WO2012116506A1 - Preparation method of composite metal oxide powder - Google Patents

Preparation method of composite metal oxide powder 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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metal oxide
composite metal
hours
oxide
oxide powder
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PCT/CN2011/072145
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French (fr)
Chinese (zh)
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颜雪冬
王蔚国
王建新
孙嘉隆
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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/en

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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)
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  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compounds Of Iron (AREA)

Abstract

A preparation method of composite metal oxide powder, comprises the following steps: 1) adding metal oxides, carbonates, acetates or oxalates and deionized water, according to stoichiometric ratio of the composite metal oxide, into a ball-milling tank, and ball-milling, to obtain a slurry; 2) adding soluble organics and a little deionized water into the slurry obtained from step 1), and ball-milling, wherein said soluble organics are organics of carboxylic acids and the amount thereof is 10 ~ 50 % by mass of the composite metal oxide; 3) moving the slurry obtained from step 2) out, and putting it into a high-temperature oven for drying; 4) putting the dried product obtained from step 3) into an electric furnace, and calcining at 600~900℃ under air atmosphere to obtain the composite metal oxide powder.

Description

说 明 书  Description
一种复合金属氧化物粉体的制备方法  Preparation method of composite metal oxide powder
技术械 Technical equipment
本发明涉及金属氧化物技术领域， 尤其是涉及一种复合金属氧化物粉体的制备方 法。  The present invention relates to the field of metal oxide technology, and more particularly to a method for preparing a composite metal oxide powder.
背景技术 Background technique
复合金属氧化物无机材料具有气敏、磁性、离子导电性和催化活性等特性，在信息、 能源、 电子、 冶金、 航天、 化工、 生物和医学领域有着广泛的应用。  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.
在复合金属氧化物中，萤石与钙钛矿由于其组成和结构多变产生的多功能性而备受 关注。 在可再生能源中， 以发电效率高、 无污染著称， 用以替代传统化石能源的固体氧 化物燃料电池 (SOFC)中，电解质材料就是具有萤石结构的氧化锆基复合氧化物或氧化铈 基复合氧化物， 其中， 氧化锆基复合氧化物可以是钇稳定的氧化锆 (Zri_xYx02_s， 简写为 YSZ), 或者钪稳定氧化锆 (Zri_xScx02_s， 简写为 ssz)， 氧化铈基复合氧化物可以是钆掺 杂的氧化铈 (Cei_xGdx02_， 简写为 GDC) ; 阴极材料就是具有钙钛矿结构的镧锶锰氧 (Lai_xSrxMn03-8 , 简写为 LSM)、
Figure imgf000003_0001
简写为 LSC)、 镧锶钴铁氧
Figure imgf000003_0002
简写为 LSCF)、 简写为 BSCF)等多元复合金属氧化物。 Among the composite metal oxides, fluorite and perovskite have attracted attention due to the versatility of their composition and structure. Among renewable energy sources, in the solid oxide fuel cell (SOFC), which is used to replace traditional fossil energy, the electrolyte material is a zirconia-based composite oxide or ruthenium oxide group with a fluorite structure. a composite oxide, wherein 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),
Figure imgf000003_0001
Abbreviated as LSC), samarium cobalt ferrite
Figure imgf000003_0002
A multi-component composite metal oxide such as LSCF), abbreviated as BSCF).
