CN110444778A - A method of double-perovskite oxide catalyst performance is improved using manganese dioxide - Google Patents

A method of double-perovskite oxide catalyst performance is improved using manganese dioxide Download PDF

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Publication number
CN110444778A
CN110444778A CN201910626369.6A CN201910626369A CN110444778A CN 110444778 A CN110444778 A CN 110444778A CN 201910626369 A CN201910626369 A CN 201910626369A CN 110444778 A CN110444778 A CN 110444778A
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mno
double
perovskite oxide
room temperature
cooled
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黄红霞
梁大铭
肖阳
陈富强
黄俊皓
黄隆勇
彭光万
杨砚文
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Guilin University of Technology
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Guilin University of Technology
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    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)

Abstract

α-MnO is utilized the invention discloses a kind of2To double-perovskite oxide S r2Ni0.4Co1.6O6The method being modified.Double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6.Prepare α-MnO2Process it is as follows: weigh 0.9482g KMnO4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic agitation 30min is subsequently poured into reaction kettle, dry 12h is placed in 140 DEG C of drying box, it is cooled to room temperature, with 12h is dried after dehydrated alcohol filtering and washing in 30 DEG C of drying box, obtains α-MnO2.In compound, Sr2Ni0.4Co1.6O6Content be 80%, 60%, 40%, 20% and 0%, α-MnO2Content is respectively 20%, 40%, 60%, 80% and 100%, sum of the two 100%, and the two is uniformly mixed, and α-MnO is made2Modified double-perovskite oxide S r2Ni0.4Co1.6O6.Utilize α-MnO2Double-perovskite oxide is modified, the performance of oxygen electrode improves.

