CN115058733A - Perovskite oxide-transition metal phosphide heterostructure composite electrode material and preparation method and application thereof - Google Patents
Perovskite oxide-transition metal phosphide heterostructure composite electrode material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention belongs to the field of new energy and new materials, and discloses a perovskite oxide-transition metal phosphide heterostructure composite electrode material and a preparation method and application thereof, wherein the perovskite oxide comprises Ln 1‑x Sr x Cr 1‑y M y O 3‑δ 、Ln 1‑x Sr x Ti 1‑y M y O 3‑δ 、Ln 0.8 Sr 1.2 MO 4+δ Etc., the transition metal phosphide includes M 2 P or MP 2 . Synthesizing perovskite oxide by a solid phase method or a sol-gel method; then reducing the perovskite oxide at high temperature to obtain a perovskite oxide-metal composite material; then carrying out low-temperature phosphating treatment on the perovskite oxide-metal composite material to obtain a perovskite oxide-transition metal phosphide heterostructure composite electrode material, wherein transition metal phosphide nano-particles grow on a perovskite oxide framework in an island-shaped and semi-embedded in-situ manner; meanwhile, the electrochemical device has excellent electrocatalytic activity and stability of oxygen reduction, oxygen precipitation, hydrogen precipitation and the like, can meet the requirements of constructing various new energy devices such as electrolytic water hydrogen production, metal-air batteries and the like, and outputs excellent and stable electrochemical performance.
Description
Technical Field
The invention belongs to the field of new energy and new materials, and particularly relates to a perovskite oxide-transition metal phosphide heterostructure composite electrode material, a special synthesis process route thereof, electrocatalytic activity thereof and application thereof.
Background
At present, in order to meet the requirements of fields such as various portable electronic products, electric vehicles and the like on higher energy density and long endurance performance, new energy sources such as fuel cells, metal-air batteries and the like are widely concerned and developed. The fuel cell and the metal-air cell take oxygen as a positive electrode reaction substance, and the oxygen reduction reaction is carried out under the action of a catalyst, so that the formation of current is realized. Then, the intrinsic kinetic process of the oxygen reduction reaction is inert, and the use of a high-efficiency catalyst is required to accelerate the oxygen reduction reaction. Due to the scarcity of resources of noble metals such as Pt and Pd, the development of non-noble metal high-efficiency oxygen catalysts has become a key ring in the development approaches of fuel cells and metal-air cells.
The perovskite oxide has a special defect structure and has strong surface adsorption to oxygen moleculesAnd dissociation, and a certain concentration of oxygen vacancies are always present in the perovskite oxide crystal, which is very favorable for oxygen ion transmission in the perovskite oxide crystal. Therefore, perovskite oxides are often used as air electrode catalysts in the fields of Solid Oxide Fuel Cells (SOFC), metal-air cells, hydrogen production by water electrolysis, and the like. The prior art reports Pr 0.4 Sr 0.6 Co 0.2 Fe 0.7 Nb 0.1 O 3 、Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O 3 、La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 And Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3 When the perovskite oxide is used as a bifunctional catalyst for efficient oxygen reduction and oxygen precipitation, the lithium-metal air battery can obviously reduce the charge-discharge polarization of the battery, and obtain high charge-discharge capacity, excellent charge-discharge rate and long cycle life; the prior patent reports a La 1-x Sr x+ a Fe 1-y-z N y M z O 3-δ The perovskite oxide, wherein N is selected from one or more of Cu, Ni or Co, M is selected from one of Ti, Nb or Mo, the material can be converted into a cubic perovskite and layered perovskite oxide composite material after high-temperature annealing treatment, a heterogeneous interface is formed, and the oxygen catalytic capacity is improved; the prior art reports a SrTi 0.2-x Nb x Co 0.8 O 3 Perovskite oxides, which have excellent oxygen evolution activator stability, are useful as electrocatalysts in the fields of renewable fuel cells, rechargeable metal-air cells, water electrolysis, and the like.
