WO2021072643A1 - Method for preparing bacl2-based nano-material - Google Patents

Method for preparing bacl2-based nano-material Download PDF

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Publication number
WO2021072643A1
WO2021072643A1 PCT/CN2019/111271 CN2019111271W WO2021072643A1 WO 2021072643 A1 WO2021072643 A1 WO 2021072643A1 CN 2019111271 W CN2019111271 W CN 2019111271W WO 2021072643 A1 WO2021072643 A1 WO 2021072643A1
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barium
powder
preparing
barium oxide
based nano
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PCT/CN2019/111271
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French (fr)
Chinese (zh)
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何洪波
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诸暨易联众创企业管理服务有限公司
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Priority to PCT/CN2019/111271 priority Critical patent/WO2021072643A1/en
Publication of WO2021072643A1 publication Critical patent/WO2021072643A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing

Definitions

  • the invention relates to a preparation method of barium oxide-based nano material.
  • Nanoparticles are located in the transition region between the clusters of atoms and macroscopic objects. They are a typical mesoscopic system and produce many special properties that bulk materials do not possess.
  • nano-barium oxide It has a wide range of applications in the fields of gas sensitive materials, lithium ion battery anode materials, conductive materials, thin film resistors, optoelectronic devices, and wave absorbing materials.
  • methods for preparing nano-barium oxide mainly physical methods (such as sputtering, vapor deposition, plasma method), chemical methods (such as hydrothermal method, alkoxide hydrolysis method, chemical precipitation method, etc.).
  • the sol-gel method in the chemical method has been widely used and developed due to its low synthesis temperature, simple process and cheap equipment required. Based on this, the researchers used the sol-gel method to prepare nano-barium oxide powder, the particle size of which is usually more than tens of nanometers. In order to prepare nano-barium oxide powder with a smaller particle size, it is necessary to improve the preparation process, or use surface modification, doping and other methods to further try.
  • the invention provides a preparation method of barium oxide-based nano material, which is used for preparing barium oxide-based nano powder with small particle size and narrow distribution.
  • the technical scheme of the present invention is as follows:
  • the present invention adopts the sol-gel method to prepare barium oxide-based nanomaterials, including the process of preparing Ba(OH)2 powder and modified barium oxide powder; wherein the modified barium oxide powder is a combination of phosphomolybdic acid and phosphomolybdic acid.
  • the Ba(OH)2 powder is mixed uniformly, added with absolute ethanol to make a slurry, kept at 80°C for 4-10h, dried for 2h-6h, and then calcined in a muffle furnace at 350-800°C for 2h-7h.
  • the dosage of phosphomolybdic acid is that the mass ratio of phosphomolybdic acid to the raw material BaCl2 ⁇ 2H2O is 0.015 ⁇ 0.075:1.
  • the effect of the present invention is that the particle size of the nano barium oxide particles prepared by the sol-gel method is between 35-45 nm, and the shapes are tetragonal and spherical.
  • the particle size of the nano-barium oxide-based material prepared after the modification is between 5-10 nm, which is obviously smaller than that of the unmodified material, and the shape is all spherical.
  • unmodified barium oxide powder was prepared by the sol-gel method: 10g of BaCl2 ⁇ 2H2O was dissolved in 80ml of absolute ethanol to form a barium alcohol solution with a concentration of 0.8mol/L; 75°C water bath , Stir with a stirrer for 4 hours; slowly add ammonia water under constant stirring and a water bath at 75°C to adjust the pH to 7-8; filter with suction, wash, and use 2% AgNO3 solution to check that there is no Cl -1 ; then dry at 90°C After 4 hours, it was calcined in a muffle furnace at 800°C for 3 hours; pure barium oxide nanopowder was prepared by grinding, which was recorded as sample TH1.
  • the particle size of the sample TH1 is distributed between 35-45nm, and the particles have a tetragonal missing angle or a spherical shape, and there is obvious agglomeration.
  • the sample TH2 is a sample modified with phosphomolybdic acid.
  • the sample TH2 has a small particle size, with an average particle size of about 35 nm, a narrow particle size distribution, and the particles are all spherical, with a certain agglomeration phenomenon.
  • the particle size of the sample TH1 is distributed between 35-45nm, and the particles have a tetragonal missing angle or a spherical shape, and there is obvious agglomeration.
  • the sample TH3 is a sample modified with phosphomolybdic acid. It can be seen from the figure that the sample TH3 has a small particle size, ranging from 35-40nm to nm, with a narrow particle size distribution, and the particles are all spherical with a certain amount of agglomeration. phenomenon.
  • the particle size of sample TH3 is larger than that of sample TH2, but it is still smaller than that of sample TH1.

