CN114005999B - Bifunctional electrocatalyst and preparation method and application thereof - Google Patents

Bifunctional electrocatalyst and preparation method and application thereof Download PDF

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CN114005999B
CN114005999B CN202111037583.1A CN202111037583A CN114005999B CN 114005999 B CN114005999 B CN 114005999B CN 202111037583 A CN202111037583 A CN 202111037583A CN 114005999 B CN114005999 B CN 114005999B
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CN114005999A (en
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贺贝贝
潘国宏
赵凌
公衍生
王欢文
汪锐
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Zhejiang Research Institute China University Of Geosciences Wuhan
China University of Geosciences
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a bifunctional electrocatalyst and a preparation method and application thereof. The core of the bifunctional electrocatalyst is perovskite-like oxide nano-fiber with a chemical formula of Pr z Sr 2‑z Ni y Co 1‑ y O 2‑ε Z = 0-2, y = 0-1, epsilon = 0-0.25, and the outer layer is hetero-atom doped CeO deposited by ALD technology 2 Film Fe x Ce 1‑ x O 2‑δ And the Fe doping ratio x = 0-0.3. The preparation method comprises the steps of firstly obtaining the perovskite-like oxide nano-fiber PSNC, placing the nano-fiber PSNC into an ALD system cavity, heating in vacuum, and carrying out cyclic deposition on the nano-fiber PSNC to obtain the iron-doped cerium oxide film deposited on the nano-fiber PSNC. The bifunctional electrocatalyst disclosed by the invention can keep excellent ORR/OER catalytic activity under an alkaline condition, and shows good multiplying power and cycle performance when being applied to a zinc-air battery cathode catalyst.

Description

Bifunctional electrocatalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a bifunctional electrocatalyst and a preparation method and application thereof.
Background
Metal-air batteries have received much attention in the energy storage and conversion field because of their green, clean, high energy density, recyclable and other advantages. The zinc air battery has a large-scale application commercial prospect due to the abundant earth reserves, low price and strong corrosion resistance in alkaline electrolyte. Oxygen Evolution Reaction (OER) and Oxygen Reduction Reaction (ORR) are used as two important half reactions of a cathode of the zinc-air battery, and due to the fact that an electron transfer process is complex and the reaction has high overpotential, the energy efficiency of the zinc-air battery is low, and therefore research on a corresponding bifunctional electrocatalyst is particularly important.
Although the noble metal-based catalyst has high catalytic activity, the noble metal-based catalyst has less reserves, high price and single function, thereby causing difficulty for large-scale application of the noble metal-based catalyst. The research of non-noble metal-based catalysts has become a hot spot in this field. The perovskite type oxide has low price, abundant reserves and adjustable electronic structure, thereby having higher potential electrocatalytic activity. However, the electronic conductivity and intrinsic catalytic activity of the perovskite material prepared by the traditional solid phase reaction method are low, and the nano-sized catalyst introduced on the surface of the oxide can obviously increase active sites and improve the catalytic activity, so that the high-efficiency and stable catalyst meeting the commercial requirement is expected to be obtained.
The current methods for nano-modification of catalysts are generally mechanical mixing and grinding method, impregnation method and chemical vapor deposition method. The contact area between the nano particles and the oxide electrode particles is small, the adhesion force is weak, and the long-term stability of the modified compound is poor; the impregnation method and the vapor deposition method require subsequent high-temperature treatment to deposit the nano catalyst on the particle surface, which may damage the structure and the original morphology of the oxide; not only the modified species are not distributed uniformly, but also the impregnation amount is poor in controllability, the modified amount is not easy to control, the process period is long, and the preparation cost is high, so that the practical application of the modified species is limited.
Disclosure of Invention
The invention aims to provide a bifunctional electrocatalyst which maintains excellent ORR/OER catalytic activity under alkaline conditions and shows good multiplying power and cycle performance when applied to a zinc-air battery cathode catalyst, and a preparation method and application thereof, aiming at the defects in the prior art.
The invention relates to a bifunctional electrocatalyst, the inner core of which is perovskite-like oxide nano fiber with a chemical formula of Pr z Sr 2-z Ni y Co 1-y O 2-ε Z = 0-2, y = 0-1, epsilon = 0-0.25, and the outer layer is hetero-atom doped CeO deposited by ALD technology 2 Film Fe x Ce 1-x O 2-δ Wherein the doping proportion x = 0-0.3 of metal Fe, and the doping proportion delta = 0-0.1.
Further, z is 0.5, 1.0 or 1.5, y is 0.5, x is 0, 0.1, 0.2 or 0.3.