Although perovskite oxides have been studied and reported in the above-mentioned fields, they still have practical problems of low conductivity, further improvement of catalytic activity, and the like. The prior art is that BaCo is mixed with BaCo 1-x Ti x O 3-δ Perovskite oxide and Co 3 O 4 Compounding, constructing a two-phase conductive catalyst, and improving the oxygen precipitation catalytic performance and stability in alkaline water electrolysis or metal-air batteries; the prior art uses plasma etching techniques in nitrogen or phosphine or hydrogen sulfide gasIn at least one atmosphere, the perovskite oxide is treated by using active groups generated in the plasma, so that the oxygen defect and/or oxygen vacancy concentration of the perovskite oxide are/is effectively improved, and the perovskite oxide is subjected to element doping, so that the electrocatalysis performance of the perovskite oxide is rapidly improved; although the prior art has many improvements over perovskite catalysts, the preparation process is complex, such as plasma treatment, and the performance is still far from the same as that of conventional noble metal catalysts.
Disclosure of Invention
The invention aims at providing a preparation method and application of a perovskite oxide-transition metal phosphide heterostructure composite electrode material. The inherent defect of low conductivity of the perovskite oxide is improved by constructing a perovskite oxide-transition metal phosphide heterostructure interface in situ, and meanwhile, the oxygen catalytic performance of the perovskite oxide is optimized by enriching the defect structure of the material and introducing functional catalysis. The invention also discloses a preparation process of the perovskite oxide-transition metal phosphide heterostructure composite electrode material and a specific application of the perovskite oxide-transition metal phosphide heterostructure composite electrode material as a high-efficiency bifunctional catalyst in water electrolysis and metal-air batteries.
In order to achieve the purpose, the invention adopts the technical scheme that:
a perovskite oxide-transition metal phosphide heterostructure composite electrode material, the perovskite oxide comprising Ln 1-x Sr x Cr 1-y M y O 3-δ 、Ln 1-x Sr x Ti 1-y M y O 3-δ 、Ln 0.8 Sr 1.2 MO 4+δ One of (1); the transition metal phosphide comprises M 2 P or MP 2 (ii) a M is transition metal, Ln is rare earth metal. Preferably, Ln is La, Pr or Gd; m is Fe, Co or Ni; 0<x≤0.5；0<y≤0.5。
In the invention, the size of the transition metal phosphide is 5-50 nm, such as 10-30 nm; the transition metal phosphide nanoparticles are grown on the perovskite oxide framework in an island-shaped and semi-embedded in-situ manner.
The invention adopts a solid phase method or a sol-gel methodForming a perovskite oxide; then reducing the perovskite oxide at high temperature to obtain a perovskite oxide-metal (alloy) composite material; and then carrying out low-temperature phosphating treatment on the perovskite oxide-metal (alloy) composite material to obtain the perovskite oxide-transition metal phosphide heterostructure composite electrode material. Specifically, in the solid phase method, the calcining temperature is 800-1100 ℃, and the calcining time is 4-12 h; in the sol-gel method, dried gel is dried at 250-300 ℃ and then calcined at 800-1000 ℃ for 4-12 h; in high-temperature reduction, the atmosphere is hydrogen or Ar/H 2 Reducing the mixed gas at 700-900 ℃ for 2-4 h; in the low-temperature phosphating treatment, the phosphorus source is sodium hypophosphite or ammonium hypophosphite; the mass ratio of the phosphorus source to the metal-containing perovskite oxide is 1-2: 1; the carrier gas is Ar or Ar/H 2 Mixing gas; the temperature of the phosphorization is 300-700 ℃, and the time of the phosphorization is 1-3 h.