Abstract

Disclosed is a method for preparing a barium-oxide-based nano-material. The method is used for preparing a barium-oxide-based nano-powder with a small particle size and a narrow distribution. The technical solution is as follows: a barium-oxide-based nano-material is prepared using a sol-gel method, wherein the preparation comprises preparing a Ba(OH)2 powder and a modified barium oxide powder, and a drying procedure; and nano barium oxide particles prepared using the sol-gel method have a particle size between 35 nm and 45 nm, and shapes including both a square shape lacking an angle and a spherical shape.

Description

一种BaCl2基纳米材料的制备方法A kind of preparation method of BaCl2-based nano material 技术领域Technical field
本发明涉及一种氧化钡基纳米材料的制备方法。The invention relates to a preparation method of barium oxide-based nano material.
技术背景technical background
极细的晶粒和大量处于晶界和晶粒内缺陷中心的原子，导致了纳米微粒结构的特殊性。纳米微粒处在原子簇和宏观物体交界的过渡区域，是一种典型的介观系统，产生了许多体相材料不具备的特殊性能。The extremely fine grains and a large number of atoms at the center of the grain boundaries and defects in the grains lead to the particularity of the nanoparticle structure. Nanoparticles are located in the transition region between the clusters of atoms and macroscopic objects. They are a typical mesoscopic system and produce many special properties that bulk materials do not possess.
在气敏材料、锂离子电池负极材料、导电材料、薄膜电阻器、光电子器件、吸波材料等领域有着广泛的应用。制备纳米氧化钡的方法很多，主要有物理法(如溅射法、气相沉积法、等离子体法)、化学法(如水热法、醇盐水解法和化学沉淀法等)。其中化学法中的溶胶-凝胶法以其合成温度低、工艺简单、所需设备便宜，因而得到了广泛的应用和发展。基于此，研究者们用溶胶-凝胶法制备出了纳米氧化钡粉体，其粒度通常在几十纳米以上。为了制备出粒度更小的纳米氧化钡粉体，需要对制备工艺进行改进，或者用表面修饰、掺杂等方法来进一步尝试。It has a wide range of applications in the fields of gas sensitive materials, lithium ion battery anode materials, conductive materials, thin film resistors, optoelectronic devices, and wave absorbing materials. There are many methods for preparing nano-barium oxide, mainly physical methods (such as sputtering, vapor deposition, plasma method), chemical methods (such as hydrothermal method, alkoxide hydrolysis method, chemical precipitation method, etc.). Among them, the sol-gel method in the chemical method has been widely used and developed due to its low synthesis temperature, simple process and cheap equipment required. Based on this, the researchers used the sol-gel method to prepare nano-barium oxide powder, the particle size of which is usually more than tens of nanometers. In order to prepare nano-barium oxide powder with a smaller particle size, it is necessary to improve the preparation process, or use surface modification, doping and other methods to further try.
发明内容Summary of the invention
本发明提供一种氧化钡基纳米材料的制备方法，用于制备粒径小、分布窄的氧化钡基纳米粉体。The invention provides a preparation method of barium oxide-based nano material, which is used for preparing barium oxide-based nano powder with small particle size and narrow distribution.
本发明的技术方案如下：本发明采用溶胶-凝胶法制备氧化钡基纳米材料，包括制备Ba(OH)2粉末、改性氧化钡粉末过程；其中改性氧化钡粉末是将磷钼酸与的Ba(OH)2粉末混合均匀，加入无水乙醇调成浆状，80℃恒温4～10h，干燥2h～6h，再用马弗炉350～800℃焙烧2h～7h。磷钼酸的用量为磷钼酸与原料BaCl2·2H2O的质量比为0.015～0.075∶1。The technical scheme of the present invention is as follows: The present invention adopts the sol-gel method to prepare barium oxide-based nanomaterials, including the process of preparing Ba(OH)2 powder and modified barium oxide powder; wherein the modified barium oxide powder is a combination of phosphomolybdic acid and phosphomolybdic acid. The Ba(OH)2 powder is mixed uniformly, added with absolute ethanol to make a slurry, kept at 80°C for 4-10h, dried for 2h-6h, and then calcined in a muffle furnace at 350-800°C for 2h-7h. The dosage of phosphomolybdic acid is that the mass ratio of phosphomolybdic acid to the raw material BaCl2·2H2O is 0.015～0.075:1.
本发明的效果是：用溶胶凝胶法制得的纳米氧化钡粒子粒径在35-45nm之间，形状即有四方缺角形也有球形。改性后制得的纳米氧化钡基材料粒径在5～10nm之间，明显比未改性的材料粒径减小，形状皆为球形。The effect of the present invention is that the particle size of the nano barium oxide particles prepared by the sol-gel method is between 35-45 nm, and the shapes are tetragonal and spherical. The particle size of the nano-barium oxide-based material prepared after the modification is between 5-10 nm, which is obviously smaller than that of the unmodified material, and the shape is all spherical.