A method for preparing the bifunctional electrocatalyst, comprising the following steps:
s1: according to the chemical formula Pr z Sr 2-z Ni y Co 1-y O 2-ε Respectively weighing Pr source, sr source, ni source and Co source according to stoichiometric ratio, sequentially dissolving in organic solvent, stirring until completely dissolved, adding polyvinylpyrrolidone, and continuously stirring until the solution is viscous;
s2: spinning the solution by using an electrostatic spinning technology, and drying after the spinning is finished;
s3: the dried spinning is pre-oxidized and kept warm to form a phase, thus obtaining the perovskite-like oxide nanofiber Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 2-ε Recorded as PSNC;
s4: putting the nanofiber PSNC into an ALD system cavity, raising the temperature in vacuum, performing cyclic deposition on the nanofiber PSNC by adopting an atomic layer deposition technology to obtain a layer of iron-doped cerium oxide film which is uniformly deposited on the nanofiber PSNC, and controlling the thickness of the deposited film by the number of cycles; and controlling the proportion of Fe and Ce in the film according to the circulation times of each element in the circulation ring.
Further, the Pr source in step S1 is Pr (NO) 3 ) 3 ·6H 2 O, sr source is Sr (NO) 3 ) 3 The Ni source is Ni (NO) 3 ) 2 ·6H 2 O or Ni (CH) 3 COO) 2 ·4H 2 O, co sources including Co (NO) 3 ) 2 ·6H 2 O; the Pr (NO) 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 The molar ratio of O is 1; the organic solvent is N, N-dimethylformamide.
Further, the electrostatic spinning technology in the step S2 adopts the negative pressure of 2.5-3 kV, the positive pressure of 15-20 kV, the receiving distance of 15-20 cm and the injection speed of 0.06-0.08 mm min -1 。
Further, in step S3, the temperature is controlled at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 Heating to 850-900 ℃ and preserving the temperature for 5 hours to carry out phase formation to obtain the nano fiber PSNC;
further, in step S4, the iron source used is ferrocene Fe (Cp) 2 The cerium source is Ce (iPrCp) 2 (iPr-amd)。
Further, the specific operation of performing cyclic deposition on the nanofiber PSNC in step S4 is as follows: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → nx (H) 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2 s), the value of n is determined by the composition ratio of the deposits.
Further, in step S4, the atomic layer deposition parameters are: the ALD system has a chamber pressure of 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and an iron source heating temperature of 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the number of cycles is 26-105.
The application of the bifunctional electrocatalyst is coated on carbon paper of a positive current collector of a zinc-air battery.
The bifunctional electrocatalyst can keep excellent ORR/OER catalytic activity under an alkaline condition, shows good multiplying power and cycle performance when being applied to a zinc-air battery cathode catalyst, can obviously reduce the overpotential on an air electrode, improves the energy density and power efficiency, and enhances the long-term charge and discharge stability when being applied to the assembly and test of a zinc-air battery.
The preparation method of the invention is to deposit a layer of cerium oxide with different iron doping amounts outside the nanofiber prepared by electrostatic spinning by utilizing an atomic layer deposition technology, and can carry out precise modification on the composition and thickness of a coating layer of the cerium oxide. According to the preparation method, the surface modification of the nano catalyst can be efficiently and quickly realized through the ALD technology, the components, the proportion and the thickness of the deposit can be accurately controlled, the ALD-modified perovskite-based composite material is applied to the cathode catalyst of the zinc-air battery, and the commercial application approach of the zinc-air battery can be expanded.
Drawings
FIG. 1 is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ -79cycles X-ray powder diffraction pattern;
FIG. 2a is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ SEM (scanning Electron microscope) picture of 79 cycles;
FIGS. 2b and 2c are PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ TEM (transmission electron microscopy) images of 79 cycles;
FIG. 2d is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ -79cycles of element maps;
FIG. 3a is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ 79cycles with PSNC and commercial iridium oxide catalyst at 0.1mol L -1 LSV curve of OER performance in KOH solution;
FIG. 3b is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ 79cycles with PSNC and commercial iridium oxide catalyst at 0.1mol L -1 LSV curve of ORR performance in KOH solution;
FIG. 4 is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ -79cycles and PSNC nanofibers assembled zinc air cell polarization performance test curve;
FIG. 5 shows PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ -79cycles and PSNC nanofibers assembled zinc air battery to perform a rate capability test curve;
FIG. 6 is PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ Zinc air battery assembled by-79 cycles and PSNC nano-fiber at current density of 5mA cm -2 A discharge performance test curve performed under the condition;
FIG. 7 shows PSNC @ Fe prepared in example 2 0.1 Ce 0.9 O 2-δ A zinc-air battery assembled by nano fibers of 79cycles and PSNC at 10mA cm -2 The cycle performance test curve performed under the conditions of (1).