During solid phase synthesis, oxides or carbonates of all metal elements are used as raw materials, and the metal elements are prepared by the processes of ball milling, tabletting, high-temperature air calcination, crushing, ball milling and the like after being weighed according to stoichiometric ratio, wherein the calcination temperature is 800-1100 ℃, and the calcination time is 4-12 h; the method comprises the steps of taking nitrates of all metal elements as raw materials during synthesis by a sol-gel method, taking citric acid and ethylenediamine tetraacetic acid as chelating agents, adjusting the pH value to 7-9 with ammonia water, heating and stirring until dried gel is formed, drying at 250-300 ℃, burning to discharge carbon, and calcining at high temperature for 4-12 hours at 800-1000 ℃.
The prepared perovskite oxide is subjected to high-temperature reduction treatment in a tube furnace, transition metal or transition metal alloy nanoparticles are precipitated in situ, and the reduction atmosphere is hydrogen or Ar/H 2 And (3) reducing the mixed gas at 800 ℃ for 2-4 h.
The perovskite oxide after the high-temperature reduction treatment is put into a tubular furnace for low-temperature phosphating treatment, the phosphorus source is sodium hypophosphite or ammonium hypophosphite, and the carrier gas is high-purity Ar or Ar/H 2 The phosphorization temperature is 300-500 ℃, the phosphorization time is 2h, a phosphorus source and the reduction-treated perovskite oxide are sequentially placed along the flow direction of carrier gas during phosphorization, and the mass ratio of the phosphorus source to the reduction-treated perovskite oxide is 1-up to 12:1。
Further, the perovskite oxide preferably has a composition of: la 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3-δ 、La 0.6 Sr 0.4 Ti 0.8 Ni 0.2 O 3-δ 、La 0.8 Sr 1.2 Co 0.2 Fe 0.8 O 4+δ And Pr 0.8 Sr 1.2 Fe 0.5 Ni 0.5 O 4+δ (ii) a The transition metal phosphide preferably consists of: ni 2 P、CoFeP 2 、FeNiP 2 。
The synthesis process route of the perovskite oxide-transition metal phosphide heterostructure composite electrode material is as follows: solid phase method or sol-gel method → high temperature reduction → low temperature phosphorization. During solid phase synthesis, ball milling conditions are 600 revolutions per minute and 12 hours, and the preferred calcining condition is 12 hours at 1000 ℃; in the synthesis by the sol-gel method, the preferred calcination condition is 900 ℃ for 6 hours. Carrying out high-temperature reduction treatment in a tube furnace, in-situ precipitating transition metal or transition metal alloy nanoparticles in a reducing atmosphere of hydrogen or Ar/H 2 The mixed gas is optimized to reduce the treatment conditions as follows: Ar/H 2 The mixed gas is used as carrier gas, the reduction temperature is 800 ℃, and the reduction time is 4 h. Carrying out low-temperature phosphating treatment in a tubular furnace, wherein the preferable phosphating treatment conditions are as follows: Ar/H 2 The mixed gas is used as carrier gas, the phosphating temperature is 350 ℃, the phosphating time is 2 hours, and the mass ratio of the phosphorus source to the perovskite oxide is 2: 1.
The perovskite oxide-transition metal phosphide heterostructure composite electrode material disclosed by the invention has excellent electrocatalytic activity and stability of oxygen reduction, oxygen precipitation, hydrogen precipitation and the like, can meet the requirements of constructing various new energy devices such as electrolytic water hydrogen production, metal-air batteries and the like, and can output excellent and stable electrochemical properties, and the application range of the perovskite oxide-transition metal phosphide heterostructure composite electrode material comprises the electrolytic water hydrogen production, the zinc-air batteries, the lithium-air batteries and the like. The invention discloses a device containing the perovskite oxide-transition metal phosphide heterostructure composite electrode material, and an electrode of the device comprises the perovskite oxide-transition metal phosphide heterostructure composite electrode material. The invention discloses an application of the perovskite oxide-transition metal phosphide heterostructure composite electrode material in preparation of an oxygen reduction electrode material, an oxygen evolution electrode material or a hydrogen evolution electrode material.
