CN102658152B - Method for preparing oxygen electrode perovskite-type catalyst - Google Patents
Method for preparing oxygen electrode perovskite-type catalyst Download PDFInfo
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- CN102658152B CN102658152B CN201210115318.5A CN201210115318A CN102658152B CN 102658152 B CN102658152 B CN 102658152B CN 201210115318 A CN201210115318 A CN 201210115318A CN 102658152 B CN102658152 B CN 102658152B
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Abstract
The invention relates to the technical field of an oxygen electrode catalyst, in particular to a method for preparing an oxygen electrode perovskite-type catalyst. The method comprises the steps as follows: (1), nitrate of needed metallic elements is accurately weighed based on determinated stoichiometric proportion according to components of the perovskite-type catalyst needing to be prepared, and is mixed and dissolved in a solvent, wherein, the solvent is one of organic solvents such as acetone, ethylene glycol, alcohol and propyl alcohol or is mixed solution comprising a plurality of the organic solvents; (2) citric acid is added in the dissolved mixture and used as a complexing agent, uniform ultrasonic dispersion is carried in an ultrasonic dispersion instrument, and punchy stirring is carried out through a stirrer at the same time, and so that an amorphous precursor is generated; and (3) wet gel is obtained after the dehydration is performed in a water bath case and then is put in a drying cabinet for drying to obtain honeycomb dried gel, and the dried gel is ground, is put in a muffle furnace for calcination, and then is cooled down until the room temperature is reached so as to obtain the catalyst with a perovskite structure. The oxygen electrode perovskite-type catalyst can be widely used in basic metal-air batteries, fuel cells and electrolyzed water industry.
Description
Technical field
The present invention relates to oxygen electrode catalyst technical field, especially a kind of preparation method of oxygen electrode perovskite type catalyst.
Background technology
Difunctional oxygen electrode, due to its application in fuel cell, metal-air battery, basic hydrolysis industry, is the study hotspot in electrochemical field for a long time always.Develop that single to make again oxygen generation evolution reaction have the oxygen electrode difficulty of catalytic activity to oxygen generation reduction reaction very large.First, in the aqueous solution oxygen to separate out with the irreversible degree of hydrogen reduction be very high; Secondly, oxygen evolution reaction will carry out under higher positive potential, there will be in this case electrode holder dissolving and migration in electrolyte solution as the corrosion of (material with carbon element) and catalyst, thus the life-span of having reduced difunctional oxygen electrode.So it must be chemically stable requiring electrode catalyst and carrier, the corrosion of electrolyte-resistant, can sludge proof.Up to now, the oxygen reduction electrode catalyst of studying has: carbon, platinum and platinum alloy, silver, metallo-chelate, metal oxide (Mn oxide, spinel oxides, Pyrochlore oxides, perofskite type oxide) etc.
That perofskite type oxide has is inexpensive, catalytic activity is high, more stable in aqueous slkali, can resistance to oxidation, have higher electron conduction under room temperature, there is the advantage such as paramagnetism and oxygen defect, be the electrocatalysis material of the promising difunctional oxygen electrode of tool; Secondly, perovskite composite oxide is owing to having higher specific area, and chemical stability is cheap, is easy to make, and higher activity in alkaline solution, replaces noble metal gradually.In solid fuel cell and metal-air battery, be widely used.The preparation of perovskite type metal oxide mainly contains acetate decomposition method, coprecipitation, calcination, ball-milling method, microemulsion method, amorphous precursors method etc.The catalyst of wherein preparing with sol-gal process has that catalytic activity is high, purity is high, reaction is easy to the advantages such as control and extensive concern.There are patent and report domestic morning, as " air electrode perovskite catalyst and preparation method thereof " application number 03102420.3.
Summary of the invention
In order to overcome preparation method's the deficiency of existing perovskite type metal oxide, the invention provides a kind of preparation method of oxygen electrode perovskite type catalyst.
The technical solution adopted for the present invention to solve the technical problems is: the object of the present invention is to provide a kind of method of preparing high-performance oxygen electrode catalyst.This catalyst has active high, stable performance, and long service life, produces raw material source and enriches, and production technology is simple, the feature not high to equipment requirement.