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in N, N-dimethylformamide (20mL), stirring to dissolve completely, adding polyvinylpyrrolidone (2.2 g), and stirring for 10 hrSpinning by using electrostatic spinning technology after the solution is in a viscous state, wherein the parameters of a spinning machine are set to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity, 20cm of receiving distance and 0.08mm min of injection speed -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
PSNC nanofibers are placed in an ALD cavity to be heated in vacuum, ceO with different Fe doping contents is deposited after nitrogen purging and cleaning 2 Coating to obtain PSNC @ Fe x Ce 1-x O 2-δ To find the optimum Fe doping ratio, wherein the metal Fe doping ratio x =0, 0.1, 0.2, 0.3. The ALD system chamber pressure during deposition is about 1Torr, the deposition window temperature is 150-250 deg.C, the tube temperature is 150 deg.C, the cerium source heating temperature is 150 deg.C, and the iron source heating temperature is 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen (99.999%) is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the thickness of a deposited film is controlled by the number of cycles; the proportion of Fe to Ce in the composite film was controlled by the number of small cycles of each element in the cycle, and the number of deposition cycles in this example was 26 cycles. Fe x Ce 1-x O 2-δ One deposition cycle sequence of (a) is: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → nx (H) 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2 s), the value of n is determined by the composition ratio of the deposits. PSNC @ CeO obtained after ALD deposition 2 -26cycles、PSNC@Fe 0.1 Ce 0.9 O 2-δ -26cycles、PSNC@Fe 0.2 Ce 0.8 O 2-δ -26cycles, and PSNC @ Fe 0.3 Ce 0.7 O 2-δ -26cycles bifunctional catalytic material.
The OER and ORR performance of the electrocatalyst materials for each different iron doping ratio is shown in table 1. It can be seen that PSNC @ Fe is adopted when the iron doping molar ratio is 0.1 0.1 Ce 0.9 O 2-δ OER performance of 26cycles with an initial potential of 1.48V at 10mA cm -2 The corresponding potential is 1.68V, which is obviously lower than other iron doping content; in ORR Performance, PSNC @ Fe 0.1 Ce 0.9 O 2-δ Half-wave potential of-26 cycles is 0.7V, and limiting current density is-4.67 mA cm -2 Also, it is superior to other iron doping ratios, indicating that the electrocatalytic activity is the highest and the oxygen exchange kinetics are faster when the iron doping ratio is 0.1 in the iron-doped cerium oxide, and thus the optimum iron doping amount is determined to be 0.1.
TABLE 1 summary of OER and ORR Performance of deposition of cerium oxides of different iron doping ratios on PSNC nanofibers according to the invention
Figure BDA0003247837180000061
Figure BDA0003247837180000071
Example 2:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in 20mL of N, N-dimethylformamide in sequence, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity, 20cm of receiving distance and 0.08mm min of injection speed -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 Heating to 850 ℃ and preserving the temperature for 5 hours to carry out phase formation to obtain the PSNC nano fiberAnd (5) maintaining.
PSNC nanofibers are placed in an ALD cavity to be heated in vacuum, and after nitrogen purging and cleaning, iron oxide and cerium oxide are alternately deposited. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and an iron source heating temperature of 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen (99.999%) is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the thickness of a deposited film is controlled by the number of cycles; the proportion of Fe and Ce in the composite film is controlled by the small circulation times of each element in the circulation ring. The deposition cycle sequence of the Fe/Ce oxide in this example is: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2s, deposition number 79cycles in this example. PSNC @ Fe obtained after ALD deposition is finished 0.1 Ce 0.9 O 2-δ -79cycles bifunctional catalytic material.
Referring to the attached figure 1, PSNC @ Fe prepared according to the technical scheme of the embodiment 0.1 Ce 0.9 O 2-δ An X-ray powder diffraction pattern of-79 cycles, which shows a one-to-one correspondence with the peaks of PSNC, but does not show particularly distinct peaks of iron oxide or cerium oxide, which may be related to the amorphous structure of the outer coating layer and the very small amount of coating.
