CN105967655A - 一种锂铁掺杂氧化镍负温度系数热敏电阻材料 - Google Patents
一种锂铁掺杂氧化镍负温度系数热敏电阻材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 229910000480 nickel oxide Inorganic materials 0.000 title description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title description 2
- 239000002994 raw material Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 6
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 abstract description 3
- 238000009529 body temperature measurement Methods 0.000 abstract 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229910052808 lithium carbonate Inorganic materials 0.000 description 16
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 5
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- 238000012545 processing Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
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- 238000013019 agitation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 238000000034 method Methods 0.000 description 2
- 230000004899 motility Effects 0.000 description 2
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- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 229910002929 BaSnO3 Inorganic materials 0.000 description 1
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- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910009567 YMnO3 Inorganic materials 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种半导体陶瓷材料，尤其是符合制备具有电阻负温度系数(NTC)的热敏电阻材料。本发明材料可以通过改变微量掺杂元素的含量调节热敏电阻元件的室温电阻值大小和材料常数值。本发明的NTC热敏电阻材料以简单氧化物为主要成分组成，能在1200℃左右烧结成陶瓷体，可适应热敏陶瓷元件、薄膜热敏元件及低温共烧叠层热敏元器件的烧结成型。本发明的热敏电阻材料具有稳定性好、一致性好、重复性好的特点，具有电阻值、材料常数、电阻温度系数等电气特性可控的特点，适用于温度测量、温度控制和线路补偿，以及电路和电子元件的保护以及流速、流量、射线测量的仪器与应用领域。
Description
技术领域
本发明涉及一种制备具有电阻负温度系数(NTC)效应的热敏电阻元件的NTC热敏电阻材料。适用于温度测量、温度控制和线路补偿，以及电路和电子元件的保护以及流速、流量、射线测量的仪器与应用领域。
背景技术
热敏传感器是利用材料电阻率随温度变化的特性制成的器件，包括正温度系数热敏电阻(PTC)和负温度系数热敏电阻(NTC)。NTC热敏材料泛指具有电阻值随温度升高而减小特性的半导体材料或元器件，现已广泛应用于温度测量、控制、温度补偿，以及电路和电子元件的保护以及流速、流量、射线测量的相关仪器与应用领域。随着电子设备微型化、集成化设计和电子设备轻、薄、多功能化的发展以及高新科技领域的不断突破，NTC热敏电阻受到越来越多的关注。