具体实施方式Detailed ways
实施例1Example 1
将10g地BaCl2·2H 2O溶于80ml的无水乙醇中配置成浓度为0.8mol/L的钡醇溶液；75℃水浴，用搅拌器搅拌4h；在不断搅拌、75℃水浴下，缓慢加入氨水，将pH值调为7～8；抽滤，洗涤，用2％AgNO3溶液检验无Cl -1为止；干燥后将粉末研磨加入0.1g12-磷钼酸(与原料BaCl2·2H2O的换算量为0.015g·g -1)混合均匀，加入无水乙醇调成浆状，80℃恒温8h；再90℃干燥4h后马弗炉800℃焙烧3h，研磨制备出氧化钡基纳米粉末，记为样品TH2。 Dissolve 10g of BaCl2·2H 2 O in 80ml of absolute ethanol to form a barium alcohol solution with a concentration of 0.8mol/L; in a 75℃ water bath, stir with a stirrer for 4 hours; add slowly under constant stirring and a 75℃ water bath Ammonia water, adjust the pH value to 7-8; suction filter, wash, check with 2% AgNO3 solution to check for Cl -1 ; after drying, grind the powder and add 0.1g 12-phosphomolybdic acid (converted with the raw material BaCl2·2H2O to 0.015g·g -1 ) Mix evenly, add absolute ethanol to make a slurry, keep at 80°C for 8h; dry at 90°C for 4h, calcinate in a muffle furnace at 800°C for 3h, grind to prepare barium oxide-based nano-powder, record it as sample TH2.
为了进行对比，用溶胶—凝胶法制备了未改性的氧化钡粉末：将10g的BaCl2·2H2O溶于80ml的无水乙醇中配置成浓度为0.8mol/L的钡醇溶液；75℃水浴，用搅拌器搅拌4h；在不断搅拌、75℃水浴下，缓慢加入氨水，将pH值调为7～8；抽滤，洗涤，用2％AgNO3溶液检验无Cl -1为止；再90℃干燥4h后马弗炉800℃焙烧3h；研磨制备出纯氧化钡纳米粉末，记为样品TH1。 For comparison, unmodified barium oxide powder was prepared by the sol-gel method: 10g of BaCl2·2H2O was dissolved in 80ml of absolute ethanol to form a barium alcohol solution with a concentration of 0.8mol/L; 75°C water bath , Stir with a stirrer for 4 hours; slowly add ammonia water under constant stirring and a water bath at 75°C to adjust the pH to 7-8; filter with suction, wash, and use 2% AgNO3 solution to check that there is no Cl -1 ; then dry at 90°C After 4 hours, it was calcined in a muffle furnace at 800°C for 3 hours; pure barium oxide nanopowder was prepared by grinding, which was recorded as sample TH1.
样品TH1粒子粒径分布在35-45nm之间，粒子有四方缺角形也有球形，有明显团聚现象。样品TH2是掺杂磷钼酸改性的样品，样品TH2粒径较小，平均粒径在35nm左右，粒径分布窄，粒子皆为球形，有一定的团聚现象。The particle size of the sample TH1 is distributed between 35-45nm, and the particles have a tetragonal missing angle or a spherical shape, and there is obvious agglomeration. The sample TH2 is a sample modified with phosphomolybdic acid. The sample TH2 has a small particle size, with an average particle size of about 35 nm, a narrow particle size distribution, and the particles are all spherical, with a certain agglomeration phenomenon.
实施例2Example 2
将10g的BaCl2·2H2O溶于80ml的无水乙醇中配置成浓度为 0.8mol/L的钡醇溶液；75℃水浴，用搅拌器搅拌4h；在不断搅拌、75℃水浴下，缓慢加入氨水，将pH值调为7～8；抽滤，洗涤，用2％AgNO3溶液检验无Cl -1为止；干燥后将粉末研磨加入0.3g11-磷钼酸(与原料BaCl2·2H2O的换算量为0.045g·g -1)混合均匀，加入无水乙醇调成浆状，80℃恒温4h；再90℃干燥4h后马弗炉800℃焙烧3h，研磨制备出氧化钡基纳米粉末，记为样品TH3。 Dissolve 10g of BaCl2·2H2O in 80ml of absolute ethanol to form a barium alcohol solution with a concentration of 0.8mol/L; in a 75℃ water bath, stir with a stirrer for 4h; under constant stirring and 75℃ water bath, slowly add ammonia, Adjust the pH value to 7-8; filter and wash with a 2% AgNO3 solution to check that there is no Cl -1 ; after drying, grind the powder and add 0.3g of 11-phosphomolybdic acid (converted with the raw material BaCl2·2H2O to 0.045g ·G -1 ) Mix uniformly, add anhydrous ethanol to make a slurry, keep at 80°C for 4h; dry at 90°C for 4h, calcinate in a muffle furnace at 800°C for 3h, grind to prepare barium oxide-based nanopowder, record it as sample TH3.
样品TH1粒子粒径分布在35-45nm之间，粒子有四方缺角形也有球形，有明显团聚现象。样品TH3是掺杂磷钼酸改性的样品，从图中可以看到样品TH3粒径较小，粒径在35-40nm nm之间，粒径分布窄，粒子皆为球形，有一定的团聚现象。样品TH3粒径较样品TH2粒径有所增大，但是仍然小于样品TH1的粒径。The particle size of the sample TH1 is distributed between 35-45nm, and the particles have a tetragonal missing angle or a spherical shape, and there is obvious agglomeration. The sample TH3 is a sample modified with phosphomolybdic acid. It can be seen from the figure that the sample TH3 has a small particle size, ranging from 35-40nm to nm, with a narrow particle size distribution, and the particles are all spherical with a certain amount of agglomeration. phenomenon. The particle size of sample TH3 is larger than that of sample TH2, but it is still smaller than that of sample TH1.

