WO2012116506A1 - Procédé de préparation d'une poudre d'oxyde métallique composite - Google Patents

Procédé de préparation d'une poudre d'oxyde métallique composite Download PDF

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Publication number
WO2012116506A1
WO2012116506A1 PCT/CN2011/072145 CN2011072145W WO2012116506A1 WO 2012116506 A1 WO2012116506 A1 WO 2012116506A1 CN 2011072145 W CN2011072145 W CN 2011072145W WO 2012116506 A1 WO2012116506 A1 WO 2012116506A1
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WIPO (PCT)
Prior art keywords
metal oxide
composite metal
hours
oxide
oxide powder
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PCT/CN2011/072145
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English (en)
Chinese (zh)
Inventor
颜雪冬
王蔚国
王建新
孙嘉隆
Original Assignee
中国科学院宁波材料技术与工程研究所
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Publication of WO2012116506A1 publication Critical patent/WO2012116506A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • the present invention relates to the field of metal oxide technology, and more particularly to a method for preparing a composite metal oxide powder.
  • Composite metal oxide inorganic materials have characteristics such as gas sensitivity, magnetic properties, ionic conductivity and catalytic activity, and are widely used in information, energy, electronics, metallurgy, aerospace, chemical, biological and medical fields.
  • the electrolyte material is a zirconia-based composite oxide or ruthenium oxide group with a fluorite structure.
  • the zirconia-based composite oxide may be yttrium-stabilized zirconia (Z ri _ x Y x 0 2 _ s , abbreviated as YSZ), or yttrium-stabilized zirconia (Z ri _ x Sc x 0 2 _ s , abbreviated as ssz),
  • the cerium oxide-based composite oxide may be cerium-doped cerium oxide (C ei _ x Gd x 0 2 _, abbreviated as GDC);
  • the cathode material is cerium manganese having a perovskite structure Oxygen (L ai _ x Sr x Mn03-8 , abbreviated as LSM), Abbreviated as LSC), samarium cobalt ferrite
  • a multi-component composite metal oxide such as LSCF), abbreviated as BSCF).
  • the structure of the material is closely related to its performance, and different preparation processes have a direct impact on its structure.
  • liquid phase methods such as coprecipitation method, citrate method, EDTA-CA compound method, spray pyrolysis, etc. are often used in laboratory preparation.
  • the publication number is CN1586020A, and the Chinese invention patent entitled “Composite Oxide for Solid Oxide Fuel Cell and Its Manufacturing Method” is prepared by coprecipitation method (La Srx zCo ⁇ FeyO ⁇ powder, which is complicated in process and powder The agglomeration is serious; the publication number is CN1471188A, the Chinese invention patent entitled “A Method for Preparing Superfine Powder of Medium Temperature Solid Oxide Fuel Cell Electrolyte”, the cathode powder is prepared by the EDTA-CA composite method.
  • Organic matter and ammonia water have low atomic utilization rate, and excessive gas is generated during the post-treatment process, causing the precursor to be seriously expanded or even the powder is ejected, and the product is difficult to collect, and the yield is low, which is not suitable for industrial production.
  • the product prepared by the liquid phase method has small particles and narrow particle size distribution, it is first necessary to configure a clear and transparent precursor solution.
  • these metal salts only nitrate has good solubility and low price, so nitrate is often used as its reaction system.
  • the high-valent metal ion salt has a large amount of nitrate, and in order to keep the composition uniform, during the drying process, A large amount of complexing agent is added, and these nitrates and complexing agents are finally decomposed and stripped off. Therefore, the atomic utilization rate of the reaction system is very low, not efficient green synthesis, and the decomposition of these nitrates produces a large amount of NO and N0 2 Harmful gas, which is highly polluting to the environment and cannot be industrially produced.
  • the solid phase method is the main method for producing composite metal oxide powders in the industry due to its simple process and low cost.
  • due to the complex composition of the composite metal oxide it is difficult to form a phase, requiring a high synthesis temperature and a long synthesis time.
  • the publication No. 101222060 entitled “A Medium and Low Temperature Solid Oxide Fuel Cell Cathode Material” Chinese invention patent, uses the solid phase method to prepare B ai _ x Sr x C 0l - y Fe y 0 3 _ s powder After calcination at 1100 ° C for 10 hours, the energy consumption is high, the product particles are large, the particle size is uneven, and the agglomeration is serious.
  • the technical problem to be solved by the invention is to prepare a composite metal oxide powder by the existing solid phase method and the liquid phase method. Disadvantages, providing a method for preparing a composite metal oxide powder, which overcomes the disadvantages of high cost, complicated process, and unfriendly to the liquid phase method; the disadvantage of high energy consumption and poor product performance of the solid phase method is low Cost, high performance, environmentally friendly preparation process for industrial production.
  • a method for preparing a composite metal oxide powder specifically comprising the following steps:
  • Step 1 According to the stoichiometric ratio of the composite metal oxide, a corresponding dose of oxide, carbonate, acetate or oxalate of each metal element, and an appropriate amount of deionized water are added to the ball mill tank for ball milling for 5 hours. ⁇ 10 hours to get the slurry;
  • Step 2 adding a readily soluble organic substance and a small amount of deionized water to the slurry obtained in the step 1, and performing ball milling for 1 hour to 5 hours, wherein the easily soluble organic substance is a carboxylic acid organic substance, and the mass percentage is The readily soluble organic matter accounts for 10% to 50% of the composite metal oxide;
