WO2012151798A1 - 一种黑色导电陶瓷复合材料及其制备方法 - Google Patents

一种黑色导电陶瓷复合材料及其制备方法 Download PDF

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WO2012151798A1
WO2012151798A1 PCT/CN2011/078550 CN2011078550W WO2012151798A1 WO 2012151798 A1 WO2012151798 A1 WO 2012151798A1 CN 2011078550 W CN2011078550 W CN 2011078550W WO 2012151798 A1 WO2012151798 A1 WO 2012151798A1
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solution
nitrate
conductive ceramic
preparation
ceramic composite
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PCT/CN2011/078550
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English (en)
French (fr)
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林保平
曹艺
杨洪
张雪勤
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东南大学
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Definitions

  • the invention relates to the field of materials, in particular to a conductive ceramic, in particular to a composite conductive ceramic powder of a lanthanum manganate salt and a silver oxide doped with a transition metal and a preparation method thereof.
  • Conductive solid materials generally include metal materials, organic conductive polymers, conductive ceramic materials, etc., but ceramic materials are mostly composed of ionic bonds and covalent bonds, generally insulating materials, so the application range is greatly limited.
  • conductive ceramics mainly refer to BaPb1-xBixO3, RuO2, LaCaO3, Li2O. • LiCl • B2O3 and other bulk conductive ceramics, because the conductive mechanism of ceramics is more complex, the particles involved in conduction can be electrons, positive ions or negative ions.
  • the conductivity of ceramics is related to the carrier concentration and mobility of the materials, or the conductivity of the materials. Performance is closely related to material composition, doping, microstructure, crystal defects, preparation processes, and post-treatment processes.
  • these conductive ceramics have defects of one kind or the like, such as the required conductive temperature is too high; or the required materials contain materials such as SiC, Si3N4, etc. which are difficult to prepare, which are costly; or poor in high temperature resistance, use The lifetime is too short; or the conductivity is too low and it is difficult to modulate over a large range.
  • mixed oxides have good electronic and ionic conductivity at the same time, ceramics with mixed conductivity have more problems in the preparation process.
  • a variety of mixed oxide ceramic materials with higher conductivity have been discovered, but as practical materials, stable physical and chemical properties are required over a wide temperature and humidity range, and electrical conductivity is high, and can be applied to high temperatures and Low temperature operation, large blackness and high mechanical strength, and low manufacturing cost.
  • several practical mixed oxide conductive ceramics are known, such as: Ba0.9Na0.1 (Fe0.5Nb0.5) 0.5O3, La0.90Ba0.10Ga0.75Mg0.25O3-a, etc.
  • the formula is (Re1-xAx)(B1-yFey)O3, wherein Re is La or part of La is replaced by Nd or Y, A is one or more of Sr, Ba, Ca, and B is Ni, Mn, Co
  • Re is La or part of La is replaced by Nd or Y
  • A is one or more of Sr, Ba, Ca
  • B is Ni, Mn, Co
  • a black conductive ceramic composite material according to the present invention is characterized in that the composition formula is LaxSryM1-x-yMnO3 • zAg2O, M is Al a composition of one or more of Fe, Ca, Ba, Ce, Bi, Nd, Mo, Cu, Co, Zn, Mg, Ni, Zr, Ti, Nb, Y, Sm, Cd, In, x, y, z are the number of moles, 0.5 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.4, x + y ⁇ 1, 0 ⁇ z ⁇ 0.1.
  • lanthanum manganate As a matrix material of ceramics, lanthanum manganate is made by doping other transition metal elements in the lattice of lanthanum manganate which has lattice defects, so that the lattice defects are greatly changed, thereby generating more oxygen vacancies. It is beneficial to the oxygen ion conduction; at the same time, it is compounded with silver oxide, thereby greatly increasing the electronic conductivity of the ceramic material, thereby further increasing the overall mixed conductivity. Therefore, the electrical conductivity of the composite conductive ceramic can be effectively modulated by doping different metal elements and their different amounts and varying amounts of silver oxide.
  • the composite black conductive ceramic powder of the present invention is prepared by dissolving cerium nitrate or cerium carbonate, cerium nitrate or cerium carbonate, silver nitrate, manganese nitrate and nitrate or carbonate of M in water in proportion. Stir well, adjust the pH of the solution with nitric acid to ⁇ 1, completely dissolve it, add ethylene glycol and citric acid solution as a complexing agent, add ethylene glycol and citric acid solution to 1.5 times the molar amount of manganese nitrate.