Refer to FIG. 2a for PSNC @ Fe prepared according to the embodiment 0.1 Ce 0.9 O 2-δ SEM (scanning Electron microscope) image of 79cycles, from which it can be seen that it is a one-dimensional nanofiber structure with a diameter of about 250nm and is relatively uniformly distributed. FIGS. 2b and 2c are PSNC @ Fe prepared according to the embodiment 0.1 Ce 0.9 O 2-δ TEM (Transmission Electron microscopy) image of 79cycles, from which it can be seen that the nanofibers have a uniform amorphous coating outside, the thickness of the coating being related to the number of ALD depositions cycles, indicating the successful preparation of the core-shell structure. FIG. 2d is PSNC @ Fe 0.1 Ce 0.9 O 2-δ 79cycles element map, it can be observed that each element distribution isThe fiber is uniform and has no segregation, and in addition, a small amount of Fe and Ce elements are distributed on the fiber, thereby further illustrating the existence of the surface coating layer.
To demonstrate the electrocatalytic properties of the catalyst, the amount of the catalyst was 0.1mol L -1 Oxygen evolution and oxygen reduction performance tests were performed in KOH solution at 1600 rpm. The test is completed by using a three-electrode test system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a platinum electrode, and a working electrode is formed by coating 2 mu L of catalyst slurry on a platinum-carbon electrode. The catalyst slurry was prepared by mixing 40mg of catalyst, 10mg of Ketjen black, 5mL of ethanol, and 250. Mu.L of Nafion solution and sonicating for two hours.
Refer to FIG. 3a, which is PSNC @ Fe prepared according to the embodiment 0.1 Ce 0.9 O 2-δ 79cycles with PSNC and commercial iridium oxide catalyst at 0.1mol L -1 LSV curve of OER performance in KOH solution. PSNC @ Fe 0.1 Ce 0.9 O 2-δ The-79 cycles show excellent OER catalytic activity, the initial potential is 1.4V, and compared with 1.5V of iridium oxide, the catalyst has lower cost and higher commercial value. At 10mA cm -2 At a current density of (3), PSNC @ Fe 0.1 Ce 0.9 O 2-δ The potential for the-79 cycles is 1.55V, which is clearly lower than PSNC (1.72V) and the commercial catalyst iridium oxide (1.69V), indicating a faster oxygen exchange kinetics. Refer to FIG. 3b for PSNC @ Fe prepared according to the embodiment 0.1 Ce 0.9 O 2-δ 79cycles with PSNC and commercial iridium oxide catalyst at 0.1mol L -1 LSV curve of ORR performance in KOH solution. In comparison with PSNC (0.67V, 4.51mA cm) -2 ) And platinum carbon (0.89V, 5.26mA cm) -2 )，PSNC@Fe 0.1 Ce 0.9 O 2-δ -79cycles(0.72V，5.56mA cm -2 ) Has higher half-wave potential and limiting current density, and shows that the catalyst has optimal ORR catalytic activity.
The zinc-air battery is a liquid water system zinc-air battery assembled by taking a zinc sheet as a negative electrode and air as an electrochemical reaction substance of a positive electrode and taking the prepared bifunctional electrocatalyst as an air cathode catalyst. 25mg of catalyst and 6.25mg of Ketjen blackAfter mixing and grinding for 20 minutes, 1mL of ethanol and 380mL of Nafion solution are added and fully mixed, then the mixture is uniformly coated on 10 carbon paper blocks of 2X 2cm, and the carbon paper blocks are placed in a vacuum oven at 60 ℃ to be dried for 10 hours for later use. The negative electrode of the zinc-air battery uses a zinc sheet, and the electrolyte is 6mol L -1 KOH and 0.2mol L of -1 The mixed solution of zinc acetate. And assembling the anode, the cathode, the electrolyte, the diaphragm and the like into the zinc-air battery for testing.
See attached FIG. 4 for PSNC @ Fe 0.1 Ce 0.9 O 2-δ The polarization performance test curve of a zinc-air battery assembled by 79cycles and PSNC nano fibers can be seen from the graph, PSNC @ Fe 0.1 Ce 0.9 O 2-δ The maximum power density of a zinc-air battery assembled by 79cycles of catalysts can reach 195mW cm -2 Obviously higher than PSNC 102mW cm -2 Is also higher than the commercial catalyst Pt/C + IrO 2 84mW cm -2 Its good output performance may be due to the excellent bifunctional catalytic activity of the catalyst itself.
See FIG. 5, PSNC @ Fe 0.1 Ce 0.9 O 2-δ -79cycles and PSNC nanofibers assembled zinc air battery to carry out rate performance test curve. Shown in the figure, PSNC @ Fe 0.1 Ce 0.9 O 2-δ The 79cycles catalyst showed a relatively smooth plateau at each current density plateau and when the current density was returned to 1mA cm -2 When the voltage was restored to 1.24V, indicating that the zinc-air cell was excellent in reversibility.