Perovskite type catalyst prepared by this technology, chemical formula is AB
xb'
1-Xo
3(0≤X≤1), the present invention takes collosol and gel ultrasonic method to prepare the catalyst of the type, takes to make solvent with organic solvent.In general, the preparation of gel is all in water system environment, and this can cause serious particle agglomeration phenomenon, and in the time of gel-forming, the liquid water molecules being mingled in gel is to cause the nanoparticle main cause of combination again.In the time that wet gel forms, if with common sol-gal process, so a large amount of free water molecules reacts with the hydroxyl on colloidal particles surface and forms hydrogen bond.In the time of start vaporizer, what evaporate is solvent, therefore this can not produce capillarity, follow the continuation evaporation of solution, the gel on liquid curved surface can produce a large amount of defects, therefore, particulate is meeting combination again under capillarity, this contributes to hydrone and hydroxyl to form hydrogen bond, and when gel is during in roasting, this hydrogen bond can produce strong again in conjunction with the combination degree again between effect and strengthening particulate.In order to reduce the surface tension of wet gel and to improve the dispersibility of particle, crucial problem is blocks moisture and combination bridge hydroxy.The present invention replaces deionized water can well avoid above-mentioned problem with organic solvent, obviously increases catalytic performance thereby this technology can effectively reduce the dispersiveness of the size increase particle of nano-perovskite particle; If adopt miscible organic solvent mutually to make double solvents, due in the gel water smoking, the boiling point difference of each solvent, after when evaporation, the volatilization of solvent has and first has, carry out so continuous dehydration, be aided with again at this moment ultrasonic wave and disperse, utilize the strong ultrasonic cavitation of ultrasonic wave, effectively stop agglomeration, the gel quality affects making is better.
The preparation method of above-mentioned catalyst adopts collosol and gel ultrasonic method, the method comprises the following steps: take metal nitrate as raw material, (1) composition of the perovskite type catalyst of preparing according to need, the nitrate of required metallic element is mixed by definite stoichiometric proportion, and solvent is one or more mixed solution of the organic solvents such as acetone, ethylene glycol, ethanol, propyl alcohol;
(2) add citric acid to make complexing agent to the dissolving mixt in step (1), adding proportion is metal ion mol ratio: citric acid is 1:1 ~ 1:10, ultrasonic being uniformly dispersed in ultrasonic wave separating apparatus, ultrasonic power is 0.1W-10W/g citric acid, ultrasonic time is 4-24 hour, carry out strong stirring with agitator simultaneously, make it generate amorphous precursor.
(3) in water bath, in 30-90 ℃, dehydration obtains wet gel, proceed to again 100-200 ℃ of oven dry in drying box and obtain cellular xerogel, after grinding, proceed in Muffle furnace under air or oxygen atmosphere in 500-800 ℃ of calcining 1～6 hour, then cool to room temperature obtains having the catalyst of perovskite structure.
The invention has the beneficial effects as follows, 1, high to hydrogen reduction catalytic activity, the oxygen electrode making at-0.4V(with respect to Hg/HgO electrode) current density can reach 267mA/cm
2, see accompanying drawing 1;
2, the life-span long, cyclic voltammetry shows: after 60 circle circulations, catalytic performance, without obvious decay, is shown in accompanying drawing 2;
3, manufacture craft is simple, and raw material source is abundant, and manufacturing process does not produce pollution, is easy to amplify and produces.
4, applied widely, this catalyst can be widely used in alkalinous metal air cell, fuel cell, and brine electrolysis industry.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is polarization curve of the present invention;
Fig. 2 is cyclic voltammogram of the present invention;
Fig. 3 is catalyst XRD figure of the present invention.
The specific embodiment
The invention provides the preparation method of oxygen electrode perovskite type catalyst, detailed preparation process is described and is seen above face summary of the invention part, below further sets forth the present invention with example.
Embodiment 1
Be that 1:0.8:0.2 takes lanthanum nitrate 10.83g, nickel nitrate 5.82g, cobalt nitrate 1.46g is raw material by stoichiometry mol ratio La:Ni:Co, after dissolving in acetone, by metal ion mol ratio: citric acid is that 1:2 adds citric acid thing to make complexing agent, in ultrasonic wave separating apparatus, disperse, ultrasonic temperature is 28 ℃, and ultrasonic power is 80W, ultrasonic time is 15 hours, stir with agitator, until form thickness colloid, adjustment bath temperature is 80 ℃ and dewaters simultaneously; The wet gel obtaining is proceeded in drying box to 120 ℃ and dryly within 4 hours, obtain xerogel, proceed in Muffle furnace and in 600 ℃, calcine and within 3 hours, obtain required catalyst after grinding, chemical formula is
laNi 0.8 co 0.2 o 3 , crystal structure is shown in accompanying drawing 3.
