CN1211819C - 电容器粉末及其制备方法以及包含该电容器粉末的电容器 - Google Patents
电容器粉末及其制备方法以及包含该电容器粉末的电容器 Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
- H01G9/0525—Powder therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12181—Composite powder [e.g., coated, etc.]
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- Powder Metallurgy (AREA)
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Abstract
本发明涉及一种包含铌阳极、氧化铌耗尽层、半导体阴极和电解质的电解电容器，其中氧化铌耗尽层包含至少一种选自铝、硅、钛、锆、钼、钨、钇和钽的金属。
Description
本发明涉及生产电解电容器用的粉末，尤其是生产电解电容器阳极用的粉末。
文献中描述了特别是作为此种类型电容器生产用原料的土酸(earth acid)金属铌和钽。电容器的生产过程包括，精细分散的粉末经烧结生成具有大表面面积的结构，该烧结体表面再经氧化生成非导电绝缘层，然后施加层状二氧化锰或导电聚合物形式的相反电极。土酸金属之所以特别适用是由于其五氧化物的相对介电常数大。
目前，只有钽粉末在电容器生产中取得工业重要性。这一方面归功于精细分散钽粉末的可重现性生产，另一方面是五氧化钽绝缘氧化物层具有特别卓越的稳定性。这很可能是由于钽，不同于铌，不生成稳定的低氧化物。
然而，在微电子技术的发展过程中，钽的缺点正变得越来越突出。首先，钽具有16.6g/cm3的非常高的密度。这限制了朝轻质化，特别是移动电子设备，例如移动电话之类的方向发展。鉴于铌的密度只有钽的一半，在相同几何和相同氧化物层性质的前提下与钽相比，每单位重量的铌粉末能达到约是钽粉末两倍的比电容。决定电容器电容的五氧化物绝缘层的材料性质以铌的情况为一方与以钽的情况为另一方，具有部分相反的影响。
譬如，电容器电容越高，绝缘层的相对介电常数就越高。它越低，规定电压下每种情况所需要的绝缘层厚度就越厚。因此，具有介电常数41的五氧化铌要高于五氧化钽的介电常数26，却因铌的情况比钽的情况所需五氧化物层厚度更大所抵消。在预先规定的阳极化电压条件下，五氧化钽层厚度的增加为约2nm/V，而五氧化铌层则为约3.7nm/V。因此，按电容器的表面面积计，二者电容则不相上下。
至今，铌电容器的应用一直局限于低比电容、小比表面面积和较低品质的领域。
本发明的目的是克服已知铌电容器的缺点。具体地说，本发明目的是改进铌电容器中五氧化铌阻挡层，使之可达到较高比电容。
现已发现，具有元素铝、硅、钛、锆、钼、钨、钇和钽当中至少一种的表面涂层的铌粉末非常适合生产铌电容器。特别是现已发现，按电容器阳极的表面积计，由涂层的铌粉末生产的此种类型电容器的比电容高于纯铌阳极的比电容，并且可获得低残余电流的铌阳极。再有，还首次存在与钽阳极不相上下的长期稳定性的迹象。
因此，本发明涉及具有元素铝、硅、钛、锆、钼、钨、钇和钽当中至少一种的表面涂层的铌粉末。
本发明还涉及由铌组成的电容器烧结阳极，其中该阳极具有一定表面含量的元素铝、硅、钛、锆、钼、钨、钇和钽当中至少一种。
进而，本发明涉及具有氧化铌阻挡层的烧结铌阳极，其中阻挡层具有一定表面含量的元素铝、硅、钛、锆、钼、钨、钇和钽当中至少一种。
另外，本发明还涉及由铌阳极、氧化铌阻挡层、半导体阴极和电解质组成的电解电容器，其中氧化铌阻挡层具有至少一种表面改性元素。
表面改性元素在阻挡层中的优选含量小于25％(原子)，以阻挡层总金属含量为基准，尤其优选最高20％(原子)。更优选氧化物阻挡层中表面改性元素的含量介于2～15％(原子)。