See FIG. 6, PSNC @ Fe 0.1 Ce 0.9 O 2-δ The zinc-air battery assembled by the-79 cycles and the PSNC nano fibers is at 5mA cm -2 Discharge performance test curve performed under the conditions of (1). PSNC @ Fe is shown in the figure 0.1 Ce 0.9 O 2-δ The-79 cycles discharge continuously for nearly 39 hours, better than 27 hours for PSNC, and the voltage is more stable without significant drop.
See FIG. 7 for PSNC @ Fe 0.1 Ce 0.9 O 2-δ The zinc-air battery assembled by-79 cycles and PSNC nano fibers is at 10mA cm -2 Conditions of (2)The cycle performance test curve performed below. Load PSNC @ Fe 0.1 Ce 0.9 O 2-δ The zinc-air battery of the-79 cycles catalyst is continuously charged and discharged for about 280 hours, 1375 cycle periods, and has better cycle stability than PSNC.
PSNC@Fe 0.1 Ce 0.9 O 2-δ The 79cycles catalyst has excellent OER and ORR dual-function catalytic activity and zinc-air battery performance, because the ohmic loss is reduced due to the doping of Fe in the coating layer, the ionic conductivity is improved, and meanwhile, the substrate with the fiber structure also provides larger surface area and exposes more active sites.
Example 3:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in 20mL of N, N-dimethylformamide in sequence, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity, 20cm of receiving distance and 0.08mm min of injection speed -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
PSNC nanofibers are placed in an ALD cavity to be heated in vacuum, nitrogen is blown and cleaned, and iron oxide and cerium oxide are alternately deposited. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and an iron source heating temperature of 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen (99.999%) is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the thickness of a deposited film is controlled by the number of cycles; to be provided withThe small circulation times of each element in the circulation ring control the proportion of Fe and Ce in the composite film. The deposition cycle sequence of the Fe/Ce oxide in this example is: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2s, deposition turns 53 in this example. PSNC @ Fe obtained after ALD deposition is finished 0.1 Ce 0.9 O 2-δ -53cycles bifunctional catalytic material.
The main XRD structure and SEM appearance of the catalyst are similar to those of example 2, the electrocatalytic performance and the zinc-air battery performance of the catalyst are superior to those of a PSNC catalyst, but the electrocatalytic performance and the zinc-air battery performance of the catalyst are not as good as those of a PSNC @ Fe catalyst 0.1 Ce 0.9 O 2-δ Catalysts of 79cycles, e.g. PSNC @ Fe 0.1 Ce 0.9 O 2-δ OER curves at 10mA cm for-53 cycles -2 Corresponding to a potential of 1.66V at a current density of 1.66V, and half-wave potential and limiting current density of 0.69V and 5.22mA cm in ORR test, respectively -2 。
Example 4:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in 20mL of N, N-dimethylformamide in sequence, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity, 20cm of receiving distance and 0.08mm min of injection speed -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
Putting PSNC nano-fiber into ALD cavity in vacuumAnd heating, purging and cleaning by nitrogen, and simultaneously alternately depositing iron oxide and cerium oxide. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and an iron source heating temperature of 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen (99.999%) is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the thickness of a deposited film is controlled by the number of cycles; the proportion of Fe and Ce in the composite film is controlled by the small circulation times of each element in the circulation ring. The deposition cycle sequence of the Fe/Ce oxide in this example is: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2s, deposition turns of 105 in this example. PSNC @ Fe is obtained after ALD deposition is finished 0.1 Ce 0.9 O 2-δ -105cycles bifunctional catalytic material.
The main XRD structure and SEM appearance of the catalyst are similar to those of example 1, the electrocatalytic performance and the zinc-air battery performance of the catalyst are superior to those of a PSNC catalyst, but the electrocatalytic performance and the zinc-air battery performance of the catalyst are not as good as those of a PSNC @ Fe catalyst 0.1 Ce 0.9 O 2-δ Catalysts of 79cycles, e.g. PSNC @ Fe 0.1 Ce 0.9 O 2-δ OER curve at 10mAcm for-105 cycles -2 The corresponding potential is 1.64V at a current density of 1.64V, and the half-wave potential and the limiting current density in the ORR test are 0.7V and 5.46mA cm, respectively -2 。
Example 5:
according to the chemical formula Pr 1.0 Sr 1.0 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in 20mL of N, N-dimethylformamide in sequence, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, spinning by using an electrostatic spinning technology, setting the parameters of a spinning machine to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity and 20cm of receiving distance, and injectingThe speed is 0.08mm min -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
PSNC nanofibers are placed in an ALD cavity to be heated in vacuum, nitrogen is blown and cleaned, and iron oxide and cerium oxide are alternately deposited. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and an iron source heating temperature of 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen (99.999%) is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the thickness of a deposited film is controlled by the number of cycles; the proportion of Fe and Ce in the composite film is controlled by the small circulation times of each element in the circulation ring. The deposition cycle sequence of the Fe/Ce oxide in this example is: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2s, deposition number 79cycles in this example. Pr after ALD deposition 1.0 Sr 1.0 Ni 0.5 Co 0.5 O 4-ε @Fe 0.1 Ce 0.9 O 2-δ -79cycles bifunctional catalytic material.
