at room temperature is 1.59 V and its specific capacity is 968.5 mAh g Zn -1 , power density is 200mW cm -2 , both are better than commercial Pt / C+IrO 2 The battery with the catalyst as the air electrode material (open circuit voltage 1.54 V, specific capacity 741.1 mAh g Zn -1 , the power density is 116.3mW cm -2 ). The performance at low temperature (-20℃) is also better than Pt / C+IrO 2 Combined catalysts: The power density of zinc-air batteries containing multi-metal oxide catalysts can reach 87.1 mW cm at low temperature -2 , and its specific capacity is 825.6 mAh g Zn -1 , better than commercial Pt / C+IrO 2The battery with the catalyst as the air electrode material (specific capacity value is 718.1 mAh g Zn -1 , power density is less than 20mW cm -2 ). It can be seen that the multi-metal oxide catalyst of the present invention has better performance as an air electrode at both low temperature and room temperature.

[0111] Constant current charge and discharge stability of zinc-air batteries with multi-metal oxide catalysts as air electrode materials in a wide temperature range (room temperature, low temperature and high temperature):

[0112] from Figure 4 As can be seen in a, when the multi-metal oxide catalyst obtained in Example 9 is used as the air electrode material, there is almost no attenuation after 800h of constant current charge and discharge test at room temperature, while the commercial Pt / C+IrO 2 The combined catalyst had obviously deteriorated after more than 100 hours of operation. Figure 4 It can also be seen from b in 4 and c in 4 that the multi-metal oxidation catalyst has excellent cycle stability at both low and high temperatures, which is much better than the commercial Pt / C+IrO 2 The combined catalyst can run stably for more than 2000 hours at low temperature with almost no attenuation.

[0113] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, unless they are contradictory.

[0114] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A multi-metal oxide catalyst for a wide temperature range zinc-air battery, characterized in that: The multi-metal oxide catalyst includes ABCD multi-metal oxide, wherein A is one of Al, Ga, Ge, In, Sn, Sb, Ti, Pb, Bi, Nb, Mo and Cd, B and C are one of V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Zr and Y respectively, and D is one of Pt, Ir, Ru, Pd, Au and Ag.

2. The multi-metal oxide catalyst according to claim 1, characterized in that In the ABCD multi-metal oxide, the atomic percentage content of A is 0.001-99.9at%, the atomic percentage content of B is 0.001-99.9at%, the atomic percentage content of C is 0.01-99.9at%, and the atomic percentage content of D is 0.01-99.9at%.

3. The multi-metal oxide catalyst according to claim 2, characterized in that: In the ABCD multi-metal oxide, the atomic percentage content of A is 1-10 at%, the sum of the atomic percentage contents of B and C is 10-25 at%, and the atomic percentage content of D is 50-70 at%.

4. The multi-metal oxide catalyst according to any one of claims 1 to 3, characterized in that The multi-metal oxide catalyst has a porous structure.

5. A method for preparing the multi-metal oxide catalyst according to any one of claims 1 to 4, characterized in that: include: Adding a carbon source and a decomposing agent into a metal precursor salt solution and stirring the mixture to obtain a mixed solution; The mixed solution is freeze-dried to obtain a frozen intermediate product; The frozen intermediate product is calcined to obtain the multi-metal oxide catalyst, wherein the decomposition agent is decomposed to generate gas during the calcination process.

6. The method according to claim 5, characterized in that The concentration of the metal precursor salt in the metal precursor salt solution is 0.001-100 mg / mL.

7. The method according to claim 5, characterized in that The mass ratio of the carbon source to the decomposing agent is 1:100-1:

1.

8. The method according to claim 5, characterized in that The carbon source includes at least one of galactose, sucrose, fructose, glucose and maltose, and the decomposing agent includes at least one of thiourea, ammonium chloride, urea and ammonium sulfate.

9. The method according to claim 5, characterized in that The freeze-drying treatment is carried out at a temperature of -50-0°C for a time of 0.1-200 hours; and / or the calcination treatment is carried out at a temperature of 200-1500°C for a time of 0.1-1800 hours.

10. A zinc-air battery, characterized in that: The multi-metal oxide catalyst comprises the catalyst described in any one of claims 1 to 4.

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