Description

A method of double-perovskite oxide catalyst performance is improved using manganese dioxide
Technical field
The invention belongs to materials chemistry and electrochemical research fields, in particular to a kind of to utilize α-MnO2To double-perovskite Oxide S r2Ni0.4Co1.6O6The method being modified.
Background technique
Metal-air battery, also referred to as " half fuel " battery are a kind of one between primary battery and fuel cell Kind cleaning, efficient green battery, are made of anode, cathode and electrolyte solution.For rechargeable type metal-air battery, Catalyst has the performance of reduction oxygen, is provided simultaneously with the performance of oxidation oxonium ion.Perovskite is a kind of novel combined oxidation Object, the Acid-Base with good thermal stability, thermistor, superconducting characteristic, Capability of oxygen adsorption, ionic conductivity, surface are special Property, ferromagnetism and the features such as oxidation-reduction quality, most typical perovskite general molecular formula is ABO3.Perovskite composite oxide Stable structure, it is cheap, just have higher electron conduction at room temperature, and all have very to hydrogen reduction and oxygen evolution reaction High electro catalytic activity, therefore become the bifunctional air electrode elctro-catalyst with very big future.The present invention passes through compound difference α-MnO2Amount study the optimum value compound with double-perovskite, improve the chemical property of air electrode.
Summary of the invention
α-MnO is utilized the object of the present invention is to provide a kind of2To double-perovskite oxide S r2Ni0.4Co1.6O6Catalytic It can be carried out modified method.
Thinking of the invention: α-MnO is utilized2As modifying agent, with ABO3Type double-perovskite oxide S r2Ni0.4Co1.6O6 Modified catalyst is prepared by the method for addition, to improve the chemical property of oxygen electrode.
Specific steps are as follows:
(1) double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6.Stoichiometrically weigh respectively Strontium nitrate, nickel nitrate, cobalt nitrate and monohydrate potassium are added dehydrated alcohol dissolution, then stir 30 minutes, adjust in beaker The pH value of solution is saved, water-bath is evaporated to ethyl alcohol and is evaporated, and puts by cooled to room temperature after the drying of resulting product, then by beaker Obtained black powder is placed again into horse by 350 DEG C of pre-burning 30min in Muffle furnace, cooled to room temperature and after being fully ground Not furnace, 800 DEG C of calcining 5h after cooled to room temperature, are fully ground to obtain black powder double-perovskite oxide.
(2) 0.9482g KMnO is weighed4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic force 30min is stirred, is subsequently poured into the autoclave of polytetrafluoroethyllining lining, dry 12h is placed in 140 DEG C of drying box, it is cold But to room temperature, dehydrated alcohol filtering and washing is then used, 12h is dried after washing at 30 DEG C, obtains α-MnO2。
(3) by Sr made from step (1)2Ni0.4Co1.6O6Oxide presses 80%, 60%, 40%, 20% and 0% and step (2) α-MnO made from2It is mixed by 20%, 40%, 60%, 80% and 100% mass ratio, the sum of the two ratio is 100%, obtain α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6Modified catalyst.
The method of the present invention utilizes α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6It is modified to carry out surface, oxygen electrode Chemical property increase.
Specific embodiment
Embodiment 1:
(1) double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6.Stoichiometrically weigh respectively Strontium nitrate, nickel nitrate, cobalt nitrate and monohydrate potassium are added dehydrated alcohol dissolution, then stir 30 minutes, adjust in beaker The pH value of solution is saved, water-bath is evaporated to ethyl alcohol and is evaporated, and puts by cooled to room temperature after the drying of resulting product, then by beaker Obtained black powder is placed again into horse by 350 DEG C of pre-burning 30min in Muffle furnace, cooled to room temperature and after being fully ground Not furnace, 800 DEG C of calcining 5h after cooled to room temperature, are fully ground to obtain black powder double-perovskite oxide.
(2) 0.9482g KMnO is weighed4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic force 30min is stirred, is subsequently poured into the autoclave of polytetrafluoroethyllining lining, dry 12h is placed in 140 DEG C of drying box, it is cold But to room temperature, dehydrated alcohol filtering and washing is then used, 12h is dried after washing at 30 DEG C, obtains α-MnO2。
(3) by Sr made from step (1)2Ni0.4Co1.6O6α-MnO made from oxide and step (2)2With 80%:20% Mass ratio mixed, obtain α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6Modified catalyst.
Embodiment 2:
(1) double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6.Stoichiometrically weigh respectively Strontium nitrate, nickel nitrate, cobalt nitrate and monohydrate potassium are added dehydrated alcohol dissolution, then stir 30 minutes, adjust in beaker The pH value of solution is saved, water-bath is evaporated to ethyl alcohol and is evaporated, and puts by cooled to room temperature after the drying of resulting product, then by beaker Obtained black powder is placed again into horse by 350 DEG C of pre-burning 30min in Muffle furnace, cooled to room temperature and after being fully ground Not furnace, 800 DEG C of calcining 5h after cooled to room temperature, are fully ground to obtain black powder double-perovskite oxide.
(2) 0.9482g KMnO is weighed4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic force 30min is stirred, is subsequently poured into the autoclave of polytetrafluoroethyllining lining, dry 12h is placed in 140 DEG C of drying box, it is cold But to room temperature, dehydrated alcohol filtering and washing is then used, 12h is dried after washing at 30 DEG C, obtains α-MnO2。
(3) by Sr made from step (1)2Ni0.4Co1.6O6α-MnO made from oxide and step (2)2With 60%:40% Mass ratio mixed, obtain α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6Modified catalyst.
Embodiment 3:
(1) double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6.Stoichiometrically weigh respectively Strontium nitrate, nickel nitrate, cobalt nitrate and monohydrate potassium are added dehydrated alcohol dissolution, then stir 30min, adjust in beaker The pH value of solution is saved, water-bath is evaporated to ethyl alcohol and is evaporated, and puts by cooled to room temperature after the drying of resulting product, then by beaker Obtained black powder is placed again into horse by 350 DEG C of pre-burning 30min in Muffle furnace, cooled to room temperature and after being fully ground Not furnace, 800 DEG C of calcining 5h after cooled to room temperature, are fully ground to obtain black powder double-perovskite oxide.
(2) 0.9482g KMnO is weighed4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic force 30min is stirred, is subsequently poured into the autoclave of polytetrafluoroethyllining lining, dry 12h is placed in 140 DEG C of drying box, it is cold But to room temperature, dehydrated alcohol filtering and washing is then used, 12h is dried after washing at 30 DEG C, obtains α-MnO2。
(3) by Sr made from step (1)2Ni0.4Co1.6O6α-MnO made from oxide and step (2)2With 40%:60% Mass ratio mixed, obtain α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6Modified catalyst.
Embodiment 4:
(1) double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6.Stoichiometrically weigh respectively Strontium nitrate, nickel nitrate, cobalt nitrate and monohydrate potassium are added dehydrated alcohol dissolution, then stir 30min, adjust in beaker The pH value of solution is saved, water-bath is evaporated to ethyl alcohol and is evaporated, and puts by cooled to room temperature after the drying of resulting product, then by beaker Obtained black powder is placed again into horse by 350 DEG C of pre-burning 30min in Muffle furnace, cooled to room temperature and after being fully ground Not furnace, 800 DEG C of calcining 5h after cooled to room temperature, are fully ground to obtain black powder double-perovskite oxide.
(2) 0.9482g KMnO is weighed4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic force 30min is stirred, is subsequently poured into the autoclave of polytetrafluoroethyllining lining, dry 12h is placed in 140 DEG C of drying box, it is cold But to room temperature, dehydrated alcohol filtering and washing is then used, 12h is dried after washing at 30 DEG C, obtains α-MnO2。
(3) by Sr made from step (1)2Ni0.4Co1.6O6α-MnO made from oxide and step (2)2With 20%:80% Mass ratio mixed, obtain α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6Modified catalyst.
Catalyst made from above embodiments is tested using CHI660E electrochemical workstation, as a result as follows:
(1) in cathodic polarization curve, with the increase of current density, the absolute value of voltage value is all being become larger.In electricity Current density is 100mA.cm-2, α-MnO2Additive amount is the voltage difference of oxygen electrode corresponding to 20%, 40%, 60%, 80% For -0.518V, -0.375V, -0.468V and -0.433V.
(2) in anodic polarization curves, in current density 100mA.cm-2When, oxygen corresponding to 20%, 40%, 60%, 80% The voltage of electrode is respectively 0.761V, 0.65V, 0.705V, 0.692V；When testing blanking voltage 1V, α-MnO2Additive amount Limiting current density for oxygen electrode corresponding to 40% is 362mA.cm-2, greater than carrying current corresponding to other catalyst, Catalytic activity is best.
(3) it is added to α-MnO2Afterwards, the absolute value of electrode stable state is obviously lower, and stability is more preferable, wherein α-MnO2Add The activity of dosage catalyst corresponding when being 40% is more preferable.