  • the product prepared by the invention is a composite conductive ceramic material, which is obtained by forming a dry gel by a sol-gel method and then forming a composite material of a transition metal-doped lanthanum manganate salt and silver oxide formed by calcination. It has high electrical conductivity, high temperature resistance, high electrical conductivity at normal temperature, wear resistance, thermal conductivity, non-toxicity, easy processing, and high blackness. It can be used for the modulation of electronic paste and the preparation of electrode materials.
  • the method provided by the invention is simple to prepare, non-polluting, easy to industrialize, and the conductivity can be adjusted.
  • Figure 1 is an XRD diagram of Embodiment 1 of the present invention.
  • Figure 2 is a TEM image of Embodiment 1 of the present invention.
  • Figure 3 is an electron diffraction diagram of Example 1 of the present invention.
  • LaxSryM1-x-yMnO3 • zAg2O is used to calculate the amount of each component, and the raw materials are weighed by the percentage of the elements.
  • x, y, and z are the atomic percentages of the respective elements in the material, 0.5 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.4, x + y ⁇ 1, 0 ⁇ z ⁇ 0.1.
  • the M element is at least one or more selected from the group consisting of the following metal elements: Al , Fe, Ca, Ba, Ce, Bi, Nd, Mo, Cu, Co, Zn, Mg, Ni, Zr, Ti, Nb, Y, Sm, Cd, In.
  • the M element is added in the form of a nitrate.
  • the mixture was uniformly ground, placed in a crucible, and calcined at 900 ° C for 2 hours to obtain a black powder.
  • the obtained product was subjected to energy fraction X-ray spectroscopy, and its composition formula was La0.6Sr0.3Cu0.1MnO3, and the average particle diameter was 0.6 ⁇ m.
  • the powder was carefully ground in an agate mortar and then subjected to conductivity measurement after tableting, and its conductivity was 13.9 S/cm.
  • the mixture was uniformly ground, placed in a crucible, and calcined at 900 ° C for 2 hours to obtain a black powder.
  • the obtained product was subjected to energy fraction X-ray spectroscopy, and its composition formula was La0.9Sr0.1MnO3•0.05Ag2O, and the average particle diameter was 0.9 ⁇ m.
  • the powder was carefully ground in an agate mortar and then subjected to electrical conductivity measurement after tableting, and its electrical conductivity was 10.7 S/cm.
  • the mixture was uniformly ground, placed in a crucible, and calcined at 900 ° C for 2 hours to obtain a black powder.
  • the obtained product was subjected to energy fraction X-ray spectroscopy and its composition formula was La0.5Sr0.3Al0.1Zn0.1.
  • In0.1MnO3 has an average particle diameter of 1.1 ⁇ m.
  • the powder was carefully ground in an agate mortar and then subjected to conductivity measurement after tableting, and its conductivity was 7.4 S/cm.
  • the mixture was uniformly ground, placed in a crucible, and calcined at 900 ° C for 2 hours to obtain a black powder.
  • the obtained product was subjected to energy fraction X-ray spectroscopy and its composition formula was La0.6Sr0.1Ce0.05Zr0.1Mg0.1 Bi0.05MnO3•0.1Ag2O, and the average particle diameter was 1.7 ⁇ m.
  • the powder was carefully ground in an agate mortar and then subjected to electrical conductivity measurement after tableting, and its electrical conductivity was 86.2 S/cm.
  • the mixture was uniformly ground, placed in a crucible, and calcined at 900 ° C for 3 hours to obtain a black powder.
  • the obtained product was subjected to energy fraction X-ray spectroscopy, and its composition formula was La0.5Sr0.4Cu0.1MnO3•0.05Ag2O, and the average particle diameter was 0.7 ⁇ m.
  • the powder was carefully ground in an agate mortar and then subjected to electrical conductivity measurement after tableting. The conductivity was 1.5 ⁇ 102. S/cm.
  • Example 1 is an XRD pattern of Example 1. From the figure, we can visually observe several diffraction peaks of the embodiment as a perovskite crystal, but the intensity of the diffraction peak is low due to the complicated structure of the product.
  • Fig. 3 is an electron diffraction diagram of Example 1. It can be seen from the figure that the diffraction pattern of the crystal is a parallelogram lattice structure, indicating that the crystallinity of the product is excellent.
  • 2 is a TEM image of Example 1, and the appearance and particle size of Example 1 can be visually observed from the figure.

