CN100404428C - 低氧化铌、其制造方法和含有它的电容器 - Google Patents

低氧化铌、其制造方法和含有它的电容器 Download PDF

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CN100404428C
CN100404428C CNB2004100545226A CN200410054522A CN100404428C CN 100404428 C CN100404428 C CN 100404428C CN B2004100545226 A CNB2004100545226 A CN B2004100545226A CN 200410054522 A CN200410054522 A CN 200410054522A CN 100404428 C CN100404428 C CN 100404428C
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niobium
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C·施尼特尔
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Tantalum Niobium Obisheng Innovative Materials Co Ltd
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Abstract

本发明涉及生产近似组成为NbO的低氧化铌的方法，该低氧化铌特别适合于固体电解质电容器阳极的生产。

Description

低氧化铌、其制造方法和含有它的电容器
技术领域
本发明涉及一种制造近似组成为NbO的低氧化铌的方法，该低氧化铌特别适合于固体电解质电容器阳极的生产。
背景技术
固体电解质电容器具有非常大的有效电容器表面积，因而具有较小的整体结构，适合用于移动通信电子器件，其主要是具有应用于相应导电基底上的铌或钽的五氧化物阻挡层的电容器，并且其利用了这些化合物(“阀金属”)的稳定性、相对高的介电常数以及通过电化学方法可以制造出层厚非常均匀的绝缘五氧化物层的事实。所用的基底是金属或相应五氧化物的导电的低氧化物(低氧化物)前体。基底，其同时构成了电容器电极(阳极)，包含通过烧结那些已经是类海绵状形式的极细微粒初级或次级结结构而产生的高度多孔的、类海绵状的结构。基底结构的表面被电解氧化(“成形”)来产生五氧化物，且五氧化物层厚度由最大的电解氧化电压(“成形电压”)确定。反电极通过向类海绵状结构注入硝酸锰而制得，硝酸锰加热转变成二氧化锰，或者注入聚合物电解质的液态前体并接着进行聚合。对电极的电接触一方面由在基底结构制造过程中烧结而成的钽或铌金属线来产生，另一方面由对所述金属线绝缘的金属电容器护层构成。
电容器电容通过下列方程计算：
C＝(F·ε)/(d·VF)
式中F表示电容器表面积，ε为介电常数，d为每V成形电压的绝缘层厚度，并且VF为成形电压。由于五氧化二铌或五氧化二钽的介电常数ε分别是27.6或41，但其每伏成形电压的层厚度增长d分别是16.6或25
Figure C20041005452200031
/V，两种五氧化物拥有几乎相同的ε/d商值，分别等于1.64或1.69。基于两种五氧化物的电容器，其阳极结构的几何形状是相同的，因此具有相同的电容。关于与重量相关的具体容量在细节上的细微差异是源于Nb，NbOx(0.7＜x＜1.3；特别地0.95＜x＜1.1)和Ta的密度的不同。因此，由Nb和NbOx做成的阳极结构具有节省重量的优点，例如，当用于移动电话的时候。在移动电话中每克重量的节省都是优先的。考虑到费用的因素，由于阳极结构的某此体积由氧来提供，因此NbOx比Nb更为有利。