在众多NTC材料体系中，较为常见的、应用最多的是以Mn、Ni、Cu、Co、Fe、Zn等两种或两种以上的金属氧化物制备而成的半导体热敏陶瓷。这类热敏陶瓷的烧结温度根据所加的助烧剂等不同可在在1100～1200℃内变化，材料电阻率在100Ω·cm～10MΩ·cm范围内可调，相应的热敏常数B值在2000～7000K内变化，并且具有较大的电阻温度系数(-1％～-6％)和较宽的使用温区(-100～200℃)，工作性能稳定，占据了整个NTC热敏材料体系中最重要的位置。如，中国发明专利CN100395849C公布的以硝酸钴、硝酸锰和硫酸铁为原料制备的Co-Mn-Fe-O系NTC热敏陶瓷材料；中国发明专利CN1006667B公布的CoO-Co2O3-Fe2O3陶瓷系NTC热敏材料；中国发明专利CN1332405C公布的以锰、镍、镁、铝的硝酸盐为原材料、采用液相共沉淀法合成的NTC热敏电阻材料；美国发明专利6861622公开专利描述的锰-镍-钴-铁-铜系NTC热敏材料。这些NTC热敏电阻材料的共同特征是含有至少两种过渡金属的氧化物，且以尖晶石型立方晶体结构为主晶相组成。
但是传统过渡金属锰、镍、钴、铁、铜的氧化物制成的尖晶石结构NTC热敏电阻材料又有很多不足之处，如，过渡金属氧化物的挥发温度较低，这类NTC热敏电阻元件在制备过程中会产生原料的挥发，从而影响产品的性能和均一性；长期使用产生成分的挥发从而影响精度；生产过程中产品一致性差；材料的电阻值、温度系数和材料系数等难于控制和调节；易发生结构弛豫而造成材料老化等。
近年来，为了开发新型氧化物基NTC热敏电阻材料，科技工作者也开发了一些新的材料体系，如六方BaTiO3体系(中国发明专利ZL 2009 10043274.8；中国发明专利ZL 2009 1 0303525.1)，金红石型SnO2陶瓷(电子元件与材料,2009(6):56-59；J.Mater.Sci.:Mater.El.,2014,25(12):5552-5559)、Feltz首先发现LaCoO3基钙钛矿结构陶瓷具有优异的NTC特性(J.Eur.Ceram.Soc.,2000,20(14-15):2367-2376.)，接下来BaSnO3、BaBiO3、SrTiO3、YMnO3和LaMnO3等材料均通过掺杂、复合等手段成功制得NTC热敏陶瓷(J.Am.Ceram.Soc.,1997,80(8):2153-2156；Appl.Phys.Lett.,2003,82(14):2284-2286；Acta Phys.Chim.Sin.,2008,24(5):767-771；J.Electroceram,2008,20(2):113-117；Solid State Sci.,2006,8(2):137-141；J.Eur.Ceram.Soc.,2002,22(4):567-572)。随着空调、电冰箱、微波设备和汽车等产业对NTC热敏电阻器的稳定性要求越来越高，改善现有成分体系或开发新型成分体系就显得十分重要。针对以上状况，本发明采用以氧化镍为主要成分、通过微量元素掺杂改性的材料，得到了具有良好NTC效应的热敏电阻材料体系，并且可以通过改变微量掺杂元素来调节热敏电阻元件的室温电阻率和材料的温度常数。
发明内容
本发明的目的是提供一种能够制造具有负电阻温度系数效应的NTC热敏电阻材料体系。这种热敏电阻材料可以通过改变微量掺杂元素以调节热敏电阻元件的室温电阻率和材料的温度常数。
本发明的NTC热敏电阻材料的成分组成为：Ni1-x-yLixFeyO，其中x＝0.001～0.09；y＝0.001～0.09。
本发明组成NTC材料的关键组成为Ni1-x-yLixFeyO，配方成分中含有镍、锂和铁元素，其原材料可以是含这些元素的单质，氧化物、无机盐或有机盐等化合物。其中，半导化元素锂是为了调整热敏电阻元件的室温电阻率，元素铁是由于调节热敏电阻元件的室温电阻率和体现热敏特性的材料常数与温度系数。
按本发明实施例所述制备方法能获得高纯单相的物相组成，所制备的NTC热敏电阻元件的性能稳定高、可靠性高。
本发明的主要重点在于热敏电阻材料的成分配方，实际应用过程中可以根据需要对合成方法和生产工艺进行相应调整，灵活性大。如，原材料可选用含有这些元素的单质，氧化物、无机盐或有机盐等化合物；合成方法可采用固态反应法、溶胶-凝胶法、共沉淀法、气相沉积法或其它陶瓷材料的合成方法来实现。
本发明的热敏电阻材料特性的检测是采用涂覆银浆为电极，测量元件的室温电阻及电阻-温度特性。实际生产可以选用其它电极材料，如铝电极、In-Ga合金电极或镍电极材料。
本发明涉及的NTC热敏电阻材料的特色和优势表现在：①材料成分简单，原材料比较丰富、无毒，环境友好；②制备过程中烧结温度低，烧结温度为1200±50℃，适合陶瓷元件、薄膜、低温共烧等NTC热敏电阻元件的生产；③通过调整半导化掺杂元素的含量可大范围调整热敏电阻元件的室温电阻值；④通过调节成分组成中的Fe的含量，可以较大范围地调节热敏元件的材料常数与温度系数。
本发明NTC热敏电阻材料的电性能可实现以下参数要求：室温电阻率ρ25＝1Ω·cm～8MΩ·cm，材料常数B＝60～5500K。
本发明的内容结合以下实施例作进一步的说明。以下实施例只是符合本发明技术内容的几个实例，并不说明本发明仅限于下述实例所述的内容。本发明的重点在于成分配方，所述原材料、工艺方法和步骤可以根据实际生产条件进行相应的调整，灵活性大。
附图说明
图1是实施例中NTC热敏陶瓷电阻材料中不同Fe含量的电阻-温度特性曲线。该图说明所有材料均呈现典型的NTC特性，且Fe的微量引入能明显改变材料的电阻率和NTC材料常数。