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Description

一种黑色导电陶瓷复合材料及其制备方法 技术领域
本发明涉及材料领域，具体是导电陶瓷，尤其是掺杂了过渡族金属的锰酸镧锶盐与氧化银的复合导电陶瓷粉及其制备方法。
背景技术
导电固体材料一般包括金属材料、有机导电聚合物、导电陶瓷材料等，但陶瓷材料多由离子键和共价键组成，一般为绝缘材料，因此应用范围受到很大限制。目前，导电陶瓷主要是指BaPb1-xBixO3、RuO2、LaCaO3、Li2O • LiCl •B2O3等本体式导电陶瓷，由于陶瓷的导电机制比较复杂，参与导电的粒子可以是电子、正离子或负离子，陶瓷导电能力与材料中载流子浓度及其迁移率有关，或者说材料的导电性能与材料组成、掺杂、微结构、晶体缺陷、制备工艺及后处理过程密切相关。然而，这些导电陶瓷都具有这样或那样的缺陷，如需要的导电温度过高；或所需要的物质中含有如SiC，Si3N4等难以制备的材料，使成本过高；或者耐高温能力差，使用寿命过短；或者电导率太低并难以在较大的范围内进行调制。
虽然一些混合氧化物同时具有很好的电子和离子导电性能，但具有混合导电性的陶瓷在制备工艺上还有着较多的问题。现在已经发现了多种具备较高电导率的混合氧化物陶瓷材料，但作为实用材料，要求在较宽的温度和湿度范围内具有稳定的物理和化学性能，电导率高、可适用于高温和低温工作，有较大的黑度和较高的机械强度，并且制造成本较低等。目前，已知的几种实用型混合氧化物导电陶瓷如：Ba0.9Na0.1(Fe0.5Nb0.5) 0.5O3、La0.90Ba0.10Ga0.75Mg0.25O3-a等为数不多的几种陶瓷材料制备方法，不能很好的用于大规模生产，只能应用于实验室研究，而如申请号为200810204483的xAlO3：（1-x）SrTiO3（x为0.001～0.015）的导电陶瓷因为其电导率太低，对外可见光吸收小，而无法满足要求；而专利号为01107727.1的专利中说所提及的通式为(Re1-xAx)(B1-yFey)O3，其中Re为La或者是部分La被Nd或者Y取代，A为Sr、Ba、Ca中的一种或几种，B为Ni、Mn、Co中的一种或几种，0≤x≤0.5，0≤y≤0.5的导电陶瓷材料，因为其导热系数低，对紫外可见光吸收小，电导率可调范围窄，因为其具有抗粘结性，故其机械成型性能差。
因此，现在亟需一种新型黑色导电陶瓷能克服以前的各种缺陷，并具备有上述所需的各种条件，可以成功的投入到电子浆料等产品的实际应用中去。而本发明恰好能满足目前所需的所有要求。
 技术问题
本发明的目的是提供一种电导率可调且能够提高紫外及可见光的吸收能力的黑色导电陶瓷复合材料及其制备方法。
 技术解决方案
本发明所述的一种黑色导电陶瓷复合材料，其特征在于组成通式为LaxSryM1-x-yMnO3 •zAg2O，M为 Al 、Fe、Ca、Ba、Ce、Bi、Nd、Mo、Cu、Co、Zn、Mg、Ni、Zr、Ti、Nb、Y、Sm、Cd、In中的一种或一种以上的组合物，x，y，z为摩尔数，0.5≤x＜1，0＜y≤0.4，x+ y≤1，0≤z≤0.1。
锰酸镧锶作为陶瓷的基体材料，通过在本来就有晶格缺陷的锰酸镧锶晶格中掺杂其它过渡金属元素，使其晶格缺陷发生较大变动，从而产生更多的氧空位，有利于氧离子导电；同时与氧化银进行复合，从而大大增加陶瓷材料的电子导电性，从而更加增加整体的混合导电能力。因此通过掺杂不同的金属元素及其加入量的不同以及符合不同量的氧化银，可有效调制复合导电陶瓷的电导率。
本发明所述的复合黑色导电陶瓷粉通过以下方法制备：将硝酸镧或碳酸镧，硝酸锶或碳酸锶，硝酸银、硝酸锰以及M的硝酸盐或碳酸盐按比例称量溶于水中，搅拌均匀，并用硝酸调节溶液的pH＜1，使其完全溶解，加入的乙二醇和柠檬酸溶液做络合剂，乙二醇加入量和柠檬酸溶液加入量分别为硝酸锰摩尔数的1.5倍和3倍，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为凝胶，然后放入真空干燥箱65℃真空干燥24小时，取出后研磨均匀后，放入坩埚，在900～1100℃焙烧2～4小时，得黑色粉末。焙烧可以在空气氛或氧气氛中进行。
 有益效果
本发明所制备的产品为复合导电陶瓷材料，是通过溶胶凝胶法形成干凝胶再通过焙烧形成的掺杂了过渡族金属的锰酸镧锶盐与氧化银的复合的陶瓷材料，在获得了较高导电性的同时，具有耐高温，常温下电导率高，耐磨，导热，无毒，易于加工，并且黑度高等特征，可用于电子浆料的调制和电极材料的制备。本发明提供的方法制备简单，无污染，易于工业化，且电导率可调节。
 附图说明
图1是本发明实施例1的XRD图。
图2是本发明实施例1的TEM图。
图3是本发明实施例1的电子衍射图。
 本发明的实施方式
按照配方LaxSryM1-x-yMnO3 •zAg2O来计算各组分的用量，将原料按元素百分比称取。
式中x，y，z为各自元素在材料中所占的原子百分比，0.5≤x＜1，0＜y≤0.4，x+ y≤1，0≤z≤0.1.