The main XRD structure and SEM appearance of the zinc-air battery are similar to those of example 2, and the electrocatalytic performance and the zinc-air battery performance of the zinc-air battery are superior to those of undeposited pure Pr 1.0 Sr 1.0 Ni 0.5 Co 0.5 O 4-ε Catalyst, but with a higher OER-ORR potential difference than PSNCC @ Fe in example 2 0.1 Ce 0.9 O 2-δ 79cycles catalyst.
Example 6:
according to the chemical formula Pr 1.5 Sr 0.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Sequentially dissolving O in 20mL of N, N-dimethylformamide, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be negative pressure of 3kV, positive pressure of 16kV, humidity of 30%, receiving distance of 20cm and injection speed of 0.08mm min -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
PSNC nanofibers are placed in an ALD cavity to be heated in vacuum, and after nitrogen purging and cleaning, iron oxide and cerium oxide are alternately deposited. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and an iron source heating temperature of 80 deg.C to provide sufficient saturated vapor pressure. High-purity nitrogen (99.999%) is used as carrier gas for deposition, the flow rate of ozone is 400sccm, and the thickness of a deposited film is controlled by the number of cycles; the proportion of Fe and Ce in the composite film is controlled by the small circulation times of each element in the circulation ring. The deposition cycle sequence of the Fe/Ce oxide in the embodiment is as follows: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purge 2s → H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2s, deposition number 79cycles in this example. Pr after ALD deposition 1.5 Sr 0.5 Ni 0.5 Co 0.5 O 4-ε @Fe 0.1 Ce 0.9 O 2-δ -79cycles bifunctional catalytic material.
The main XRD structure and SEM appearance of the zinc-air battery are similar to those of example 2, and the electrocatalytic performance and the zinc-air battery performance of the zinc-air battery are superior to those of undeposited pure Pr 1.5 Sr 0.5 Ni 0.5 Co 0.5 O 4-ε Catalyst, but with a higher OER-ORR potential difference than PSNCC @ Fe in example 2 0.1 Ce 0.9 O 2-δ 79cycles catalyst.
Example 7:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Sequentially dissolving O in 20mL of N, N-dimethylformamide, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be negative pressure of 3kV, positive pressure of 16kV, humidity of 30%, receiving distance of 20cm and injection speed of 0.08mm min -1 . After spinning, the fiber was dried in a forced air drying oven at 60 ℃ for 12 hours, and then dried at 0.5 ℃ for min -1 Heating to 220 deg.C at a heating rate for 2 hr for pre-oxidation, and maintaining at 0.5 deg.C for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
Putting the PSNC nano-fiber into an ALD (atomic layer deposition) cavity, heating in vacuum, purging and cleaning by nitrogen, and depositing titanium oxide and cerium oxide alternately. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150 deg.C, a manifold temperature of 150 deg.C, a cerium source heating temperature of 150 deg.C, and a titanium source TDMAT heating temperature of 75 deg.C to provide sufficient saturated vapor pressure. The deposition uses high-purity nitrogen (99.999%) as carrier gas, and the thickness of the deposited film is controlled by the number of cycles; and controlling the ratio of Ti to Ce in the composite film by using the small cycle times of each element in the cycle ring. The deposition cycle sequence of the Ti/Ce oxide in this example is: h 2 O pulse 0.02s → dwell 30s → Ti (NMe) 2 ) 4 Pulse 0.4s → dwell 20s → N 2 Purge 2s → H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2s, deposition number 79cycles in this example. PSNC @ Ti is obtained after ALD deposition is finished 0.1 Ce 0.9 O 2-δ -79cycles bifunctional catalytic material. The main XRD structure and SEM appearance are similar to those of example 2.
Example 8:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in 20mL of N, N-dimethylformamide in sequence, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity, 20cm of receiving distance and 0.08mm min of injection speed -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And (4) heating to 850 ℃, and keeping the temperature for 5 hours to carry out phase formation to obtain the PSNC nanofiber.