  • Step 3 Remove the slurry obtained in step 2 and put it in a high temperature oven for drying;
  • Step 4 The dried product obtained in the step 3 is placed in an electric furnace and calcined at 600 ° C to 900 ° C in an air atmosphere to obtain a composite metal oxide powder product.
  • the composite metal oxide is preferably a composite metal oxide having a fluorite structure or a composite metal oxide having a perovskite structure.
  • the composite metal oxide of the fluorite structure is preferably a zirconia-based composite oxide or a cerium oxide-based composite oxide, and the composite metal oxide of the perovskite structure is preferably lanthanum manganese oxide or lanthanum cobalt oxide. , samarium cobalt ferrite or samarium cobalt ferrite.
  • the soluble organic matter is preferably one or a mixture of two or more of citric acid, glucose, sucrose, acrylic acid, oxalic acid, and ascorbic acid.
  • the drying temperature in the step 3 is preferably from 100 ° C to 300 ° C, and the drying time is preferably from 3 hours to 8 hours.
  • the invention adds a low-cost soluble organic matter in the process of preparing the composite metal oxide powder by the solid phase method, and utilizes the energy of the ball mill to complex the soluble organic matter with the metal ion, so that the reaction system is in the process of drying and calcining.
  • the composition is kept uniform, stable, and does not cause segregation, thereby preventing element precipitation, reducing the phase formation difficulty of the composite metal oxide powder product, and improving the purity of the product; secondly, the soluble organic matter is uniformly dispersed after being dissolved, during the heat treatment process.
  • the preparation method of the present invention has the following advantages as compared with the prior art:
  • the composite metal oxide powder prepared by the preparation method of the present invention has small crystal grains, pure phase phase, uniform particle size, less agglomeration, and good sintering activity.
  • the raw material does not need to be dissolved, that is, the nitrate system is not used, so no NO, N0 2 harmful gas is generated; and the amount of soluble organic matter is small, and the active ingredient is large, so the atomic utilization rate of the reaction system is high; Only a small amount of H 2 0, C0 2 is emitted, and the amount of exhaust gas emissions is small relative to other reaction systems, and the preparation method of the present invention is environmentally friendly as compared with the liquid phase method.
  • the high-purity composite metal oxide powder product can be produced at a relatively low temperature and for a short period of time, and the preparation method of the present invention saves energy compared with the solid phase method.
  • Example 1 is an X-ray diffraction pattern of a perovskite-type LSM powder prepared in Example 1;
  • Example 2 is a scanning electron micrograph of a perovskite-type LSM powder prepared in Example 1;
  • Figure 3 is an X-ray diffraction pattern of the fluorite-type YSZ powder prepared in Example 2;
  • Fig. 4 is a scanning electron micrograph of the fluorite-type YSZ powder prepared in Example 2.
  • step (3) The slurry obtained after the ball milling in step (2) is transferred into an oven and dried at 120 ° C for 7 hours;
  • Figure 1 is an X-ray diffraction pattern of the perovskite-type LSM powder prepared by the above method. It can be seen from the figure that the LSM powder prepared by the method is a high-purity perovskite powder at 750 ° C. That is, completely pure phase, which significantly reduces the pure phase temperature compared to the conventional solid phase method.
  • Fig. 2 is a scanning electron micrograph of the perovskite-type LSM powder prepared by the above method. It can be seen that the LSM powder has a small particle size and a uniform particle size, ranging from 200 nm to 500 nm with substantially no agglomeration.
  • Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 250 ° C for 4 hours;
  • FIG. 3 is an X-ray diffraction pattern of the fluorite-type YSZ powder prepared by the above method. It can be seen from the figure that the YSZ powder prepared by the method is a high-purity fluorite type powder, and the conventional solid phase method is very It is difficult to prepare high-purity fluorite-based YSZ o.
  • Figure 4 is a scanning electron micrograph of the fluorite-type YSZ powder prepared by the above method. It can be seen from the figure that the YSZ powder particles are small, the agglomeration is small, and the particle size is Powders from 200 nm to 500 nm.
  • Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 150 ° C for 8 hours;
  • the dried product obtained in the step (3) is placed in an electric furnace and heat-treated at 800 ° C to obtain LSC powder having a small particle size, a narrow particle size distribution range, and a particle diameter of 200 nm to 500 nm.
  • Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 200 ° C for 5 hours;
  • the dried product obtained in the step (3) is placed in an electric furnace and heat-treated at 850 ° C to obtain a LSCF powder having a small particle size, a narrow particle size distribution range, and a particle diameter of 200 nm to 500 nm.
  • Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 250 ° C for 4 hours;
  • the dried product obtained in the step (3) is placed in an electric furnace and heat-treated at 900 ° C to obtain a SSZ powder having a small particle size, a narrow particle size distribution range, and a particle diameter of 200 nm to 500 nm.
  • Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 300 ° C for 3 hours;
  • the dried product obtained in the step (3) is placed in an electric furnace and heat-treated at 850 ° C to obtain a GDC powder having a small particle size, a narrow particle size distribution range, and a particle diameter of 200 nm to 500 nm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compounds Of Iron (AREA)