而M元素至少选自下列金属元素中的一种或几种： Al 、Fe、Ca、Ba、Ce、Bi、Nd、Mo、Cu、Co、Zn、Mg、Ni、Zr、Ti、Nb、Y、Sm、Cd、In。在制备工艺中，M元素以硝酸盐的形式来添加。
以下通过实施实例进一步说明本发明，但应理解以下实例只是示例性的，本发明并不局限于此。
实施例1
称取1.9506g（0.006mol）La(NO3)3，0.6352g（0.003mol）Sr(NO3)2， 0.2419g（0.001mol）Cu(NO3)2，及3.58g（0.01mol）Mn(NO3)2溶液，溶于25ml去离子水中，加入1.0g（0.016mol）乙二醇，搅拌均匀后，加入25%HNO3溶液调教pH=1。称取6.2g（0.032mol）柠檬酸固体，溶于20ml去离子水中，以3滴/秒的速度滴加入混合溶液中，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为凝胶。然后放入真空干燥箱65℃真空干燥24小时，得深绿色固体。
取出后研磨均匀后，放入坩埚，在900℃焙烧2小时，得黑色粉末。
所得产物进行能量分数X射线谱测定，其组成式为La0.6Sr0.3Cu0.1MnO3，平均粒径为0.6μm。将粉末在玛瑙研钵中仔细研磨，然后压片后进行电导率测定，其电导率为13.9S/cm。
实施例2
称取2.9261g（0.009mol）La(NO3)3，0.2114g（0.001mol）Sr(NO3)2， 0.1687g（0.001mol）Ag(NO3)2及3.58g（0.01mol）Mn(NO3)2溶液，溶于25ml去离子水中，加入1.0g（0.016mol）乙二醇，搅拌均匀后，加入25%HNO3溶液调教pH=1。称取6.2g（0.032mol）柠檬酸固体，溶于20ml去离子水中，以3滴/秒的速度滴加入混合溶液中，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为粘稠状。然后放入真空干燥箱65℃真空干燥24小时，得深绿色固体。
取出后研磨均匀后，放入坩埚，在900℃焙烧2小时，得黑色粉末。
所得产物进行能量分数X射线谱测定，其组成式为La0.9Sr0.1MnO3•0.05Ag2O，平均粒径为0.9μm。将粉末在玛瑙研钵中仔细研磨，然后压片后进行电导率测定，其电导率为10.7S/cm。
实施例3
称取1.6257g（0.005mol）La(NO3)3，0.4238g（0.002mol）Sr(NO3)2， 0.2992g（0.001mol）Zn(NO3)2，0.3757g（0.001mol）Al(NO3)3，0.3821g（0.001mol）In(NO3)3，及3.58g（0.01mol）Mn(NO3)2溶液，溶于25ml去离子水中，加入1.0g（0.016mol）乙二醇，搅拌均匀后，加入25%HNO3溶液调教pH=1。称取6.2g（0.032mol）柠檬酸固体，溶于20ml去离子水中，以3滴/秒的速度滴加入混合溶液中，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为粘稠状。然后放入真空干燥箱65℃真空干燥24小时，得深绿色固体。
取出后研磨均匀后，放入坩埚，在900℃焙烧2小时，得黑色粉末。
所得产物进行能量分数X射线谱测定，其组成式为La0.5Sr0.3Al0.1Zn0.1 In0.1MnO3，平均粒径为1.1μm。将粉末在玛瑙研钵中仔细研磨，然后压片后进行电导率测定，其电导率为7.4S/cm。
实施例4
