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WO2024000742A1 - Matériau d'électrode composite à hétérostructure oxyde de pérovskite-phosphure de métal de transition, procédé de préparation pour celui-ci, et utilisation de celui-ci - Google Patents

Matériau d'électrode composite à hétérostructure oxyde de pérovskite-phosphure de métal de transition, procédé de préparation pour celui-ci, et utilisation de celui-ci Download PDF

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WO2024000742A1
WO2024000742A1 PCT/CN2022/111461 CN2022111461W WO2024000742A1 WO 2024000742 A1 WO2024000742 A1 WO 2024000742A1 CN 2022111461 W CN2022111461 W CN 2022111461W WO 2024000742 A1 WO2024000742 A1 WO 2024000742A1
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perovskite oxide
transition metal
composite electrode
metal phosphide
electrode material
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Chinese (zh)
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金超
陆正义
李聪
王恩丽
杨瑞枝
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material

Definitions

  • the invention belongs to the field of new energy and new materials, specifically relates to a perovskite oxide-transition metal phosphide heterostructure composite electrode material, and also relates to its special synthesis process route and its electrocatalytic activity and application.
  • Fuel cells and metal-air batteries use oxygen as the cathode reaction substance. Through the action of a catalyst, an oxygen reduction reaction occurs, thereby achieving the formation of electric current.
  • the intrinsic kinetic process of the oxygen reduction reaction is inert, and the use of efficient catalysts is required to accelerate the oxygen reduction reaction. Due to the scarcity of precious metals such as Pt and Pd, the development of non-noble metal high-efficiency oxygen catalysts has become a key link in the development of fuel cells and metal-air batteries.
  • Perovskite oxide has a special defect structure, which has strong surface adsorption and dissociation effects on oxygen molecules, and there is often a certain concentration of oxygen vacancies inside the perovskite oxide crystal, which is very conducive to the diffusion of oxygen ions therein. Internal transmission. Therefore, perovskite oxides are often used as air electrode catalysts in solid oxide fuel cells (SOFC), metal-air batteries, and water electrolysis for hydrogen production.
  • SOFC solid oxide fuel cells
  • perovskite oxides can be used in lithium-metal air batteries to significantly reduce the charge and discharge polarization of the battery, and obtain high charge and discharge capacity, excellent charge and discharge rates and long cycles.
  • the material can be converted into a cubic perovskite and layered perovskite oxide composite material to form a heterogeneous interface and improve Oxygen catalytic ability; the prior art reports a SrTi 0.2-x Nb x Co 0.8 O 3 perovskite oxide, which has excellent oxygen evolution activator stability and can be used as a renewable fuel cell, rechargeable metal-air Electrocatalysts in batteries, water electrolysis and other fields.
  • perovskite oxides have been studied and reported in the above fields, they still have practical problems such as low conductivity and catalytic activity that needs to be further improved.
  • the existing technology combines BaCo 1 ⁇ x Ti x O 3 ⁇ ⁇ perovskite oxide with Co 3 O 4 to construct a dual-phase conductive catalyst to improve the catalytic performance and oxygen evolution in alkaline water electrolysis or metal-air batteries.
  • the existing technology uses plasma etching technology to treat perovskite oxide with active groups generated in the plasma in at least one atmosphere of nitrogen, phosphine or hydrogen sulfide gas, effectively improving calcium Oxygen defects and/or oxygen vacancy concentrations of titanium oxides, and element doping of perovskite oxides can quickly improve the electrocatalytic performance of perovskite oxides.
  • existing technologies have improved perovskite catalysts, However, the preparation process is complicated, such as plasma treatment, and compared with conventional precious metal catalysts, there is still a performance gap.
  • the primary purpose of the present invention is to provide a preparation method and application of a perovskite oxide-transition metal phosphide heterostructure composite electrode material.
  • a perovskite oxide-transition metal phosphide heterostructure composite electrode material By constructing the perovskite oxide-transition metal phosphide heterostructure interface in situ, the inherent shortcomings of low conductivity of perovskite oxide are improved.
  • the perovskite oxide is optimized by enriching the material defect structure and introducing functional catalysis. oxygen catalytic performance.
  • the invention also discloses the preparation process of this type of perovskite oxide-transition metal phosphide heterostructure composite electrode material and its specific application as a high-efficiency bifunctional catalyst in water electrolysis and metal-air batteries.