材料的结构与其性能密切相关，而不同的制备工艺对其结构有着直接的影响。目前， 合成复合金属氧化物粉体的方法有很多， 实验室制备多采用液相法， 如共沉淀法、 柠檬 酸盐法， EDTA-CA复合方法、 喷雾热解等方法。 公开号为 CN1586020A, 名称为 《固体 氧化物燃料电池用复合氧化物及其制造方法》 的中国发明专利， 采用共沉淀法制备 (La Srx zCo^FeyO^粉体，此方法工艺复杂，且粉体团聚严重；公开号为 CN1471188A, 名称为《一种制备中温固体氧化物燃料电池电解质超细粉的方法》 的中国发明专利， 采 用 EDTA-CA复合方法制备阴极粉体。 由于该方法中需加入大量有机物和氨水， 原子利 用率低， 而且后处理过程中产生过多的气体， 使前驱体严重膨胀甚至将粉体喷出， 产物 难以收集， 产率低， 不适于工业生产。 另外， 以上几种液相法制备的产物虽然颗粒小， 粒度分布窄， 但是首先要配置澄清透明的前躯体溶液， 而这几种金属盐中只有硝酸盐溶 解度好， 价格低， 故而多采用硝酸盐为其反应体系， 高价金属离子盐带有大量硝酸根， 在干燥过程中为了保持组分的均一稳定， 需要加入大量的络合剂， 而这些硝酸根、 络合 剂最后都要分解、 剥离开， 因此， 反应体系的原子利用率很低， 不是高效的绿色合成， 并且这些硝酸盐分解产生大量 NO与 N02有害气体， 对环境污染大， 无法工业化生产。 The structure of the material is closely related to its performance, and different preparation processes have a direct impact on its structure. At present, there are many methods for synthesizing composite metal oxide powders, and 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. Although 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. Among 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.
固相法由于工艺简单、 成本低廉， 是工业上生产复合金属氧化物粉体的主要方法。 但是， 由于复合金属氧化物成分复杂， 成相困难， 需要很高的合成温度和很长的合成时 间。 例如， 公开号为 101222060， 名称为 《一种中低温固体氧化物燃料电池阴极材料》 的中国发明专利， 采用固相法制备 Bai_xSrxC0l-yFey03_s粉体， 在 1100°C煅烧 10个小时， 能耗高， 产物颗粒大、 粒度不均， 且团聚严重。 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. However, 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. For example, 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.
发明内容 Summary of the invention
本发明要解决的技术问题是针对现有固相法与液相法制备复合金属氧化物粉体的 缺点， 提供一种复合金属氧化物粉体的制备方法， 该方法克服了液相法成本高、 工艺复 杂、 对环境不友好； 固相法能耗高、 产物性能差的缺点， 是一种低成本、 高性能、 适合 工业化生产的环境友好型制备工艺。 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.
本发明解决上述技术问题所采用的技术方案为： 一种复合金属氧化物粉体的制备方 法， 具体包括以下步骤：  The technical solution adopted by the present invention to solve the above technical problems is as follows: A method for preparing a composite metal oxide powder, specifically comprising the following steps:
步骤 1 : 按照复合金属氧化物的化学计量比，将对应剂量的各个金属元素的氧化物、 碳酸盐、乙酸盐或草酸盐，以及适量的去离子水加入球磨罐中进行球磨 5小时〜 10小时， 得到浆料；  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;
步骤 2: 在步骤 1得到的浆料中加入易溶有机物及少量的去离子水， 进行球磨 1小 时〜 5小时， 所述的易溶有机物为羧酸类有机物， 按照质量百分比计， 所述的易溶有机 物占复合金属氧化物的 10%〜50%；  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;
步骤 3: 将步骤 2得到的浆料移出， 放入高温烘箱中烘干；  Step 3: Remove the slurry obtained in step 2 and put it in a high temperature oven for drying;
步骤 4: 将步骤 3得到的干燥产物放入电炉中， 在空气气氛下 600°C〜900°C进行煅 烧， 得到复合金属氧化物粉体产物。  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.
所述的复合金属氧化物优选为具有萤石结构的复合金属氧化物或者具有钙钛矿结 构的复合金属氧化物。  The composite metal oxide is preferably a composite metal oxide having a fluorite structure or a composite metal oxide having a perovskite structure.
所述的萤石结构的复合金属氧化物优选为氧化锆基复合氧化物或氧化铈基复合氧 化物， 所述的钙钛矿结构的复合金属氧化物优选为镧锶锰氧、 镧锶钴氧、 镧锶钴铁氧或 钡锶钴铁氧。  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.
所述的易溶有机物优选为柠檬酸、 葡萄糖、 蔗糖、 丙烯酸、 草酸、 抗坏血酸中的一 种或两种以上的混合物。  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.
