CN102044680A - Densification method of Sr2MgMoO6 type cell anode material - Google Patents

Densification method of Sr2MgMoO6 type cell anode material Download PDF

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CN102044680A
CN102044680A CN2010105625487A CN201010562548A CN102044680A CN 102044680 A CN102044680 A CN 102044680A CN 2010105625487 A CN2010105625487 A CN 2010105625487A CN 201010562548 A CN201010562548 A CN 201010562548A CN 102044680 A CN102044680 A CN 102044680A
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mgmoo
sintering
sample
reducing
electrode
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CN102044680B (en
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赵海雷
谢志翔
杜志鸿
陈婷
周雄
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a densification method of a Sr2MgMoO6 type cell anode material, belonging to the field of fuel cells. The densification method uses an oxidation-reduction two-stage sintering method to improve the density of the material and comprises the following steps: when sintering in an air atmosphere, adding MoO3 power to serve as a bedding for a sample so as to cause MoO3 vapour pressure to be generated in the process of sintering, thus preventing Mo loss in the material; and reducing the sample sintered in the air in a reducing atmosphere, so as to generate oxygen vacancies in the sample and expand crystal lattices, thus the material is more compact and the physical properties of the material is beneficial to be represented. For a porous electrode material, by using the two-stage sintering method, the particles of the electrode can be closely integrated, thus ensuring good structural stability of the electrode and forming a transport network of electrons and ions. In addition, the densification method is used to promote the close integration of anode materials and electrolyte materials, thus reducing the interface resistance of the cell and improving the performance characteristics of the cell.

Description

A kind of Sr 2MgMoO 6Type battery anode material densifying method
Technical field
The invention belongs to fuel cell field, be specifically related to a kind of double-perovskite type (A 2BB ' O 6) anode of solid oxide fuel cell material Sr 2MgMoO 6The preparation method, particularly to the research of this material densification.
Background technology
U.S.'s " science " magazine in 2006 (Y.H.Huang, I.D.Ronald, Z.L.Xing et al.Science, 2006, reported the orderly Sr in a kind of B position on 312:254) 2MgMoO 6The anode of solid oxide fuel cell material, it is a kind of mixed conductor of structure of double perovskite, its oxygen-ion conduction and electronic conductance are all than higher, and good sulfur poisoning-resistant and anti-carbon deposition ability are arranged, the electrochemical reaction of combustion gas occurs on entire electrode/gas boundary, and being not limited to three phase boundary, this greatly reduces the polarization resistance of battery.Sr 2MgMoO 6It is a kind of very rising SOFC anode material.But, Sr 2MgMoO 6Complicated process of preparation since under reducing atmosphere MoO 3Change MoO easily into 2, MoO 2In lower temperature generation gas takes place easily to decompose, it is fine and close to cause final material to be difficult to, and the conductivity of its intrinsic and the mechanism of action of doped chemical just are difficult to characterize.On the other hand,, also need between the particle of electrode to combine closely, form the transmission network of electronic and ionic to guarantee good electrode structure stability though in battery, require anode material to have certain porosity.Simultaneously, the anode material good sintering property helps combining closely of itself and electrolyte, reduces the interface resistance of battery, improves battery working characteristic.
According to document D.Marrero-Lopez, J.Pena-Martinez, J.C.Ruiz-Morales, et al.Synthesis, phase stability and electrical conductivity of Sr2MgMoO 6-δAnode, Materials Research Bulletin, 2008 (43): the 2441-1450 report: material is difficult to densification under reducing atmosphere, has a large amount of intercommunicating pores.The material of sintering has density relatively preferably in air atmosphere, but conductivity is lower again, only is 3 * 10 -3S/cm.In order to make material have good density, and keep higher conductivity, we adopt the redox two-step method to carry out sintering.
Summary of the invention
The objective of the invention is to improve Sr by the redox two-step method 2MgMoO 6The density of material is guaranteeing between the anode material particle and in anode material and the electrolyte good combination, the accuracy of assurance material furnish component, and can improve this material electric conductivity.
A kind of Sr 2MgMoO 6The densifying method of type battery anode material is characterized in that:
Step a, to uniform Sr 2MgMoO 6-δPowder adds the 1-10%PVA solution of powder quality mark, and dry-pressing formed in the steel casting mould after mixing, wherein crucible is put into the material of moulding in 0≤δ≤1, crucible bottom layer overlay MoO 3Powder, sintering 5-12h under 1300-1600 ℃, in the air atmosphere, the Sr that obtains having certain intensity 2MgMoO 6Material;
Step b, the Sr that will have certain intensity 2MgMoO 6The H of material under 800-1500 ℃ 2With reduce 10-30h, wherein H in the mixed atmosphere of Ar 2Volumn concentration be 2-10%, obtain fine and close Sr 2MgMoO 6Material is used for material structure and characterizes and electric performance test.
The present invention is by add MoO in crucible 3Powder, thus in the process of heating, produce MoO 3Vapour pressure prevents the disappearance under the Mo high temperature in the sample, guarantees the consistency of materials chemistry component.At first sintering under oxidizing atmosphere makes each component formation solid solution in the material, and preliminary densification, solid-solution material with gained reduces under reducing atmosphere then, owing in reduction process, can produce oxygen loss, thus produce the oxygen room, material generation lattice dilatation further makes the material densification.Simultaneously, the generation in oxygen room has also improved the ionic conductance and the electronic conductance of material.
Description of drawings
The Sr that Fig. 1 synthesizes for the present invention 2MgMoO 6-δ(0≤δ≤1), synthesis temperature are 1500 ℃ of air atmospheres, the surface sweeping Electronic Speculum figure of insulation 10h
The Sr that Fig. 2 synthesizes for the present invention 2MgMoO 6-δ(0≤δ≤1), synthesis temperature are 1500 ℃ of insulations of air atmosphere 10h, then at H 2With reductase 12 4h, wherein H in the mixed atmosphere of Ar 2Volumn concentration be that 5% reduction temperature is 1300 ℃ a sem photograph
Embodiment
Embodiment 1
To the uniform Sr for preparing 2MgMoO 6-δAdding mass fraction in the powder is 1%PVA solution, mixes 115MPa is used in the back in the steel casting mould pressure dry-pressing rectangularity bar, puts into Al 2O 3In the ceramic crucible, and put into one deck MoO in crucible bottom 3Powder, under 1300 ℃, sintering 5h makes it obtain having the Sr of certain intensity in the air atmosphere 2MgMoO 6Material.With the sample that obtains with certain intensity at H 2In the mixed atmosphere of Ar, H wherein 2Volumn concentration be 2%, reduction temperature is 800 ℃, reduction 10h obtains final fine and close sample.
Embodiment 2
To the uniform Sr for preparing 2MgMoO 6-δAdding mass fraction in the powder is 3%PVA solution, mixes 115MPa is used in the back in the steel casting mould pressure dry-pressing rectangularity bar, puts into Al 2O 3In the ceramic crucible, and put into one deck MoO in crucible bottom 3Powder, under 1500 ℃, sintering 10h makes it obtain having the Sr of certain intensity in the air atmosphere 2MgMoO 6Material.With the sample that obtains with certain intensity at H 2In the mixed atmosphere of Ar, H wherein 2Volumn concentration be 5%, reduction temperature is 1300 ℃, reductase 12 4h obtains final fine and close sample.
Embodiment 3
To the uniform Sr for preparing 2MgMoO 6-δAdding mass fraction in the powder is 10%PVA solution, mixes back dry-pressing rectangularity bar in the steel casting mould, puts into Al 2O 3In the ceramic crucible, and put into one deck MoO in crucible bottom 3Powder, under 1600 ℃, sintering 12h makes it obtain having the Sr of certain intensity in the air atmosphere 2MgMoO 6Material.With the sample that obtains with certain intensity at H 2In the mixed atmosphere of Ar, H wherein 2Volumn concentration be 10%, reduction temperature is 1500 ℃, reduction 30h obtains final fine and close sample.