  • the technical solution adopted by the present invention is: a perovskite oxide-transition metal phosphide heterostructure composite electrode material, the perovskite oxide includes Ln 1-x Sr x Cr 1- One of y M y O 3- ⁇ , Ln 1-x Sr x Ti 1-y M y O 3- ⁇ , Ln 0.8 Sr 1.2 MO 4+ ⁇ ; the transition metal phosphide includes M 2 P or MP 2 ; M is a transition metal, and Ln is a rare earth metal.
  • Ln is La, Pr or Gd; M is Fe, Co or Ni; 0 ⁇ x ⁇ 0.5;0 ⁇ y ⁇ 0.5.
  • the size of the transition metal phosphide is 5 to 50 nm, such as 10 to 30 nm; the transition metal phosphide nanoparticles are grown in an island shape and semi-embedded in situ on the perovskite oxide skeleton.
  • the present invention adopts solid phase method or sol-gel method to synthesize perovskite oxide; then the perovskite oxide is reduced at high temperature to obtain perovskite oxide-metal (alloy) composite material; and then the perovskite is oxidized
  • the material-metal (alloy) composite material is subjected to low-temperature phosphating treatment to obtain a perovskite oxide-transition metal phosphide heterostructure composite electrode material.
  • the calcination temperature is 800 ⁇ 1100°C and the calcination time is 4 ⁇ 12h
  • the xerogel is dried at 250 ⁇ 300°C and then calcined at 800 ⁇ 1000°C 4 ⁇ 12h
  • the atmosphere is hydrogen or Ar/H 2 mixed gas
  • the reduction temperature is 700 ⁇ 900°C
  • the reduction time is 2 ⁇ 4h
  • the phosphorus source is sodium hypophosphite or Ammonium hypophosphite
  • the mass ratio of phosphorus source and metal-containing perovskite oxide is 1 to 2:1
  • the carrier gas is Ar or Ar/H 2 mixed gas
  • the phosphating temperature is 300 to 700°C
  • the phosphating temperature is 300 to 700°C.
  • the time is 1 ⁇ 3h.
  • the oxides or carbonates of each metal element are used as raw materials. After weighing according to the stoichiometric ratio, it is produced through ball milling, tableting, high-temperature air calcination, crushing, ball milling and other processes.
  • the calcination temperature is 800 ⁇ 1100°C, calcination time is 4 ⁇ 12h;
  • sol-gel method synthesis uses nitrates of various metal elements as raw materials, citric acid and ethylenediaminetetraacetic acid as chelating agents, ammonia water to adjust the pH value to 7 ⁇ 9, heat and stir
  • the xerogel is dried at 250-300°C, burned and carbonized, and then calcined in high-temperature air.
  • the calcination temperature is 800-1000°C and the calcination time is 4-12 hours.
  • the perovskite oxide prepared above is subjected to high-temperature reduction treatment in a tube furnace to precipitate transition metal or transition metal alloy nanoparticles in situ.
  • the reduction atmosphere is hydrogen or Ar/H 2 mixed gas, the reduction temperature is 800°C, and the reduction time It is 2 ⁇ 4h.
  • the above-mentioned high-temperature reduction treated perovskite oxide is subjected to low-temperature phosphating treatment in a tube furnace.
  • the phosphorus source is sodium hypophosphite or ammonium hypophosphite.
  • the carrier gas is high-purity Ar or Ar/H 2 mixed gas.
  • the phosphorus The phosphating temperature is 300 to 500°C, and the phosphating time is 2 hours.
  • the phosphorus source and the reduced perovskite oxide are placed sequentially along the direction of the carrier gas flow. The mass ratio of the two is 1 to 2:1.
  • the preferred composition of the perovskite oxide is: La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3- ⁇ , La 0.6 Sr 0.4 Ti 0.8 Ni 0.2 O 3- ⁇ , La 0.8 Sr 1.2 Co 0.2 Fe 0.8 O 4+ ⁇ and Pr 0.8 Sr 1.2 Fe 0.5 Ni 0.5 O 4+ ⁇ ;
  • the preferred composition of transition metal phosphide is: Ni 2 P, CoFeP 2 , FeNiP 2 .
  • the synthesis process route of the perovskite oxide-transition metal phosphide heterostructure composite electrode material of the present invention is: solid-phase method or sol-gel method synthesis ⁇ high-temperature reduction ⁇ low-temperature phosphating.
  • the ball milling conditions are 600 rpm, ball milling for 12 hours, and the preferred calcination conditions are 12 hours at 1000°C; when synthesized by the sol-gel method, the preferred calcination conditions are 6 hours at 900°C.