所述的步骤 3中的烘干温度优选为 100°C〜300°C， 烘干时间优选 3小时〜 8小时。 本发明在固相法制备复合金属氧化物粉体过程中添加了一种价格低廉的易溶有机 物， 利用球磨的能量使该易溶有机物与金属离子络合， 使反应体系在干燥、 煅烧过程中 保持组分均一、 稳定、 不产生偏析， 从而防止元素析出， 降低了复合金属氧化物粉体产 物的成相难度， 提高了产物的纯度； 其次， 易溶有机物溶解后分散均匀， 在热处理过程 中起到空间位阻的作用， 从而抑制了复合金属氧化物粉体产物的晶粒过度生长， 以及有 效降低了复合金属氧化物粉体产物团聚的发生， 从而能够制备出晶粒小、 物相纯、 粒度 均匀、 团聚少、 烧结活性好的亚微米级粉体。  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. It acts as a steric hindrance, thereby suppressing the excessive grain growth of the composite metal oxide powder product and effectively reducing the occurrence of agglomeration of the composite metal oxide powder product, thereby enabling the preparation of small crystal grains and pure phase phases. Submicron-sized powder with uniform particle size, less agglomeration and good sintering activity.
因此， 与现有技术相比， 本发明的制备方法具有如下优点：  Therefore, the preparation method of the present invention has the following advantages as compared with the prior art:
(1) 利用本发明的制备方法制备出的复合金属氧化物粉体晶粒小、 物相纯、 粒度均 匀、 团聚少， 并且烧结活性好。  (1) 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.
(2) 原料成本低， 制备工艺简单， 只需要球磨， 烘干， 以及热处理三个步骤， 并且 效率高， 适合工业化生产。  (2) Low raw material cost, simple preparation process, only three steps of ball milling, drying, and heat treatment, and high efficiency, suitable for industrial production.
(3) 原料不需要溶解， 即不用硝酸盐体系， 因而没有 NO, N02有害气体生成； 并且 易溶有机物的添加量少， 有效成分多， 因而反应体系的原子利用率高； 另外， 制备过程 中只有少量 H20， C02排放， 相对于其他反应体系， 废气排放量少， 与液相法相比， 本 发明的制备方法对环境友好。 (4) 能够在较低的温度， 较短的时间下制备出高纯度复合金属氧化物粉体产物， 与 固相法相比， 本发明的制备方法节约能源。 (3) 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. (4) 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.
附图说明 DRAWINGS
图 1是实施例 1制备的钙钛矿型 LSM粉体的 X射线衍射图谱；  1 is an X-ray diffraction pattern of a perovskite-type LSM powder prepared in Example 1;
图 2是实施例 1制备的钙钛矿型 LSM粉体的扫描电镜图；  2 is a scanning electron micrograph of a perovskite-type LSM powder prepared in Example 1;
图 3是实施例 2制备的萤石型 YSZ粉体的 X射线衍射图谱；  Figure 3 is an X-ray diffraction pattern of the fluorite-type YSZ powder prepared in Example 2;
图 4是实施例 2制备的萤石型 YSZ粉体的扫描电镜图。  Fig. 4 is a scanning electron micrograph of the fluorite-type YSZ powder prepared in Example 2.
具体实施方式 detailed description
以下结合附图与实施例对本发明作进一步详细描述。  The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.
实施例 1 :  Example 1
制备 1千克 LSM亚微米粉体， 以下是具体的制备方法：  Preparation 1 kg of LSM submicron powder, the following is the specific preparation method:
(1) 按照 LSM化学式的化学计量比，将对应剂量的氧化镧，碳酸锶和乙酸锰加入到 球磨罐中， 加入一定量去离子水， 球磨 5小时， 得到浆料；  (1) According to the stoichiometric ratio of the LSM chemical formula, the corresponding doses of cerium oxide, cerium carbonate and manganese acetate are added to the ball milling tank, a certain amount of deionized water is added, and ball milling is carried out for 5 hours to obtain a slurry;
(2) 称量 0.1千克蔗糖溶于去离子水中， 将溶液加入步骤 (1)中的浆料中， 再球磨 2 小时使其混合均匀；  (2) Weigh 0.1 kg of sucrose dissolved in deionized water, add the solution to the slurry in step (1), and then ball mill for 2 hours to make it evenly mixed;
(3) 将步骤 (2)球磨后得到的浆料移入烘箱中， 120°C干燥 7个小时；  (3) The slurry obtained after the ball milling in step (2) is transferred into an oven and dried at 120 ° C for 7 hours;
(4) 将步骤 (3)得到的干燥产物放入电炉中， 在 750°C热处理， 得到钙钛矿型 LSM粉 体。  (4) The dried product obtained in the step (3) is placed in an electric furnace and heat-treated at 750 ° C to obtain a perovskite-type LSM powder.