称取1.9506g（0.006mol）La(NO3)3，0.2117g（0.001mol）Sr(NO3)2， 0.2174g（0.0005mol）Ce(NO3)3，0.2568g（0.001mol）Mg(NO3)2，0.4291g（0.001mol）Zr(NO3)4，0.2427g（0.0005mol）Bi(NO3)3，0.3754g（0.001mol）AgNO3及3.58g（0.01mol）Mn(NO3)2溶液，溶于25ml去离子水中，加入1.0g（0.016mol）乙二醇，搅拌均匀后，加入25%HNO3溶液调教PH=1。称取6.2g（0.032mol）柠檬酸固体，溶于20ml去离子水中，以3滴/秒的速度滴加入混合溶液中，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为粘稠状。然后放入真空干燥箱65℃真空干燥24小时，得深绿色固体。
取出后研磨均匀后，放入坩埚，在900℃焙烧2小时，得黑色粉末。
所得产物进行能量分数X射线谱测定，其组成式为La0.6Sr0.1Ce0.05Zr0.1Mg0.1 Bi0.05MnO3•0.1Ag2O，平均粒径为1.7μm。将粉末在玛瑙研钵中仔细研磨，然后压片后进行电导率测定，其电导率为86.2S/cm。
实施例5
称取1.6255g（0.005mol）La(NO3)3，0.8461g（0.004mol）Sr(NO3)2， 0.2419g（0.001mol）Cu(NO3)2，0.3754g（0.001mol）AgNO3及3.58g（0.01mol）Mn(NO3)2溶液，溶于25ml去离子水中，加入1.0g（0.016mol）乙二醇，搅拌均匀后，加入25%HNO3溶液调整pH=1。称取6.2g（0.032mol）柠檬酸固体，溶于20ml去离子水中，以3滴/秒的速度滴加入混合溶液中，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为粘稠状。然后放入真空干燥箱65℃真空干燥24小时，得深绿色固体。
取出后研磨均匀后，放入坩埚，在900℃焙烧3小时，得黑色粉末。
所得产物进行能量分数X射线谱测定，其组成式为La0.5Sr0.4Cu0.1MnO3•0.05Ag2O，，平均粒径为0.7μm。将粉末在玛瑙研钵中仔细研磨，然后压片后进行电导率测定，其电导率为1.5×102 S/cm。
图1为实施例1的XRD图谱，从图中我们能够较为直观的观察到该实施例作为钙钛矿型晶体的几个衍射峰，但由于产品结构复杂，所以衍射峰的强度较低，而图3为实施例1的电子衍射图，从图中可以看出其晶体的衍射花纹为平行四边形点阵结构，说明该产物的结晶性能很好。而图2为实施例1的TEM图，从图中可以较为直观的观察到实施例1的外貌及颗粒大小。

Claims (3)

  1. 一种黑色导电陶瓷复合材，其特征在于组成通式为：
    LaxSryM1-x-yMnO3 •zAg2O，M为 Al 、Fe、Ca、Ba、Ce、Bi、Nd、Mo、Cu、Co、Zn、Mg、Ni、Zr、Ti、Nb、Y、Sm、Cd、In中的一种或一种以上的组合物，x，y，z为摩尔数，0.5≤x＜1，0＜y≤0.4，x+ y≤1，0≤z≤0.1。
  2. 一种权利要求1所述黑色导电陶瓷复合材料的制备方法，其特征在于，将硝酸镧或碳酸镧，硝酸锶或碳酸锶，硝酸银、硝酸锰以及M的硝酸盐或碳酸盐按比例称量溶于水中，搅拌均匀，并用硝酸调节溶液的pH＜1，使其完全溶解，加入的乙二醇和柠檬酸溶液做络合剂，乙二醇加入量和柠檬酸溶液加入量分别为硝酸锰摩尔数的1.5倍和3倍，恒温30℃搅拌1小时，再将溶液转移到蒸发皿中，80℃下不断搅拌蒸发直至溶液变为凝胶，然后放入真空干燥箱65℃真空干燥24小时，取出后研磨均匀后，放入坩埚，在900～1100℃焙烧2～4小时，得黑色粉末。
  3. 如权利要求2所述的制备方法，其特征在于，焙烧在空气氛或氧气氛中进行。
PCT/CN2011/078550 2011-05-09 2011-08-18 一种黑色导电陶瓷复合材料及其制备方法 WO2012151798A1 (zh)

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