Putting the PSNC nano-fiber into an ALD (atomic layer deposition) cavity, heating in vacuum, purging and cleaning by nitrogen, and simultaneously alternately depositing zinc oxide and cerium oxide. Wherein the ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-170 deg.C, a tube temperature of 150 deg.C, and a cerium source heating temperature of 150 deg.C to provide sufficient saturated vapor pressure without the need for heating the zinc source DEZ. The deposition uses high-purity nitrogen (99.999%) as carrier gas, and the thickness of the deposited film is controlled by the number of cycles; and controlling the proportion of Zn and Ce in the composite film by using the small cycle times of each element in the cycle ring. The number of deposition turns in this example was 79. PSNC @ Zn is obtained after ALD deposition is finished 0.1 Ce 0.9 O 2-δ -79cycles bifunctional catalytic material. The main XRD structure and SEM appearance are similar to those of example 2.
Example 9:
according to the chemical formula Pr 0.5 Sr 1.5 Ni 0.5 Co 0.5 O 4-ε Separately weighing Pr (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 Dissolving O in 20mL of N, N-dimethylformamide in sequence, stirring until the O is completely dissolved, adding 2.2g of polyvinylpyrrolidone, continuously stirring for 10 hours until the solution is in a viscous state, and spinning by using an electrostatic spinning technology, wherein the parameters of a spinning machine are set to be 3kV of negative pressure, 16kV of positive pressure, 30% of humidity, 20cm of receiving distance and 0.08mm min of injection speed -1 . After spinning, the fiber was dried in a 60 ℃ forced air drying oven for 12 hours and then at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And heating to 850 ℃ and preserving the temperature for 5 hours to carry out phase formation to obtain the PSNC nano fiber.
Putting the PSNC nano-fiber into an ALD (atomic layer deposition) cavity, raising the temperature in vacuum, purging and cleaning by nitrogen, and simultaneously alternately depositing aluminum oxide and cerium oxide. The ALD system has a chamber pressure of about 1Torr, a deposition window temperature of 150-250 deg.C, a tube temperature of 150 deg.C, and a cerium source heating temperature of 150 deg.C to provide sufficient saturated vapor pressure, and the aluminum source TMA does not need to be heated. The deposition uses high-purity nitrogen (99.999%) as carrier gas, and the thickness of the deposited film is controlled by the number of cycles; the proportion of Al and Ce in the composite film is controlled by the small circulation times of each element in the circulation ring. The number of deposition turns in this example was 79. PSNC @ Al is obtained after ALD deposition is finished 0.1 Ce 0.9 O 2-δ -79cycles bifunctional catalytic material. The main XRD structure and SEM appearance are similar to those of example 2.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention shall be included in the scope of the present invention.

Claims (10)

1. A bifunctional electrocatalyst, characterized by: the core of the bifunctional electrocatalyst is perovskite-like oxide nano-fiber with a chemical formula of Pr z Sr 2-z Ni y Co 1-y O 2-ε Z = 0-2, y = 0-1, epsilon = 0-0.25, and the outer layer is hetero-atom doped CeO deposited by ALD technology 2 Film Fe x Ce 1-x O 2-δ Wherein the doping proportion x = 0-0.3 of metal Fe, and the doping proportion delta = 0-0.1.
2. A bifunctional electrocatalyst according to claim 1, wherein: z is 0.5, 1.0 or 1.5, y is 0.5, x is 0, 0.1, 0.2 or 0.3.
3. A method of preparing a bifunctional electrocatalyst according to claim 1 or 2, characterised in that: the method comprises the following steps:
s1: according to the chemical formula Pr z Sr 2-z Ni y Co 1-y O 2-ε Respectively weighing Pr source, sr source, ni source and Co source according to stoichiometric ratio, sequentially dissolving in organic solvent, stirring until completely dissolved, adding polyvinylpyrrolidone, and continuously stirring until the solution is viscous;
s2: spinning the solution by using an electrostatic spinning technology, and drying after the spinning is finished;
s3: the dried spinning is pre-oxidized and kept warm to form a phase, and the perovskite-like oxide nanofiber Pr is obtained z Sr 2-z Ni y Co 1- y O 2-ε Recorded as PSNC;
s4: putting the nanofiber PSNC into an ALD system cavity, raising the temperature in vacuum, performing cyclic deposition on the nanofiber PSNC by adopting an atomic layer deposition technology to obtain a layer of iron-doped cerium oxide film which is uniformly deposited on the nanofiber PSNC, and controlling the thickness of the deposited film by large number of cycles; and controlling the proportion of Fe and Ce in the film according to the circulation times of each element in the circulation ring.