By combining all the technical schemes, the invention has the advantages and beneficial effects that: the heterostructure composite electrode material with a perovskite oxide/transition metal phosphide heterostructure is disclosed for the first time, and an in-situ construction method thereof is also disclosed. The perovskite oxide and the transition metal phosphide both have high-efficiency oxygen catalysis capability, can increase the conductivity of an electrode material, have strong electron withdrawing capability, can generate charge compensation effect in a heterostructure, and improve the oxygen vacancy concentration, thereby further improving the catalytic activity. As a high-efficiency oxygen reduction, oxygen precipitation and hydrogen precipitation catalyst, the perovskite oxide-transition metal phosphide heterostructure composite electrode material disclosed by the invention is used as an electrocatalyst of a metal-air battery and hydrogen production by electrolyzing water, and the performance and stability of electrochemical devices are remarkably improved.
The invention discloses a perovskite oxide-transition metal phosphide heterostructure composite electrode material for the first time, which has the characteristics and advantages that:
firstly, perovskite oxide and transition metal phosphide are functional materials and have high-efficiency oxygen catalysis capability, and in the material system disclosed by the invention, the perovskite oxide and the transition metal phosphide are highly coupled and have a synergistic effect, so that the catalysis performance of the heterostructure composite electrode is improved;
secondly, the transition metal phosphide grows on the surface of the perovskite oxide in situ, and the preparation process is simple, convenient and controllable;
and thirdly, the transition metal phosphide nanoparticles grow on the perovskite oxide skeleton in an island-shaped and semi-embedded in-situ manner, so that the stability of the electrode process is improved.
Drawings
FIG. 1 shows La of the first embodiment 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3-δ (LSCN) reduction of La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3-δ (r-LSCN) and post-phosphated La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3-δ XRD pattern of (r-LSCN-P);
FIG. 2 shows LSCN/Ni formed in example one 2 A TEM image of the P-heterostructure composite electrode material;
FIG. 3 shows the stability and the system for hydrogen production by water electrolysis with symmetric electrodes constructed by r-LSCN-P in the first embodiment;
FIG. 4 shows La used in the second embodiment 0.6 Sr 0.4 Ti 0.8 Fe 0.1 Ni 0.1 O 3-δ / (FeNi) 2 The power curve, the rate capability and the charge-discharge cycle stability of the zinc-air battery assembled by the P heterostructure composite electrode material;
FIG. 5 is the LSCF/CoFeP in example III 2 An XRD pattern of the heterostructure composite electrode material;
FIG. 6 is the LSCF/CoFeP in example III 2 A TEM image of the heterostructure composite electrode material;
FIG. 7 shows the utilization of LSCF/CoFeP in example III 2 And (c) a lithium-air battery performance output graph (a, b) assembled by adopting the heterostructure composite electrode as a catalyst and a lithium-air battery performance output graph (c, d) assembled by adopting the CoP as a catalyst.
Detailed Description
The medicine or the reagent related to the invention can be purchased through the market and is a conventional raw material. The physical characterization means of materials such as X-ray diffraction analysis (XRD), Scanning Electron Microscope (SEM), scanning electron microscope (TEM) and the like, which are related by the invention, are conventional instrument analysis methods, and no special sample treatment and test methods exist. When a water electrolysis hydrogen production device, a liquid zinc-air battery and a lithium-air battery are manufactured and tested, the electrode manufacturing method, the electrolytic cell and the battery assembly method related by the invention have no difference from the conventional electrode and battery manufacturing method, and the test method and conditions have no special requirements.
The invention is further described with reference to the following figures and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example one
Firstly, weighing La (NO) with the mass ratio of 8:2:6.9:3.1 3 ) 3 、Sr(NO 3 ) 2 、(NH 4 ) 2 Cr 2 O 7 And Ni (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water, adding ethylene diamine tetraacetic acid and citric acid (the amount of substances of the ethylene diamine tetraacetic acid and the citric acid is 1.5 times and 2 times of the amount of the total cationic substances respectively), stirring at 80 ℃ for 5 hours to obtain sol, and drying at 160 ℃ for 2 hours to obtain xerogel; the xerogel is firstly calcined in a tubular furnace for 3h at 320 ℃ in the air and then calcined for 8h at 1000 ℃ to obtain La 0.8 Sr 0.2 Cr 0.69 Ni 0.31 O 3-δ （LSCN）。
Placing LSCN in a tube furnace in Ar/H 2 （5vol% H 2 ) Annealing for 2h at 800 ℃ in the atmosphere, reducing LSCN, precipitating simple substance Ni nano particles in situ, and marking the product as r-LSCN.