  • High-temperature reduction treatment is performed in a tube furnace to precipitate transition metal or transition metal alloy nanoparticles in situ.
  • the reduction atmosphere is hydrogen or Ar/H 2 mixed gas.
  • the optimized reduction treatment conditions are: Ar/H 2 mixed gas is the carrier gas.
  • the reduction temperature is 800°C and the reduction time is 4h.
  • Low-temperature phosphating treatment is performed in a tube furnace.
  • the preferred phosphating treatment conditions are: Ar/H 2 mixed gas as carrier gas, phosphating temperature of 350°C, phosphating time of 2 hours, phosphorus source and perovskite oxide The mass ratio is 2:1.
  • the perovskite oxide-transition metal phosphide heterostructure composite electrode material of the present invention simultaneously has excellent electrocatalytic activity and stability such as oxygen reduction, oxygen evolution, and hydrogen evolution, and can meet the requirements for the construction of electrolytic water hydrogen production, metal-air Various new energy devices such as batteries, and output excellent and stable electrochemical performance. Its application range includes electrolysis of water for hydrogen production, zinc-air batteries and lithium-air batteries.
  • the invention discloses a device containing the above-mentioned perovskite oxide-transition metal phosphide heterostructure composite electrode material.
  • the electrode of the device includes the above-mentioned perovskite oxide-transition metal phosphide heterostructure composite electrode material. .
  • the invention discloses the application of the above-mentioned perovskite oxide-transition metal phosphide heterostructure composite electrode material in preparing oxygen reduction, oxygen evolution or hydrogen evolution electrode materials.
  • a heterostructure composite electrode material with a perovskite oxide/transition metal phosphide heterostructure is disclosed, and its original structure is disclosed. bit construction method.
  • Both perovskite oxides and transition metal phosphides have high-efficiency oxygen catalytic capabilities, which can increase the conductivity of electrode materials. Their strong electron-pulling ability can produce a charge compensation effect within the heterostructure and increase the oxygen vacancy concentration. Thereby further improving the catalytic activity.
  • the perovskite oxide-transition metal phosphide heterostructure composite electrode material disclosed in the present invention is used as an electrocatalyst for water electrolysis for hydrogen production and metal-air batteries, significantly The performance and stability of these electrochemical devices are improved.
  • the present invention discloses a perovskite oxide-transition metal phosphide heterostructure composite electrode material for the first time. Its characteristics and advantages can be reflected in the following aspects: First, both perovskite oxide and transition metal phosphide are are functional materials, both of which have high-efficiency oxygen catalytic ability.
  • the two are highly coupled and have a synergistic effect, improving the catalytic performance of the heterostructure composite electrode;
  • the transition metal phosphide is grown in situ on On the perovskite oxide surface, the preparation process is simple and controllable;
  • the transition metal phosphide nanoparticles are island-shaped and semi-embedded in situ grown on the perovskite oxide skeleton, which is beneficial to improving the stability of the electrode process. .
  • Figure 1 shows La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3- ⁇ (LSCN), reduced La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3- ⁇ (r-LSCN) and La 0.8 Sr 0.2 Cr after phosphating in Example 1.
  • Figure 2 is a TEM image of the LSCN/Ni 2 P heterostructure composite electrode material formed in Example 1.
  • Figure 3 shows the symmetrical electrode type water electrolysis hydrogen production system constructed using r-LSCN-P in Example 1 and its stability.
  • Figure 4 shows the power curve, rate performance and charge and discharge cycles of the zinc-air battery assembled using La 0.6 Sr 0.4 Ti 0.8 Fe 0.1 Ni 0.1 O 3- ⁇ / (FeNi) 2 P heterostructure composite electrode material in Example 2. stability.
  • Figure 5 is the XRD pattern of the LSCF/CoFeP 2 heterostructure composite electrode material in Example 3.
  • Figure 6 is a TEM image of the LSCF/CoFeP 2 heterostructure composite electrode material in Example 3.
  • Figure 7 shows the performance output diagrams (a, b) of the lithium-air battery assembled using LSCF/ CoFeP2 heterostructure composite electrodes and the performance output diagrams (c, d) of the lithium-air battery assembled using CoP as the catalyst in Example 3. .
  • the medicines or reagents involved in the present invention can be purchased through the market and are conventional raw materials.