Embodiment 2
Be that 1:0.8:0.2 takes lanthanum nitrate 21.63g, nickel nitrate 11.64g, cobalt nitrate 2.91g is raw material by stoichiometry mol ratio La:Ni:Co, after dissolving in the acetone of volume ratio 1:1 and the mixed solvent of absolute ethyl alcohol, add citric acid 31.52g to make complexing agent, in ultrasonic wave separating apparatus, disperse, ultrasonic temperature is 28 ℃, and ultrasonic power is 60W, ultrasonic time is 24 hours, stir with agitator, until form thickness colloid, adjustment bath temperature is 30 ℃ and dewaters simultaneously; The wet gel obtaining is proceeded in drying box to 100 ℃ and dryly within 4 hours, obtain xerogel, proceed in Muffle furnace and in 500 ℃, calcine and within 6 hours, obtain required catalyst after grinding, chemical formula is
laNi 0.8 co 0.2 o 3 .
Embodiment 3
Be that 1:0.8:0.2 takes lanthanum nitrate 21.63g, nickel nitrate 11.64g, cobalt nitrate 2.91g is raw material by stoichiometry mol ratio La:Ni:Co, after dissolving in the mixed solvent of absolute ethyl alcohol, add citric acid 31.52g to make complexing agent, in ultrasonic wave separating apparatus, disperse, ultrasonic temperature is 28 ℃, and ultrasonic power is 100W, ultrasonic time is 4 hours, stir with agitator, until form thickness colloid, adjustment bath temperature is 90 ℃ and dewaters simultaneously; The wet gel obtaining is proceeded in drying box to 200 ℃ and dryly within 4 hours, obtain xerogel, proceed in Muffle furnace and in 800 ℃, calcine and within 1.5 hours, obtain required catalyst after grinding, chemical formula is
laNi 0.8 co 0.2 o 3 .
Claims (1)
1. a preparation method for oxygen electrode perovskite type catalyst, catalyst, chemical formula is
laNi 0.8 co 0.2 o 3 , it is characterized in that, the method comprises the following steps:
(1) composition of the perovskite type catalyst of preparing according to need, by definite stoichiometric proportion accurately take the nitrate of required metallic element and in solvent mixed dissolution, described solvent is one or more mixed solution of acetone, ethylene glycol, ethanol, propyl alcohol;
(2) add citric acid to make complexing agent to the dissolving mixt in step (1), adding proportion is metal ion mole: citric acid is 1:1～1:10, ultrasonic being uniformly dispersed in ultrasonic wave separating apparatus, ultrasonic power is 0.1W-10W/g citric acid, ultrasonic time is 4-24 hour, carry out strong stirring with agitator simultaneously, make it generate amorphous precursor;
(3) in water bath, in 30-90 ℃, dehydration obtains wet gel, proceed to again 100-200 ℃ of oven dry in drying box and obtain cellular xerogel, after grinding, proceed in Muffle furnace under air or oxygen atmosphere in 500-800 ℃ of calcining 1～6 hour, then cool to room temperature obtains oxygen electrode perovskite type catalyst.
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| CN108579751B (en) * | 2018-04-12 | 2021-06-11 | 南京工业大学 | Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis |
| CN113451594A (en) * | 2020-03-26 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Cathode material of solid oxide fuel cell and preparation method thereof |
| JP7474328B2 (en) * | 2020-07-11 | 2024-04-24 | Ｄｏｗａエレクトロニクス株式会社 | Perovskite-type composite oxide powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426123A (en) * | 2003-01-28 | 2003-06-25 | 天津大学 | Air electrode perovskite catalyst and its preparing method |
| US7259126B2 (en) * | 2004-03-11 | 2007-08-21 | Ceramatec, Inc. | Gas diffusion electrode and catalyst for electrochemical oxygen reduction and method of dispersing the catalyst |
| CN101884930A (en) * | 2010-07-07 | 2010-11-17 | 昆明理工大学 | Perovskite LaxCa1-xCoO3/Ag Composite Powder Oxygen Reduction Catalyst and Preparation Method |
| CN102166517A (en) * | 2011-03-21 | 2011-08-31 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426123A (en) * | 2003-01-28 | 2003-06-25 | 天津大学 | Air electrode perovskite catalyst and its preparing method |
| US7259126B2 (en) * | 2004-03-11 | 2007-08-21 | Ceramatec, Inc. | Gas diffusion electrode and catalyst for electrochemical oxygen reduction and method of dispersing the catalyst |
| CN101884930A (en) * | 2010-07-07 | 2010-11-17 | 昆明理工大学 | Perovskite LaxCa1-xCoO3/Ag Composite Powder Oxygen Reduction Catalyst and Preparation Method |
| CN102166517A (en) * | 2011-03-21 | 2011-08-31 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
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