图 1是上述方法制备得到的钙钛矿型 LSM粉体的 X射线衍射图谱， 从图中可以看 出： 此方法制备的 LSM粉体为高纯的钙钛矿粉体， 在 750°C下即完全纯相， 与传统固 相法相比， 显著降低了纯相温度。 图 2是上述方法制备得到的钙钛矿型 LSM粉体的扫 描电镜图， 可以看出， 该 LSM粉体颗粒小， 粒径均匀， 在 200纳米〜 500纳米之间且 基本没有团聚。  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.
实施例 2'·  Example 2'·
制备 1千克 YSZ亚微米粉体， 以下是具体的制备方法：  Preparation of 1 kg of YSZ submicron powder, the following is a specific preparation method:
(1)按照 YSZ化学式的化学计量比，将对应剂量的氧化钇，氧化锆加入到球磨罐中， 加入一定量去离子水， 球磨 6小时， 得到浆料；  (1) According to the stoichiometric ratio of the YSZ chemical formula, the corresponding dose of cerium oxide, zirconium oxide is added to the ball mill tank, a certain amount of deionized water is added, and ball milling is carried out for 6 hours to obtain a slurry;
(2)称量 0.4千克葡萄糖溶于去离子水中， 将溶液加入步骤 (1)的浆料中， 再球磨 3 小时使其混合均匀；  (2) Weighing 0.4 kg of glucose dissolved in deionized water, adding the solution to the slurry of step (1), and ball milling for 3 hours to make it evenly mixed;
(3)将步骤 (2)球磨后得到的浆料移入烘箱中， 250°C干燥 4个小时；  (3) Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 250 ° C for 4 hours;
(4)将步骤 (3)得到的干燥产物放入电炉中，在 850°C热处理，得到萤石型 YSZ粉体。 图 3是上述方法制备得到的萤石型 YSZ粉体的 X射线衍射图谱，从图中可以看出： 该方法制备的 YSZ粉体为高纯的萤石型粉体， 而传统固相法很难制备出高纯的萤石性 YSZ o 图 4是上述方法制备得到的萤石型 YSZ粉体的扫描电镜图， 从图中可以看出： 该 YSZ粉体颗粒小， 团聚少， 是粒径为 200纳米〜 500纳米的粉体。  (4) The dried product obtained in the step (3) was placed in an electric furnace and heat-treated at 850 ° C to obtain a fluorite type YSZ powder. Figure 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.
实施例 3 :  Example 3:
制备 1千克 LSC亚微米粉体， 以下是具体的制备方法：  Preparation 1 kg of LSC submicron powder, the following is the specific preparation method:
(1)按照 LSC化学式的化学计量比， 将对应剂量的氧化镧， 乙酸锶和氧化钴加入到 球磨罐中， 加入一定量去离子水， 球磨 7小时， 得到浆料； (1) According to the stoichiometric ratio of the LSC chemical formula, the corresponding doses of cerium oxide, cerium acetate and cobalt oxide are added to In a ball mill tank, a certain amount of deionized water is added, and ball milling is performed for 7 hours to obtain a slurry;
(2)称量 0.2千克柠檬酸溶于去离子水中， 将溶液加入步骤 (1)的浆料中， 再球磨 5 小时使其混合均匀；  (2) Weighing 0.2 kg of citric acid dissolved in deionized water, adding the solution to the slurry of step (1), and ball milling for 5 hours to make it evenly mixed;
(3)将步骤 (2)球磨后得到的浆料移入烘箱中， 150°C干燥 8个小时；  (3) Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 150 ° C for 8 hours;
(4)将步骤 (3)得到的干燥产物放入电炉中， 在 800°C热处理， 得到颗粒小， 粒度分 布范围窄， 粒径在 200纳米〜 500纳米的 LSC粉体。  (4) 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.