Claims (1)

1. a kind of utilize α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6Modified method, it is characterised in that specific steps Are as follows:
(1) double-perovskite oxide S r is prepared using sol-gel method2Ni0.4Co1.6O6, nitric acid is stoichiometrically weighed respectively Strontium, nickel nitrate, cobalt nitrate and monohydrate potassium are added dehydrated alcohol dissolution, then stir 30 minutes, adjust molten in beaker The pH value of liquid, water-bath are evaporated to ethyl alcohol and are evaporated, and put Muffle by cooled to room temperature after the drying of resulting product, then by beaker Obtained black powder is placed again into Muffle furnace by 350 DEG C of pre-burning 30min in furnace, cooled to room temperature and after being fully ground, 800 DEG C of calcining 5h after cooled to room temperature, are fully ground to obtain black powder double-perovskite oxide；
(2) 0.9482g KMnO is weighed4, 2mL HCl (37%) and 30mL deionized water be added in 200mL beaker, magnetic agitation 30min is subsequently poured into the autoclave of polytetrafluoroethyllining lining, is placed in 140 DEG C of drying box dry 12h, is cooled to Room temperature then uses dehydrated alcohol filtering and washing, dries 12h after washing at 30 DEG C, obtains α-MnO2；
(3) by Sr made from step (1)2Ni0.4Co1.6O6By 80%, 60%, 40%, 20% and 0% and α-made from step (2) MnO2It is uniformly mixed by 20%, 40%, 60%, 80% and 100% mass ratio, the sum of the two ratio is 100%, system Obtain α-MnO2To double-perovskite oxide S r2Ni0.4Co1.6O6The catalyst of study on the modification.
CN201910626369.6A 2019-07-11 2019-07-11 A method of double-perovskite oxide catalyst performance is improved using manganese dioxide Pending CN110444778A (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113289612A (en) * 2021-04-30 2021-08-24 桂林理工大学 Synthesis of perovskite catalyst and application technical field of perovskite catalyst in methane oxidation coupling reaction
CN115028237A (en) * 2021-03-05 2022-09-09 中国石油化工股份有限公司 Electrode material for electrochemical desalination and preparation method thereof

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WO2009112953A2 (en) * 2008-03-13 2009-09-17 Uti Limited Partnership Perovskite-like structures
CN109231276A (en) * 2018-09-21 2019-01-18 桂林理工大学 Sulfamic acid restores potassium permanganate and prepares α-MnO2The method and application of nano wire

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2009112953A2 (en) * 2008-03-13 2009-09-17 Uti Limited Partnership Perovskite-like structures
CN109231276A (en) * 2018-09-21 2019-01-18 桂林理工大学 Sulfamic acid restores potassium permanganate and prepares α-MnO2The method and application of nano wire

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028237A (en) * 2021-03-05 2022-09-09 中国石油化工股份有限公司 Electrode material for electrochemical desalination and preparation method thereof
CN115028237B (en) * 2021-03-05 2024-06-07 中国石油化工股份有限公司 Electrode material for electrochemical desalination and preparation method thereof
CN113289612A (en) * 2021-04-30 2021-08-24 桂林理工大学 Synthesis of perovskite catalyst and application technical field of perovskite catalyst in methane oxidation coupling reaction

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