Claims (2)

1. Sr 2MgMoO 6The densifying method of type battery anode material is characterized in that:
Step a, to uniform Sr 2MgMoO 6-δPowder adds the 1-10%PVA solution of powder quality mark, and dry-pressing formed in the steel casting mould after mixing, wherein crucible is put into the material of moulding in 0≤δ≤1, crucible bottom layer overlay MoO 3Powder, sintering 5-12h under 1300-1600 ℃, in the air atmosphere obtains Sr 2MgMoO 6Material;
Step b, with the Sr that obtains 2MgMoO 6The H of material under 800-1500 ℃ 2With reduce 10-30h, wherein H in the mixed atmosphere of Ar 2Volumn concentration be 2-10%, obtain fine and close Sr 2MgMoO 6Material.
2. the densifying method of battery anode material as claimed in claim 1, it is characterized in that: among the described step a, sintering temperature is 1500 ℃, and sintering time is 10h; Among the described step b, reduction temperature is 1300 ℃, and the recovery time is 24h.
CN201010562548A 2010-11-23 2010-11-23 Densification method of Sr2MgMoO6 type cell anode material Expired - Fee Related CN102044680B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI577638B (en) * 2015-10-23 2017-04-11 行政院原子能委員會核能研究所 Strontium magnesium molybdenum oxide material having double perovskite structure and method for preparing the same
WO2019205830A1 (en) * 2018-04-25 2019-10-31 中南大学 Method for promoting densification of metal body by utilizing metal hydrogen absorption expansion
CN111471460A (en) * 2020-05-13 2020-07-31 徐州森普光电科技有限公司 High-color-purity high-thermal-stability red fluorescent material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101867048A (en) * 2010-05-10 2010-10-20 北京科技大学 High-conductivity double perovskite aluminum-doped Sr2AlxMg1-xMoO6-Delta anode material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101867048A (en) * 2010-05-10 2010-10-20 北京科技大学 High-conductivity double perovskite aluminum-doped Sr2AlxMg1-xMoO6-Delta anode material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《Journal of Solid State Chemistry》 20090306 D.Marrero-lopez et al High temperature phase transition in SOFC anodes base on Sr2MgMoO6-delta 全文 1-2 第182卷, *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI577638B (en) * 2015-10-23 2017-04-11 行政院原子能委員會核能研究所 Strontium magnesium molybdenum oxide material having double perovskite structure and method for preparing the same
WO2019205830A1 (en) * 2018-04-25 2019-10-31 中南大学 Method for promoting densification of metal body by utilizing metal hydrogen absorption expansion
US11219949B2 (en) 2018-04-25 2022-01-11 Central South University Method for promoting densification of metal body by utilizing metal expansion induced by hydrogen absorption
CN111471460A (en) * 2020-05-13 2020-07-31 徐州森普光电科技有限公司 High-color-purity high-thermal-stability red fluorescent material and preparation method thereof
CN111471460B (en) * 2020-05-13 2022-12-09 徐州森普光电科技有限公司 High-color-purity high-thermal-stability red fluorescent material and preparation method thereof

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