低氧化铌粉末使用标准的冶金反应和合金加工来生产，据此通过把低氧化铌和金属铌在氢的存在下暴露于氧浓度达到平衡的温度下而产生平均氧化物含量，请参阅例子WO 00/15555 A1：
2Nb2O5+3Nb→5NbO    (1)
因此该方法包括商业上可得的高纯五氧化二铌的使用及其与高纯金属铌的混合，二者皆为粉末状且按照化学计量比例混合，在温度为800℃-1600℃的含氢气氛中加工处理二者数小时，该气氛中优选应至多含氢10％。对于五氧化物和金属物，在氧平衡发生后，具有所期望的小于或稍大于1μm(最小)截面尺寸的初始粒度的为优选。
在该方法中，用铌或钽做成的坩埚内充满了五氧化二铌和金属铌粉末，然后在含氢气氛下在炉中被加热到反应温度。
需要与五氧化二铌进行氧交换的金属铌最好由高纯度的五氧化二铌还原形成金属而产生。
这可以通过铝热作用来实现，即点燃Nb2O5/Al的混合物，并清洗掉所形成的铝的氧化物，然后用电子束净化铌金属块锭。还原以及电子束熔化后得到的铌金属块可以通过已知的方法用氢使其脆化，并被磨细以产生薄层片晶状粉末。
依照与WO 00/67936 A1相一致的生产金属铌的优选方法，首先用氢在1000-1600℃还原高纯度的五氧化二铌粉末以形成分子式近似为NbO2的铌的二氧化物，然后用镁蒸汽在750-1100℃还原成金属。在该方法中形成的氧化镁用酸来清洗掉。上述后一种的方法是特别优选的，这是由于其能量要求相当低，以及大致上保持了五氧化二铌的初始粒度和被对电容器特性有害的物质污染的风险较低的事实。
依照反应方程式(1)反应的一个缺点是五氧化二铌体积收缩在转变成低氧化铌的过程中大约等于50％，这导致了一个相当松散的低氧化物晶体微结构，该晶体微结构只能在具有加入晶体缺陷的风险的条件下被压实，并且因此可能最终对电容器特性产生负面影响。低氧化物不良的晶体性质也是其流动特性不足的一个原因。
在电容器生产中，电容器粉末良好的流动特性代表了一个重要的加工参数，这是由于粉末通过自动高速挤压机而被挤压，而要被挤压的粉末是通过储存容器供给到高速挤压机的。良好的流动特性代表了规定的粉末量以满足当代要求的精度流入压榨模具的一个前提条件，例如+/-0.5mg的精度。
发明内容
本发明的目的是克服现有技术的缺点。
本发明进一步的目的是提供具有改良的流动特性的低氧化铌粉末。
本发明的另外一个目的是减少高纯镁的消耗和氧化镁的产生，以及同时减少涉及氧化镁清洗的费用。
此外，显著增加炉容量也是本发明的目的。
本发明另一个目的是进一步减少在生产低氧化铌所需的金属铌的生产过程中发生污染的风险。
因此，根据本发明，近似组成为NbO2的铌的二氧化物用作起始氧化物以和金属铌粉末达到冶金氧平衡。优选在1000℃到1600℃的温度下通入氢，还原五氧化二铌制备铌的二氧化物。
因此本发明的主题是一种生产NbOx的方法，其中0.7＜x＜1.3，优选0.9＜x＜1.15，特别优选1＜x＜1.05，通过NbOy与按化学计量所需的金属铌在氢的存在下反应，其中1.8＜y＜2.1，优选1.9＜y＜2。在能使所发生的反应基本上完全进行的前提下来确定的反应温度和时间。
本发明的另一个主题是分子式NbOx的低氧化铌粉末，其中0.7＜x＜1.3，优选0.9＜x＜1.15，特别优选1＜x＜1.05，此低氧化铌粉末具有根据ASTM B213最大60s/25g的流动特性，优选最大50s/25g，特别优选最大40s/25g。
具体地说，本发明涉及以下方面：
1.生产NbOx的方法，其中0.7＜x＜1.3，该方法通过将NbOy与化学计量数的金属铌在氢的存在下进行反应，其中1.8＜y＜2.1，来生产所述的NbOx。
2.根据第1项所述的方法，其特征在于，反应的温度是900℃-1600℃，以及反应的时间是0.5-4小时。