图2是实施例中NTC热敏陶瓷电阻材料的室温电阻率与材料常数随铁含量的变化曲线。说明Fe的微量引入能明显改变材料的电阻率和NTC材料常数。
图3是实施例6所制备的热敏电阻材料(Ni1-x-yLixFeyO)从室温至300℃重复测量的电阻率-温度关系图。体现出该材料具有很好的温度循环稳定性。
具体实施方式
实施例1
本实施例按分子式Ni1-x-yLixFeyO进行配料，其中x＝0.04、y＝0。初始原材料选自碱式碳酸镍NiCO3·2Ni(OH)2·4H2O、碳酸锂Li2CO3。材料制备按以下实验的工艺步骤：
(1)将初始原料按Ni0.96Li0.04O配方配料，称取NiCO3·2Ni(OH)2·4H2O 24.0787g、Li2CO3 0.2956g；
(2)将上一步骤称取的原材料溶解于稀硝酸中；
(3)将上一步骤配制的溶液利用磁力搅拌加热器搅拌混合均匀、加热干燥；
(4)将上一步骤制得的粉末进行煅烧，温度为850℃，保温5小时；
(5)将上一步骤合成的粉体进行造粒、压制成坯体；坯体为圆片型，圆片直径为15毫米，厚度为3.5～4.0毫米；
(6)将上一步骤得到的坯体进行烧结，烧结温度为1200℃，保温40分钟，升温和冷却速率均为每分钟5℃，这样就获得NTC热敏陶瓷片；
(7)将上一步骤制得的NTC热敏陶瓷片两面磨平后，涂以银浆并经600℃固化制作电极；
(8)将上一步骤制得的NTC热敏电阻元件进行电阻-温度特性测量。
所制备的材料性能如表1、图1和图2所示。
实施例2
本实施例按分子式Ni1-x-yLixFeyO进行配料，其中x＝0.04、y＝0.03。初始原材料选自碱式碳酸镍NiCO3·2Ni(OH)2·4H2O、碳酸锂Li2CO3、柠檬酸铁-水合FeC6H5O7·nH2O。材料制备按以下实验的工艺步骤：
(1)将初始原料按Ni0.93Li0.04Fe0.03O配方配料，称取NiCO3·2Ni(OH)2·4H2O23.3262g、Li2CO3 0.2956g、FeC6H5O7·nH2O 1.4698g；
(2)将上一步骤称取的原材料NiCO3·2Ni(OH)2·4H2O和Li2CO3溶解于稀硝酸中；FeC6H5O7·nH2O加热溶于去离子水。
(3)将上一步骤配制的两种溶液混合在一起，并利用磁力搅拌加热器搅拌混合均匀、加热干燥。
(4)制备工艺过程与实施例1中的步骤(4)～(8)相同。
所制备的材料性能如表1、图1和图2所示。
实施例3
本实例按分子式Ni1-x-yLixFeyO进行配料，其中x＝0.04、y＝0.04。初始原材料选碱式碳酸镍NiCO3·2Ni(OH)2·4H2O、碳酸锂Li2CO3、柠檬酸铁-水合FeC6H5O7·nH2O。材料制备按以下实验的工艺步骤：
(1)将初始原料按Ni1-x-yLixFeyO配方配料，称取NiCO3·2Ni(OH)2·4H2O23.0754g、Li2CO3 0.2956g、FeC6H5O7·nH2O 1.9596g；
(2)制备工艺过程与实施例2中的步骤(2)～(4)相同。
所制备的材料性能如表1、图1和图2所示。
实施例4
本实例按分子式Ni1-x-yLixFeyO进行配料，其中x＝0.04、y＝0.05。初始原材料选碱式碳酸镍NiCO3·2Ni(OH)2·4H2O、碳酸锂Li2CO3、柠檬酸铁-水合FeC6H5O7·nH2O。材料制备按以下实验的工艺步骤：
(1)将初始原料按Ni1-x-yLixFeyO配方配料，称取NiCO3·2Ni(OH)2·4H2O22.8246g、Li2CO3 0.2956g、FeC6H5O7·nH2O 2.4496g；
(2)制备工艺过程与实施例2中的步骤(2)～(4)相同。
所制备的材料性能如表1、图1和图2所示。
实施例5
本实例按分子式Ni1-x-yLixFeyO进行配料，其中x＝0.04、y＝0.05。初始原材料选碱式碳酸镍NiCO3·2Ni(OH)2·4H2O、碳酸锂Li2CO3、柠檬酸铁-水合FeC6H5O7·nH2O。材料制备按以下实验的工艺步骤：
(1)将初始原料按Ni1-x-yLixFeyO配方配料，称取NiCO3·2Ni(OH)2·4H2O22.8246g、Li2CO3 0.2956g、FeC6H5O7·nH2O 2.4496g；
(2)制备工艺过程与实施例2中的步骤(2)～(4)相同。
所制备的材料性能如表1、图1和图2所示。
表1 实施例材料性能指标
Claims (3)
1.一种负温度系数热敏电阻材料，其特征是该材料的成分组成为Ni1-x-yLixFeyO。其中x＝0.001～0.09；y＝0.001～0.09。
2.根据权利要求1所述的一类氧化物Ni1-x-yLixFeyO基负温度系数热敏电阻材料，其特征在于：配方成分中含有Ni、Li、Fe元素。
3.根据权利要求1、2所述的Ni1-x-yLixFeyO基负温度系数热敏电阻材料，制备这种热敏电阻的原材料可以是含这些元素的单质、氧化物、无机盐或有机盐等化合物。
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