实施例 4:  Example 4:
制备 1千克 LSCF亚微米粉体， 以下是具体的制备方法：  Preparation 1 kg LSCF submicron powder, the following is the specific preparation method:
(1)按照 LSCF化学式的化学计量比， 将对应剂量的氧化镧， 乙酸锶、 氧化钴和草 酸亚铁加入到球磨罐中， 加入一定量去离子水， 球磨 8小时， 得到浆料；  (1) According to the stoichiometric ratio of the LSCF chemical formula, the corresponding doses of cerium oxide, cerium acetate, cobalt oxide and ferrous oxalate are added to a ball mill tank, a certain amount of deionized water is added, and ball milling is performed for 8 hours to obtain a slurry;
(2)称量 0.3千克丙烯酸溶于去离子水中， 将溶液加入步骤 (1)的浆料中， 再球磨 3 小时使其混合均匀；  (2) Weighing 0.3 kg of acrylic acid dissolved in deionized water, adding the solution to the slurry of step (1), and ball milling for 3 hours to make it evenly mixed;
(3)将步骤 (2)球磨后得到的浆料移入烘箱中， 200°C干燥 5个小时；  (3) Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 200 ° C for 5 hours;
(4)将步骤 (3)得到的干燥产物放入电炉中， 在 850°C热处理， 得到颗粒小， 粒度分 布范围窄， 粒径在 200纳米〜 500纳米的 LSCF粉体。  (4) 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.
实施例 5:  Example 5
制备 1千克 SSZ亚微米粉体， 以下是具体的制备方法：  Preparation 1 kg of SSZ submicron powder, the following is the specific preparation method:
(1)按照 SSZ化学式的化学计量比，将对应剂量的氧化钪，氧化锆加入到球磨罐中， 加入一定量去离子水， 球磨 9小时， 得到浆料；  (1) According to the stoichiometric ratio of the SSZ chemical formula, the corresponding dose of cerium oxide, zirconium oxide is added to the ball mill tank, a certain amount of deionized water is added, and ball milling is performed for 9 hours to obtain a slurry;
(2)称量 0.5千克草酸溶于去离子水中， 将溶液加入步骤 (1)的浆料中， 再球磨 5小 时使其混合均匀；  (2) Weighing 0.5 kg of oxalic acid dissolved in deionized water, adding the solution to the slurry of step (1), and then ball milling for 5 hours to make it evenly mixed;
(3)将步骤 (2)球磨后得到的浆料移入烘箱中， 250°C干燥 4个小时；  (3) Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 250 ° C for 4 hours;
(4)将步骤 (3)得到的干燥产物放入电炉中， 在 900°C热处理， 得到得到颗粒小， 粒 度分布范围窄， 粒径在 200纳米〜 500纳米的 SSZ粉体。  (4) 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.
实施例 6:  Example 6:
制备 1千克 GDC亚微米粉体， 以下是具体的制备方法：  Prepare 1 kg of GDC submicron powder. The following are specific preparation methods:
(1)按照 GDC化学式的化学计量比，将对应剂量的氧化钆、乙酸铈加入到球磨罐中， 加入一定量去离子水， 球磨 8小时， 得到浆料；  (1) According to the stoichiometric ratio of the GDC chemical formula, the corresponding dose of cerium oxide and cerium acetate are added to the ball milling tank, a certain amount of deionized water is added, and ball milling is performed for 8 hours to obtain a slurry;
(2)称量 0.2千克抗坏血酸溶于去离子水中， 将溶液加入步骤 (1)的浆料中， 再球磨 3小时使其混合均匀；  (2) Weighing 0.2 kg of ascorbic acid dissolved in deionized water, adding the solution to the slurry of step (1), and ball milling for 3 hours to make it evenly mixed;
(3)将步骤 (2)球磨后得到的浆料移入烘箱中， 300°C干燥 3个小时；  (3) Step (2) The slurry obtained after ball milling is transferred into an oven and dried at 300 ° C for 3 hours;
(4)将步骤 (3)得到的干燥产物放入电炉中， 在 850°C热处理， 得到得到颗粒小， 粒 度分布范围窄， 粒径在 200纳米〜 500纳米的 GDC粉体。  (4) 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.