3.根据第1-2项之一所述的方法，其特征在于，起始物质NbOy是通过通入氢还原五氧化二铌而产生的。
4.根据第3项所述的方法，其特征在于，所述还原是在1000℃-1600℃的温度下进行的。
5.根据第3项所述的方法，其特征在于，所述通过还原五氧化二铌而产生NbOy的反应结束后，反应产物仍在900℃-1600℃的温度下保持一段时间以稳固和压实NbOy晶格。
6.根据第3项所述的方法，其特征在于，使用由最小平均粒度0.4-2μm的初始微粒的团聚物形成的粉末状五氧化二铌。
7.根据第1-2项之一所述的方法，其特征在于，使用按照第3-5项之一所述的方法用镁蒸汽还原NbOy所获得的金属铌粉末。
8.根据第7项所述的方法，其特征在于，在750℃-1150℃的温度下还原NbOy以形成所述金属。
9.分子式为NbOx的低氧化物，其中0.7＜x＜1.3，具有依照ASTM B213最大60s/25g的流动特性。
10.电容器，其包含根据第9项所述的低氧化物。
根据本发明，该方法的反应温度优选从900℃到1600℃。反应时间可以选择0.5-4小时，取决于反应温度和起始物质的成分和颗粒结构，以及最终产品的成分。
根据本发明，用于该方法的起始铌的二氧化物优选通过通入氢还原五氧化二铌来制备。优选在50到1100mbar的氢分压下发生反应。可以发现，当氢流中没有水蒸汽时，反应已经完成。反应完成后，为了稳定及压实NbOy晶格，优选地产品仍在900℃到1600℃，优选从1200℃到1600℃的温度下保持一定的时间，如0.1-0.5小时。
而且，在还原五氧化物以形成二氧化物时，优选地，温度逐渐地从950℃-1100℃范围的起始温度增加到1300℃-1600℃范围的最高温度，特别优选从1000℃-1050℃范围的起始温度到1350℃-1600℃范围的最高温度。并且，使还原在逐步降低的温度中继续进行，如果适当的话，可以先在最高温度停留一段时间。考虑到在初始还原价段中氧浓度的降低，可以通过增加温度在基本上对还原速率加以维持，或通过使用更低的起始温度来避免过快的还原速率所导致的过快的晶格扩展。然后，将高的最终温度在1300℃-1600℃范围内保持一段时间，这样晶格能够致密化而且晶格缺陷被在很大程度上退火。
另一方面，通过急速加热到1450℃-1600℃的还原温度，可能会在初始时发生非常急速的还原，从而导致早在二氧化物产生期间晶格就急速扩展，这样晶格变得很不稳定，并产生相对强的初始粒子增长。如果目的是生产30000-70000μFV/g的中容量电容器，并用超细颗粒五氧化二铌做起始物质，这可能是令人满意的。如果这样的话，为了巩固二氧化物的晶格，将温度保持在1200℃-1600℃是有益的。
所需的还原时间依赖于使用的五氧化二铌的粒度以及选择的还原温度。当五氧化物的初始粒度为0.3-0.5μm的情况下，20-40分钟的还原时间一般足够。
由于相对高的还原温度(包括第一个例子中的最高温度)，烧结的带有极高强度的跨接甚至在铌的二氧化物中形成。
通过镁蒸汽，可以在相对低的温度下，例如900℃-1100℃，实现二氧化物的进一步还原，以形成金属。在这些低的温度下，仅发生最小的初始微粒粗化。结果，由于二氧化物和金属的初始微粒和团聚物的尺寸没有差别，尤其是氧平衡后彼此几乎相同，因此，对于来源单一的铌的二氧化物来说，可能一方面部分的被进一步还原以形成金属物，而另一方面未经进一步处理而同金属物混合，然后达到氧平衡以形成低氧化物。
因此，根据本发明，低氧化物依照下列方程式产生：
NbO2+Nb→2NbO    (2)
体积收缩在NbO2转变成NbO的过程中大约仅为13％。虽然五氧化物42％的体积收缩中的多数已转移到NbO2的生产中，但这没有相反的作用，因为在氢还原期间它可能会影响作为NbO2的晶体微结构的中间稳定。