Abstract

Un procédé de préparation d'une poudre d'oxyde métallique composite est constitué des étapes suivantes : 1) ajout d'oxydes, de carbonates, d'acétates ou d'oxalates métalliques et d'eau déionisée, selon un rapport stœchiométrique de l'oxyde métallique composite, dans le réservoir d'une broyeuse à boulets, et broyage à boulets pour obtenir une suspension ; 2) ajout de produit organique soluble et d'une faible quantité d'eau déionisée dans la suspension obtenue dans l'étape 1), et broyage à boulets, lesdits produits organiques solubles étant des acides carboxyliques organiques dont la quantité est comprise entre 10 et environ 50 % en masse de l'oxyde métallique composite ; 3) sortie de la suspension obtenue dans l'étape 2) et introduction dans un four haute température pour séchage ; 4) introduction du produit séché obtenu dans l'étape 3) dans un four électrique, et calcination à une température comprise entre 600 et environ 900 °C sous atmosphère d'air pour obtenir la poudre d'oxyde métallique composite.
PCT/CN2011/072145 2011-02-28 2011-03-25 Procédé de préparation d'une poudre d'oxyde métallique composite WO2012116506A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 201110047954 CN102167403B (zh) 2011-02-28 2011-02-28 一种复合金属氧化物粉体的制备方法
CN201110047954.4 2011-02-28

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WO2012116506A1 true WO2012116506A1 (fr) 2012-09-07

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102728846B (zh) * 2012-07-12 2014-04-16 重庆文理学院 机械力化学法制备纳米球形面心立方结构钴粉的方法
CN105081352A (zh) * 2014-05-07 2015-11-25 中国科学院宁波材料技术与工程研究所 一种在基片上生长纳米颗粒的方法
CN106946282B (zh) * 2017-02-27 2018-12-28 广东省稀有金属研究所 一种多孔铈基复合氧化物的制备方法
CN109659547B (zh) * 2018-12-26 2020-11-13 泰州新滨江环保科技有限公司 一种用于锂电池的二元固溶体硼酸盐正极材料及制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003073125A (ja) * 2001-09-04 2003-03-12 National Institute For Materials Science イットリウム・アルミニウム・鉄複合酸化物の製造方法
CN1749171A (zh) * 2004-09-13 2006-03-22 广东工业大学 中低温固－固反应法制备纳米级铈锆复合氧化物固溶体的方法
CN101462060A (zh) * 2008-12-30 2009-06-24 上海纳米技术及应用国家工程研究中心有限公司 纳米钙钛矿型稀土氧化物的制备方法
CN101777646A (zh) * 2010-01-28 2010-07-14 新乡市中科科技有限公司 一种锂离子电池锂钒氧化物正极材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003073125A (ja) * 2001-09-04 2003-03-12 National Institute For Materials Science イットリウム・アルミニウム・鉄複合酸化物の製造方法
CN1749171A (zh) * 2004-09-13 2006-03-22 广东工业大学 中低温固－固反应法制备纳米级铈锆复合氧化物固溶体的方法
CN101462060A (zh) * 2008-12-30 2009-06-24 上海纳米技术及应用国家工程研究中心有限公司 纳米钙钛矿型稀土氧化物的制备方法
CN101777646A (zh) * 2010-01-28 2010-07-14 新乡市中科科技有限公司 一种锂离子电池锂钒氧化物正极材料的制备方法

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