4.0 g of NaH 2 PO 2 And 2.0 g of r-LSCN are respectively put into two corundum boats and are sequentially placed in the air flowing direction in a way of introducing Ar/H 2 （5vol% H 2 ) In a tube furnace with a protective gas, Ar/H 2 The shielding gas is blown through NaH 2 PO 2 Then blowing the mixture through r-LSCN, and introducing Ar/H before heating 2 Shielding gas for 0.5 h, heating to 500 ℃ from room temperature at the speed of 10 ℃/min, preserving heat for 2h, and naturally cooling to obtain the perovskite oxide-transition metal phosphide heterostructure composite electrode material (r-LSCN-P); stopping introducing protective gas in the temperature rising and preserving process, introducing Ar/H in the temperature reducing process 2 And (5) protective gas. XRD and TEM characterization of the product r-LSCN-P are shown in FIGS. 1 and 2, respectively. It can be seen that the LSCN still maintains the cubic perovskite structure after the reduction phosphorization treatment, and the Ni generated in situ 2 The diameter of the P nano-particle is about 20nm, the P nano-particle grows on the surface of the LSCN framework in an island shape and a semi-embedded type, and the LSCN/Ni is successfully obtained 2 P heterostructure composite material (r-LSCN-P).
Preparing electrode slurry by using foamed nickel as a current collector, r-LSCN-P as a bifunctional catalyst, acetylene black as a conductive agent and commercial Nafion as a binder, and then uniformly loading the r-LSCN-P on the foamed nickel by adopting a slurry spraying method to manufacture an electrode, wherein the area of the electrode is 2cm 2 r-LSCN-P loading of 1.5mg cm -2 And the manufactured electrodes are used as positive and negative electrodes to assemble a symmetrical water electrolytic cell, the hydrogen production performance and stability of the water electrolytic cell in a 1.0M KOH aqueous solution are measured, and the water electrolytic cell is matched with LSCN, r-LSCN, commercial Pt/C and IrO under the same condition 2 The performance of the water electrolysis cell assembled with the catalysts was compared and the results are shown in fig. 3. It can be seen that the r-LSCN-P// r-LSCN-P symmetrical electrolytic cell shows the lowest electrolytic voltage and electrolytic stability.
Example two
According to La 0.6 Sr 0.4 Ti 0.8 Fe 0.1 Ni 0.1 O 3-δ Taking lanthanum nitrate, strontium nitrate, nickel nitrate, ferric nitrate and titanium dioxide as raw materials, citric acid as a chelating agent and water as a solvent, mixing the raw materials, adjusting the pH value to 7.5 by ammonia water, stirring for 5 hours at 80 ℃ to obtain sol, drying overnight at 140 ℃ to obtain dry gel, and calcining for 6 hours at 900 ℃ in the air to obtain La 0.6 Sr 0.4 Ti 0.8 Fe 0.1 Ni 0.1 O 3-δ Cubic perovskite oxide powder (LSTFN). LSTFN was placed in a tube furnace in Ar/H 2 （5vol% H 2 ) Annealing for 2h at 800 ℃ in the atmosphere, reducing LSTN, and precipitating FeNi alloy nanoparticles in situ. According to 5% H 2 Putting sodium hypophosphite and reduction-treated LSTFN powder into a tubular furnace in sequence in an Ar airflow direction, and introducing Ar/H before heating 2 Shielding gas for 0.5 h, heating to 350 deg.C at 10 deg.C/min, maintaining for 2 hr, and naturally cooling to obtain perovskite oxide-transition metal phosphide heterostructure composite electrode material (LSTFN @ (FeNi) 2 P); stopping introducing protective gas in the temperature rising and preserving process, introducing Ar/H in the temperature reducing process 2 （5vol% H 2 ) And (5) protective gas.