一个另外的优势是，依照本发明的方法，镁的消耗、冲洗费用以及生产金属铌所需产生的氧化镁的比例均减少了20％(基于NbO2的最终产量)。
本发明另一个优势是增加了用于形成NbO的反应炉的容量。依照反应方程(1)，从起始混合物到产品的体积收缩为23.5％，而依照本发明的反应方程式体积的增加仅有6％(理论上)，其在实际中被烧结收缩所弥补。依照方程式(1)，熔炉坩埚最初100％被充满，反应结束后仅有81％被NbO充满。
因此，就依照本发明所对应的方程式(2)的反应来说，容量能(在理论上)增加(19％/81％＝)23％。实际上，考虑到烧结收缩，容量的增加甚至更大。
具体实施方式
实施例
实施例1
a)铌的二氧化物NbOy的制造
使用部分团聚的高纯度的球状五氧化二铌，此五氧化二铌经过300μm筛格尺寸的筛子筛滤，具有直径大约为0.7μm的初始粒度以及依照BET(ASTM D 3663)测定的2.4m2/g的比表面积。
在如下所述的温度条件下通入氢，使五氧化物被还原成铌的二氧化物，其中温度在40分钟的时间内从950℃升到1300℃，然后保持在1300℃下30分钟，接下来在30分钟内降温至1200℃，然后保持此温度1小时。
铌的二氧化物具有对应于式NbO2.01的组成。初始粒度被粗化到接近0.9μm(从SEM图像中观测)，并且BET表面积为1.1m2/g。
通过300μm筛格尺寸的筛子之后，使用Malvern(ASTM B 822，湿润剂Daxad 11)生产的Mastersizer Sμ测量粒度分布，得到32μm的D10值，164μm的D50值，和247μm的D90值。
b)金属铌的制造
在反应器中，部分在a)中获得的铌的二氧化物被放置在铌线筛子上。1.1倍于按化学反应计量所需的镁(基于二氧化物中氧的量)，被放置在坩埚中筛子下面。反应器用氩气从下而上清洗。然后，反应器被加热到1050℃。8小时后，冷却反应器并且空气缓慢的进入以钝化金属表面。
获得的金属铌粉末具有0.85μm的初始粒度，1.32m2/g的BET面积，并且通过300μm筛格尺寸的筛子之后，具有33μm的D10值，176μm的D50值，和263μm的D90值。
c)低氧化铌NbOx的制造
按重量计，将43份在b)中获得的铌粉末以及57份在a)中获得的铌的二氧化物粉末混合并导入坩埚中，填充到坩埚边缘。然后在2.5小时期间内，在炉中将坩埚加热到1380℃，此熔炉用含85％体积氩气和15％体积氢气的混合气清洗过。
冷却之后，获得对应于式NbO0.96的低氧化铌粉末。此低氧化物粉末具有0.95μm的初始粒度以及1.1m2/g的BET面积。通过300μm筛格尺寸的筛子之后，D10值为41μm，D50值为182μm，D90值为258μm。
d)电容器制造
在每个实例中，103mg根据c)所得的低氧化铌粉末被导入挤压模具中，以包围铌接触线，然后其被挤压以形成压制密度为2.8g/cm3的压缩体。
此压缩体被随意放置在铌平台上，在10-3Pa的高真空中在1450℃温度下烧结20分钟。在85℃温度下，在含有0.1％强度磷酸的电解质中形成阳极，成型电流为150mA，并且成型电压可高达30V，该成型电压在电流衰退后维持2小时。
阳极体的电容和残余电流，其由通过成形而得的五氧化二铌阻挡层所提供，并通过用18％强度的浓硫酸在25℃下模拟的反电极来加以测定。3分钟的充电时间之后，这些测量在21V(成型电压的70％)电压，120Hz的频率以及10V的偏压下进行。测定平均比电容为75158μFV/g并且残余电流为0.76nA/μFV。
实施例2
a)铌的二氧化物NbOy的制造：