  • the physical characterization methods of materials such as X-ray diffraction analysis (XRD), scanning electron microscope (SEM) and scanning electron microscope (TEM) involved in the present invention are conventional instrumental analysis methods, and there are no special sample processing and testing methods.
  • XRD X-ray diffraction analysis
  • SEM scanning electron microscope
  • TEM scanning electron microscope
  • Example 1 First, weigh La(NO 3 ) 3 , Sr(NO 3 ) 2 , (NH 4 ) 2 Cr 2 O 7 and Ni(NO 3 ) 2 with a mass ratio of 8:2:6.9:3.1. ⁇ Dissolve 6H 2 O in deionized water, then add ethylenediaminetetraacetic acid and citric acid (the amounts of ethylenediaminetetraacetic acid and citric acid are respectively 1.5 times and 2 times the amount of total cationic substances), and then add Stir for 5 hours at 80°C to obtain a sol, and then dry at 160°C for 2 hours to obtain a dry gel; first burn the dry gel in a tube furnace at 320°C in air for 3 hours, and then calcine at 1000°C for 8 hours to obtain La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3- ⁇ (LSCN).
  • the LSCN was annealed in a tube furnace at 800°C for 2 hours in an Ar/H 2 (5vol% H 2 ) atmosphere.
  • the LSCN was reduced and elemental Ni nanoparticles were precipitated in situ.
  • the product was labeled r-LSCN.
  • a perovskite oxide-transition metal phosphide heterostructure composite electrode material (r-LSCN-P); protective gas is stopped during the heating and heat preservation processes, and Ar/H 2 protective gas is passed during the cooling process.
  • the XRD and TEM characterization of the product r-LSCN-P are shown in Figure 1 and Figure 2 respectively. It can be seen that LSCN still maintains the cubic perovskite structure after reduction phosphating treatment.
  • the Ni 2 P nanoparticles generated in situ have a diameter of about 20 nm and grow on the surface of the LSCN skeleton in an island-like, semi-embedded manner.
  • Successfully obtained LSCN/Ni 2 P heterostructure composite material (r-LSCN-P) was developed.
  • an electrode slurry was prepared, and then the slurry spraying method was used to evenly load r-LSCN-P on the Electrodes were made on nickel foam with an electrode area of 2cm 2 and a loading capacity of r-LSCN-P of 1.5mg cm -2 .
  • the prepared electrodes were used as positive and negative electrodes to assemble a symmetrical water electrolytic cell and measure its performance in 1.0M KOH aqueous solution.
  • Example 2 According to La 0.6 Sr 0.4 Ti 0.8 Fe 0.1 Ni 0.1 O 3- ⁇ , take lanthanum nitrate, strontium nitrate, nickel nitrate, iron nitrate and titanium dioxide as raw materials, citric acid as chelating agent, water as solvent, and mix the above materials Then, adjust the pH value to 7.5 with ammonia water, stir at 80°C for 5 hours to obtain a sol, then dry at 140°C overnight to obtain a xerogel, and finally calcine at 900°C in the air for 6 hours to obtain La 0.6 Sr 0.4 Ti 0.8 Fe 0.1 Ni 0.1 O 3- delta cubic perovskite oxide powder (LSTFN).
  • LSTFN delta cubic perovskite oxide powder
  • the LSTFN was annealed in a tube furnace at 800°C for 2 hours in an Ar/H 2 (5vol% H 2 ) atmosphere to reduce the LSTN and precipitate FeNi alloy nanoparticles in situ. Put the sodium hypophosphite and the reduced LSTFN powder into the tube furnace in sequence according to the direction of 5% H 2 /Ar gas flow. Before raising the temperature, pass Ar/H 2 protective gas for 0.5 h, and then start from room temperature at 10°C/min.
  • Ar/H 2 5vol% H 2
  • Foamed nickel was used as the current collector, LSTFN@(FeNi) 2 P was used as the bifunctional catalyst, acetylene black was used as the conductive agent, and commercial PVDF was used as the binder to prepare an electrode slurry.
  • the LSTFN@(FeNi) 2 P was sprayed using the slurry spraying method.
  • the working electrode was uniformly loaded on nickel foam, in which the loading amount of LSTFN@(FeNi) 2 P was 1.2 mg cm -2 .
  • a commercial zinc plate was used as the negative electrode, and polyvinyl alcohol hydrogel saturated with 6.0M KOH was used as the solid state.