Using foamed nickel as current collector, using LSTFN @ (FeNi) 2 Preparing electrode slurry by taking P as a bifunctional catalyst, acetylene black as a conductive agent and commercial PVDF as a binder, and spraying LSTFN @ (FeNi) by adopting a slurry spraying method 2 P is loaded on the foam nickel evenly to produce the working electrode, wherein LSTFN @ (FeNi) 2 P loading was 1.2mg cm -2 The commercial zinc plate is used as a negative electrode, and polyvinyl alcohol hydrogel saturated with 6.0M KOH is used asSolid electrolyte assembled solid zinc-air battery, testing charging and discharging performance of the battery, and testing the charging and discharging performance of the battery under the same conditions with LSTFN and commercial Pt/C-IrO 2 The performance of the catalyst assembled solid-state zinc-air cells was compared and the results are shown in figure 4. Wherein LSTFN @ (FeNi) 2 The peak power density of the solid-state zinc-air battery assembled by the catalyst P can reach 35Mw cm -2 Comparative commercial Pt/C-IrO 2 The solid zinc-air battery assembled by the catalyst shows more excellent charge-discharge cycle stability, and no attenuation is caused after 200 cycles.
EXAMPLE III
LSCF is synthesized by a solid phase method. Lanthanum oxide, strontium carbonate, ferric oxide and cobaltosic oxide are taken as raw materials, weighed according to stoichiometric ratio, put into a ball mill for ball milling for 12 hours at 600 revolutions per minute, then pressed into tablets, calcined for 8 hours at 1000 ℃, and crushed to obtain La 0.8 Sr 1.2 Co 0.2 Fe 0.8 O 4+d Layered perovskite oxide powder (LSCF). Placing LSCF powder in Ar/H 2 （5vol% H 2 ) Annealing at 800 ℃ for 10 hours in a reducing atmosphere to obtain r-LSCF powder, and precipitating CoFe alloy particles on the surface of LSCF perovskite oxide. According to 5% H 2 Sequentially putting sodium hypophosphite and r-LSCF powder into a tube furnace in the flow direction of Ar gas flow, and introducing Ar/H before heating 2 Shielding gas for 0.5 h, heating from room temperature to 350 ℃ at the speed of 10 ℃/min, preserving heat for 5 h, and naturally cooling to obtain LSCF perovskite oxide-CoFeP 2 Transition metal phosphide heterostructure composite electrode material (LSCF/CoFeP) 2 ) In situ conversion of CoFe alloy particles on the surface of r-LSCF to CoFeP 2 A nanoparticle; stopping introducing protective gas in the temperature rising and preserving process, introducing Ar/H in the temperature reducing process 2 （5vol% H 2 ) And (5) protective gas. LSCF/CoFeP 2 The XRD and TEM physical properties of (a) are characterized as shown in fig. 5 and 6, respectively. It can be seen that CoFeP 2 The particle size is about 20nm, and the island-shaped semi-embedded growth is carried out on the surface of the LSCF framework.