所使用的起始物质是部分团聚的、高纯度的、实际上为球状的Nb2O5，经过筛滤使其小于300μm，并且其依照BET(ASTM D3663)测定的比表面积为2.3m2/g。通入氢气，这些Nb2O5部分被还原为组成为NbO2.02的氧化物，在其中温度在60分钟的时间内从1000℃升到1450℃，然后在1450℃下保持200分钟。此二氧化物比表面积为0.32m2/g，通过激光衍射(ASTM B 822)测定，具有D10值为67μm，D50值为176μm以及D90值为284μm的粒度分布。
b)金属铌的制造
部分在a)中制造的铌的二氧化物被放置在反应器中金属丝网上。在金属丝网下面，有1.2倍于按化学反应计量所需的镁(基于二氧化物中氧的量)。将反应器在通入氩气下加热4小时，到900℃。在此期间，镁蒸发并且把其上面的铌的二氧化物还原成金属。冷却和钝化之后，通过反复的用硫酸再用水清洗，从形成的金属铌中移除形成的氧化镁。
形成的金属铌粉末具有0.4-0.6μm的初始粒度(从SEM图像中观测)，3.87m2/g的比表面积以及通过激光衍射测定(ASTM D 3663，Malvern Mastersizer)的54μm的D10值，161μm的D50值，和272μm的D90值。
c)低氧化铌NbOx的制造
1.依照现有技术的工序
在b)中制造的金属铌的一半与在a)中所描述的Nb2O5按重量比1∶0.95混合。然后在67mbar的绝对氢分压下，在炉中加热到1400℃并维持3小时。然后使粉末通过300μm筛格尺寸的筛子。用该方法获得的低氧化物(粉末A)的组成为NbO1.01并具有0.95-1.1μm的初始粒度(从SEM图像中观测)。比表面积为1.07m2/g，以及经激光衍射测定的D10值为71μm，D50值为165μm，D90值为263μm。
2.依照本发明的工序
另一半在b)中制造的金属铌同在a)中产生的部分NbO2.02按重量比1∶1.34混合。然后在67mbar绝对氢分压下，在炉中加热2小时，到1210℃。获得的低氧化铌(粉末B)具有NbO0.98的组成以及1.13m2/g的比表面积。从SEM图像中观测的初始粒度平均为1.0μm，并且经激光衍射测定的粒度分布为62μm的D10值，158μm的D50值，和269μm的D90值。
两种粉末的流动特性根据ASTM B213测定。
结果如下：
粉末A：65s/25g
粉末B：26s/25g。
因此，与按传统方法所得的产品相比，本发明的工序产生的低氧化铌的区别在于其进步的流动特性。

Claims (10)

1.生产分子式为NbOx的低氧化物的方法，其中0.7＜x＜1.3，该低氧化物具有依照ASTM B213最大60s/25g的流动特性，该方法通过将NbOy与化学计量数的金属铌在氢的存在下进行反应，其中1.8＜y＜2.1，来生产所述的NbOx。
2.根据权利要求1所述的方法，其特征在于，反应的温度是900℃-1600℃，以及反应的时间是0.5-4小时。
3.根据权利要求1-2之一所述的方法，其特征在于，起始物质NbOy是通过通入氢还原五氧化二铌而产生的。
4.根据权利要求3所述的方法，其特征在于，所述还原是在1000℃-1600℃的温度下进行的。
5.根据权利要求3所述的方法，其特征在于，所述通过还原五氧化二铌而产生NbOy的反应结束后，反应产物仍在900℃-1600℃的温度下保持一段时间以稳固和压实NbOy晶格。
6.根据权利要求3所述的方法，其特征在于，使用由最小平均粒度0.4-2μm的初始微粒的团聚物形成的粉末状五氧化二铌。
7.根据权利要求1-2之一所述的方法，其特征在于，使用按照权利要求3-5之一所述的方法用镁蒸汽还原NbOy所获得的金属铌粉末。
8.根据权利要求7所述的方法，其特征在于，在750℃-1150℃的温度下还原NbOy以形成所述金属。
9.根据权利要求1的方法获得的分子式为NbOx的低氧化物。
10.电容器，其包含根据权利要求9所述的低氧化物。
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