  • the solid-state zinc-air battery was assembled with the electrolyte, the charge and discharge performance of the battery was tested, and the performance of the solid-state zinc-air battery assembled with LSTFN and commercial Pt/C-IrO catalyst was compared under the same conditions.
  • the results are shown in Figure 4.
  • the peak power density of the solid-state zinc-air battery assembled with LSTFN@(FeNi) 2 P as the catalyst can reach 35Mw cm -2 , which is better than the solid-state zinc-air battery assembled with the commercial Pt/C-IrO 2 catalyst.
  • Example 3 Synthesis of LSCF using solid phase method.
  • Lanthanum oxide, strontium carbonate, ferric oxide and cobalt tetroxide are used as raw materials, weighed according to the stoichiometric ratio and placed in a ball mill at 600 rpm for 12 hours, then pressed into tablets, calcined at 1000°C for 8 hours, and crushed to obtain La 0.8 Sr 1.2 Co 0.2 Fe 0.8 O 4+d layered perovskite oxide powder (LSCF).
  • the LSCF powder was annealed at 800°C for 10 hours in an Ar/H 2 (5vol% H 2 ) reducing atmosphere to obtain r-LSCF powder, and CoFe alloy particles were precipitated on the surface of the LSCF perovskite oxide.
  • LSCF/CoFeP 2 was used as the bifunctional catalyst
  • acetylene black was used as the conductive agent
  • commercial PVDF was used as the binder to prepare the electrode slurry.
  • the slurry spraying method was used to evenly load the LSCF/CoFeP 2 on the carbon paper.
  • the working electrode was made on the LSCF/CoFeP 2 loading capacity of 2.0 mg cm -2 , which was transferred to the glove box after vacuum drying.
  • the metal lithium sheet was used as the negative electrode
  • Whatman glass fiber was used as the separator
  • 1.0 M LiTFSI-TEGDME was used as the electrolyzer.
  • FIG. 7(a,b) shows the assembled lithium-air battery showing excellent rate performance, with a first discharge capacity of up to 4500 mAh g -1 at a current density of 600mA g -1 , and shows excellent charge and discharge cycle performance, after 70 cycles Cycling, no capacity drop and charge-discharge polarization change.
  • Figure 7 (c, d) shows the performance output of a lithium-air battery using pure CoP as a catalyst prepared and tested under the same conditions. In comparison, CoP shows lower charge and discharge capacity and poor charge and discharge. Cycling stability.

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Abstract

L'invention concerne un matériau d'électrode composite à hétérostructure oxyde de pérovskite-phosphure de métal de transition, un procédé de préparation de celui-ci, et une utilisation de celui-ci, se rapportant aux domaines des nouvelles énergies et des nouveaux matériaux. L'oxyde de pérovskite comprend Ln1-xSrxCr1-yMyO3- δ, Ln1-xSrxTi1-yMyO3- δ, Ln0,8Sr1,2MO4+ δ, etc., et le phosphure de métal de transition comprend M2P ou MP2. L'oxyde de pérovskite est synthétisé à l'aide d'un procédé en phase solide ou d'un procédé sol-gel ; puis l'oxyde de pérovskite est soumis à une réduction à haute température, et un matériau composite oxyde de pérovskite-métal est obtenu ; et ensuite le matériau composite oxyde de pérovskite-métal est soumis à une phosphatation à basse température, et un matériau d'électrode composite à hétérostructure oxyde de pérovskite-phosphure de métal de transition est obtenu, les nanoparticules de phosphure de métal de transition étant mises en croissance in situ sur un squelette d'oxyde de pérovskite selon une forme d'îlot et d'une manière semi-incorporée. Le matériau obtenu possède une excellente activité électrocatalytique, telle que la réduction d'oxygène, la précipitation d'oxygène et la précipitation d'hydrogène, et une excellente stabilité, est capable de satisfaire les exigences de construction de divers nouveaux dispositifs d'énergie tels que la production d'hydrogène par électrolyse de l'eau et des batteries métal-air, et délivre des performances électrochimiques excellentes et stables.
PCT/CN2022/111461 2022-06-30 2022-08-10 Matériau d'électrode composite à hétérostructure oxyde de pérovskite-phosphure de métal de transition, procédé de préparation pour celui-ci, et utilisation de celui-ci Ceased WO2024000742A1 (fr)

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CN202210770006.1A CN115058733A (zh) 2022-06-30 2022-06-30 一种钙钛矿氧化物-过渡金属磷化物异质结构复合电极材料及其制备方法与应用

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