4. A method of making a bifunctional electrocatalyst according to claim 3, wherein: the Pr source in step S1 is Pr (NO) 3 ) 3 ·6H 2 O, sr source is Sr (NO) 3 ) 3 The Ni source is Ni (NO) 3 ) 2 ·6H 2 O or Ni (CH) 3 COO) 2 ·4H 2 O, co sources including Co (NO) 3 ) 2 ·6H 2 O; the Pr (NO) 3 ) 3 ·6H 2 O，Sr(NO 3 ) 3 ，Ni(NO 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 The molar ratio of O is 1; the organic solvent is N, N-dimethylformamide.
5. A method of making a bifunctional electrocatalyst as claimed in claim 4, wherein: the electrostatic spinning technology in the step S2 adopts the negative pressure of 2.5-3 kV, the positive pressure of 15-20 kV, the receiving distance of 15-20 cm and the injection speed of 0.06-0.08 mm min -1 。
6. A method of making a bifunctional electrocatalyst according to claim 3, wherein: in step S3, the temperature is controlled at 0.5 ℃ for min -1 Raising the temperature to 220 ℃ at the heating rate, preserving the heat for 2 hours for pre-oxidation, and finally carrying out pre-oxidation at the temperature of 0.5 ℃ for min -1 And raising the temperature to 850-900 ℃ and preserving the temperature for 5 hours to carry out phase formation to obtain the nano-fiber PSNC.
7. A method of making a bifunctional electrocatalyst according to claim 3, wherein: in step S4, the iron source is ferrocene Fe (Cp) 2 The cerium source is Ce (iPrCp) 2 (iPr-amd)。
8. A method of making a bifunctional electrocatalyst according to claim 7, wherein: the specific operation of performing the cyclic deposition on the nanofiber PSNC in the step S4 is as follows: o is 3 Pulse 0.5s → dwell 8s → Fe (Cp) 2 Pulse 1s → dwell 15s → N 2 Purging 2s→n×(H 2 O pulse 0.02s → dwell 30s → Ce (iPrCp) 2 (iPr-amd) pulse 0.5s → dwell 20s → N 2 Purge 2 s), the value of n is determined by the compositional proportion of the deposit.
9. A method of making a bifunctional electrocatalyst according to claim 8, wherein: in step S4, the atomic layer deposition parameters are: the ALD system has a cavity pressure of 1Torr, a deposition window temperature of 150-250 ℃, a pipeline temperature of 150 ℃, a cerium source heating temperature of 150 ℃, and an iron source heating temperature of 80 ℃ to provide enough saturated vapor pressure, high-purity nitrogen is used as a carrier gas for deposition, the ozone flow is 400sccm, and the number of cycle turns is 26-105 turns.
10. Use of a bifunctional electrocatalyst according to claim 1, wherein: coating on the positive current collector carbon paper of the zinc-air battery.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1529374A (en) * 2003-10-08 2004-09-15 华南理工大学 Zinc-air battery electrocatalyst and preparation method thereof
CN104600324A (en) * 2015-02-02 2015-05-06 安阳工学院 Perovskite cathode film and preparation method thereof
CN108493460A (en) * 2018-01-23 2018-09-04 宁波大学 A kind of perovskite/cerium oxide VPO catalysts and its precipitation composite preparation process
CN108579751A (en) * 2018-04-12 2018-09-28 南京工业大学 Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis
CN110142039A (en) * 2019-06-12 2019-08-20 中国科学院宁波材料技术与工程研究所 A kind of preparation method of catalyst and its application in metal-air battery
CN110152677A (en) * 2019-05-20 2019-08-23 宁波大学 A kind of difunctional compound VPO catalysts of perovskite/cerium oxide with biomimetic features

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1529374A (en) * 2003-10-08 2004-09-15 华南理工大学 Zinc-air battery electrocatalyst and preparation method thereof
CN104600324A (en) * 2015-02-02 2015-05-06 安阳工学院 Perovskite cathode film and preparation method thereof
CN108493460A (en) * 2018-01-23 2018-09-04 宁波大学 A kind of perovskite/cerium oxide VPO catalysts and its precipitation composite preparation process
CN108579751A (en) * 2018-04-12 2018-09-28 南京工业大学 Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis
CN110152677A (en) * 2019-05-20 2019-08-23 宁波大学 A kind of difunctional compound VPO catalysts of perovskite/cerium oxide with biomimetic features
CN110142039A (en) * 2019-06-12 2019-08-20 中国科学院宁波材料技术与工程研究所 A kind of preparation method of catalyst and its application in metal-air battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
可充锌空气电池非贵金属阴极催化剂研究进展;安亚苹等;《现代化工》(第03期);全文 *
锌空气电池非贵金属双功能阴极催化剂研究进展;朱子岳等;《储能科学与技术》;20200905(第05期);全文 *

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