Claims

权 利 要 求 书 Claim
1、 一种复合金属氧化物粉体的制备方法， 其特征是： 包括以下步骤:  A method for preparing a composite metal oxide powder, comprising: the following steps:
步骤 1 : 按照复合金属氧化物的化学计量比，将对应剂量的各个金属元素的氧化物、 碳酸盐、乙酸盐或草酸盐，以及适量的去离子水加入球磨罐中进行球磨 5小时〜 10小时， 得到浆料；  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;
步骤 2: 在步骤 1得到的浆料中加入易溶有机物及少量的去离子水， 进行球磨 1小 时〜 5小时， 所述的易溶有机物为羧酸类有机物， 按照质量百分比计， 所述的易溶有机 物占复合金属氧化物的 10%〜50%；  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;
步骤 3 : 将步骤 2得到的浆料移出， 放入高温烘箱中烘干；  Step 3: Remove the slurry obtained in step 2 and put it in a high temperature oven for drying;
步骤 4: 将步骤 3得到的干燥产物放入电炉中， 在空气气氛下 600°C〜900°C进行煅 烧， 得到复合金属氧化物粉体产物。  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.
2、 根据权利要求 1所述的一种复合金属氧化物粉体的制备方法， 其特征是： 所述 的复合金属氧化物为萤石结构的复合金属氧化物或者钙钛矿结构的复合金属氧化物。  2. The method for preparing a composite metal oxide powder according to claim 1, wherein: the composite metal oxide is a composite metal oxide of a fluorite structure or a composite metal oxide of a perovskite structure. Things.
3、 根据权利要求 2所述的一种复合金属氧化物粉体的制备方法， 其特征是： 所述 的萤石结构的复合金属氧化物是氧化锆基复合氧化物或氧化铈基复合氧化物，所述的钙 钛矿结构的复合金属氧化物是镧锶锰氧、 镧锶钴氧、 镧锶钴铁氧或钡锶钴铁氧。  3. The method for preparing a composite metal oxide powder according to claim 2, wherein: the composite metal oxide of the fluorite structure is a zirconia-based composite oxide or a cerium oxide-based composite oxide. The composite metal oxide of the perovskite structure is barium manganese oxide, samarium cobalt oxide, samarium cobalt ferrite or samarium cobalt ferrite.
4、根据权利要求 1、 2或 3所述的一种复合金属氧化物粉体的制备方法，其特征是: 所述的易溶有机物为柠檬酸、 葡萄糖、 蔗糖、 丙烯酸、 草酸、 抗坏血酸中的一种或两种 以上的混合物。  The method for preparing a composite metal oxide powder according to claim 1, 2 or 3, wherein the soluble organic matter is citric acid, glucose, sucrose, acrylic acid, oxalic acid or ascorbic acid. One or a mixture of two or more.
5、根据权利要求 1、 2或 3所述的一种复合金属氧化物粉体的制备方法，其特征是: 所述的步骤 3中的烘干温度为 100°C〜300°C， 烘干时间为 3小时〜 8小时。  The method for preparing a composite metal oxide powder according to claim 1, 2 or 3, wherein: the drying temperature in the step 3 is 100 ° C to 300 ° C, and drying The time is from 3 hours to 8 hours.
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CN101462060A (en) * 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 Method for preparing nano perovskite type rare-earth oxide
CN101777646A (en) * 2010-01-28 2010-07-14 新乡市中科科技有限公司 Preparation method of lithium vanadium oxide positive electrode materials of lithium ion batteries

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JP2003073125A (en) * 2001-09-04 2003-03-12 National Institute For Materials Science Method for producing yttrium - aluminum - iron oxide
CN1749171A (en) * 2004-09-13 2006-03-22 广东工业大学 Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution
CN101462060A (en) * 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 Method for preparing nano perovskite type rare-earth oxide
CN101777646A (en) * 2010-01-28 2010-07-14 新乡市中科科技有限公司 Preparation method of lithium vanadium oxide positive electrode materials of lithium ion batteries

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