Claims (1)

  1. 一种氧化钡基纳米材料的制备方法，其特征是：将10g的BaCl2·2H 2O溶于80ml的无水乙醇中配置成浓度为0.8mol/L的钡醇溶液；75℃水浴，用搅拌器搅拌4h；在不断搅拌、75℃水浴下，缓慢加入氨水，将pH值调为7～8；抽滤，洗涤，用2wt％AgNO 3溶液检验无Cl -1为止；干燥后将粉末研磨加入0.5g12一磷钼酸混合均匀，加入无水乙醇调成浆状，80℃恒温6h；再90℃干燥4h后马弗炉800℃焙烧3h，研磨制备出氧化钡基纳米粉末。 A method for preparing barium oxide based nanomaterials, characterized in that: the BaCl2 · 10g 2H 2 O were dissolved in 80ml of absolute ethanol to a concentration of 0.8mol / L barium alcohol solution; 75 deg.] C water bath with stirring Stir for 4h; under constant stirring, 75℃ water bath, slowly add ammonia water to adjust the pH value to 7-8; suction filter, wash, check with 2wt% AgNO 3 solution to check that there is no Cl -1 ; after drying, grind and add the powder 0.5g of 12-phosphomolybdic acid was mixed uniformly, added with absolute ethanol and adjusted to a slurry state at 80°C for 6 hours; dried at 90°C for 4 hours, calcined in a muffle furnace at 800°C for 3 hours, and ground to prepare barium oxide-based nano-powder.
PCT/CN2019/111271 2019-10-15 2019-10-15 Method for preparing bacl2-based nano-material WO2021072643A1 (en)

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