Using commercial carbon paper as current collector and LSCF/CoFeP 2 Preparing electrode slurry by using a bifunctional catalyst, acetylene black as a conductive agent and commercial PVDF as a binder, and spraying LSCF/CoFeP by using a slurry spraying method 2 Uniformly loading on carbon paper to make working electrode, wherein LSCF/CoFeP 2 The loading capacity is 2.0mg cm -2 After vacuum drying treatment, the lithium-ion battery is transferred into a glove box, a metal lithium sheet is taken as a negative electrode, Whatman glass fiber is taken as a diaphragm, 1.0M LiTFSI-TEGDME is taken as electrolyte, a CR2032 button lithium-air battery is assembled, and the battery performance is tested by using a blue charge-discharge instrument. The results are shown in FIG. 7(a, b). It can be seen that the assembled lithium-air battery exhibited excellent rate performance at 600mA g -1 The first discharge capacity is up to 4500 mAh g -1 And the material shows excellent charge-discharge cycle performance, and has no capacity reduction and charge-discharge polarization change after 70 cycles. By way of comparison, fig. 7(c, d) shows the performance output of a lithium air battery prepared and tested under the same conditions with pure CoP as a catalyst, which in comparison shows lower charge and discharge capacity and poorer charge-discharge cycle stability.
The above detailed description is only intended to explain the object, technical embodiments and practical effects of the present invention in further detail, but the scope of the present invention is not limited thereto, and any modifications, equivalent substitutions and the like within the technical scope of the present invention disclosed herein are intended to be included within the scope of the present invention.
Claims (10)
1. A perovskite oxide-transition metal phosphide heterostructure composite electrode material, wherein the perovskite oxide comprises Ln 1-x Sr x Cr 1-y M y O 3-δ 、Ln 1-x Sr x Ti 1-y M y O 3-δ 、Ln 0.8 Sr 1.2 MO 4+δ One of (1); the transition metal phosphide comprises M 2 P or MP 2 (ii) a M is transition metal, Ln is rare earth metal.
2. The perovskite oxide-transition metal phosphide heterostructure composite electrode material of claim 1, wherein the size of the transition metal phosphide is 5 to 50 nm.
3. The perovskite oxide-transition metal phosphide heterostructure composite electrode material of claim 1, wherein Ln is La, Pr or Gd; m is Fe, Co or Ni; x is more than 0 and less than or equal to 0.5; y is more than 0 and less than or equal to 0.5.
4. A process for the preparation of a perovskite oxide-transition metal phosphide heterostructure composite electrode material as claimed in claim 1, wherein the perovskite oxide is synthesized by a solid phase method or a sol-gel method; then reducing the perovskite oxide at high temperature to obtain a perovskite oxide-metal composite material; and then carrying out low-temperature phosphating treatment on the perovskite oxide-metal composite material to obtain the perovskite oxide-transition metal phosphide heterostructure composite electrode material.
5. The preparation method of the perovskite oxide-transition metal phosphide heterostructure composite electrode material as claimed in claim 4, wherein in the solid phase method, the calcining temperature is 800-1100 ℃, and the calcining time is 4-12 h; in the sol-gel method, the dried gel is dried at 250-300 ℃ and then calcined at 800-1000 ℃ for 4-12 h.
6. The method for preparing a perovskite oxide-transition metal phosphide heterostructure composite electrode material according to claim 4, wherein in the high-temperature reduction, the atmosphere is hydrogen or Ar/H 2 And (3) reducing the mixed gas at 700-900 ℃ for 2-4 h.
7. The method for preparing a perovskite oxide-transition metal phosphide heterostructure composite electrode material according to claim 4, wherein in the low temperature phosphating treatment, the phosphorus source is sodium hypophosphite or ammonium hypophosphite; the mass ratio of the phosphorus source to the perovskite oxide is 1-2: 1.
8. The method for preparing a perovskite oxide-transition metal phosphide heterostructure composite electrode material as claimed in claim 4, wherein the carrier gas is A in the low-temperature phosphating treatmentr or Ar/H 2 Mixing gas; the temperature of the phosphorization is 300-700 ℃, and the time of the phosphorization is 1-3 h.
9. A device comprising the perovskite oxide-transition metal phosphide heterostructure composite electrode material of claim 1, wherein an electrode of the device comprises the perovskite oxide-transition metal phosphide heterostructure composite electrode material of claim 1.
10. Use of the perovskite oxide-transition metal phosphide heterostructure composite electrode material as defined in claim 1 for the preparation of an oxygen reduction, oxygen evolution or hydrogen evolution electrode material.
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