以铌粉末为基准，表面涂层的数量优选小于18％(原子)，尤其是小于15％(原子)，更优选1.5～12％(原子)。
优选的表面改性元素是钛、锆和钽，尤其优选钽。
据认为，铌粉末的表面改性元素即使在进一步加工为电容器期间依然基本上保持在表面上，因为后加工期间采用的温度，一般低于1250℃，相对于2500℃的铌熔点，就固态扩散来说是相对低的。
因此，本发明提供一种生产超过目前供应的最高电容钽电容器的铌电容器的可能。此种类型钽电容器在阳极电压例如等于40V时，具有100,000μFV/g的比电容。而具有对应几何参数的本发明铌电容器则具有大于300,000μFV/g的比电容。特别是，已成功地生产出化学改性铌电容器，其比电容，按电容器面积计，大于60,000μFV/g，尤其是大于70,000μFV/g。
本发明还涉及生产本发明电容器粉末的方法。该方法包括：将铌粉末放在表面改性元素的可水解或可分解化合物的溶液中浸泡，从溶液中分离出粉末，使附着在粉末上的化合物水解或分解，随后，将水解物还原为金属。
合适的铌粉末是这样制取的粉末：对在氢气氛中借助电子束熔融的铌金属锭进行加热；研磨该通过吸附了氢而已变脆的材料；然后通过在减压下加热而除去氢。按照WO98/19811的铌片也是适宜的。
合适的还有按照本申请人在DE 198 31 280、DE 198 47 012和PCT99/09772--尚不属现有技术出版物--中的建议制取的高孔隙率铌粉末，该制备方法包括：将五氧化铌在液态或气态镁中进行还原，任选在预先用氢气还原为低氧化物之后。
另一种合适的铌粉末是包含元素铝、钛、钼、钨、铪、锆或钽中一种或多种作为合金成分，即，以最高5wt％的含量均匀分布的铌粉末。
下面，以钽为例说明表面改性元素的施加：
作为可分解或可水解的钽化合物，这里特别是指可溶于水或有机溶剂的有机钽化合物。一种合适的、水溶性有机钽化合物是草酸钽。具有1～8个碳原子的醇溶性钽的醇盐，例如甲醇钽、乙醇钽、丙醇钽、丁醇钽等，包括辛酸钽，也适合，另外还有按照US-A 5,914,417的钽的有机金属化合物。
为了在铌粉末上生成薄钽层，有机钽化合物优选以稀溶液形式使用，只要它们本身仍然是液体即可。合适的溶剂是水，只要该钽化合物是水稳定的。醇盐优选以在绝对乙醇或者其他具有足够低的酸度，以致没有水进入便不发生水解的有机溶剂中，例如在甲苯或苯中的形式使用。这些醇盐优选采用各自对应的醇来溶解。
钽化合物在各个溶剂中的浓度优选介于1～20wt％，尤其优选1～10wt％，更优选1～5wt％。
将铌粉末悬浮在有机钽化合物的溶液中，且为保证良好润湿，令其静置一定时间。典型的时间可介于10min～1h。为保证多孔铌粉末或铌粉末聚集体的良好渗透，有利的是将铌粉末放在真空容器内、减压之下，任选用溶剂蒸汽吹洗容器，随后再向抽真空的容器中加入处理溶液。
处理过的铌粉末可通过过滤、离心或滗析从溶液中分离出来。
在采用钽的醇盐的情况下，它们在被置于空气中和不隔绝湿气的情况下，或者在增湿的空气中，优选温和加热到50～100℃的条件下进行水解。任选在接近处理的终点可通入水蒸气，以达到完全水解。在采用草酸钽的情况下，水解是在碱水溶液，例如氨溶液或氢氧化钠溶液中实施的。水解尤其优选在含氨气流中进行。
为生产出均匀附着的氧化钽涂层，水解应在数小时期间逐渐进行。
浸泡和水解可反复进行多次。优选的是，铌粉末的浸渍应在较低浓度的溶液中实施，不过这样做需要进行多次。
在任选一个中间干燥步骤之后，如此处理的铌粉末优选利用蒸汽压足够高的吸气剂金属在850～1000℃下进行还原。合适的吸气剂金属是：镁、钙、锶、钡、铝和/或镧。关键是，反应期间形成的氧化物应能采用无机酸轻易地洗掉。尤其优选的还原剂是镁。
经如此还原、无机酸洗涤以及随后以去离子水洗涤至不含酸且最后干燥的铌粉末，放在适当模具中压缩至2.5～3.5g/cm3的压缩密度，从而获得粒料，然后按本身已知的方式在1100～1250℃进行烧结。给烧结的阳极装配钽和/或铌，优选铌，的接触导线，如果压缩期间尚未在模具中插入接触导线的话。
随后，该阳极按已知方式在0.1％浓度磷酸中成型到要求的形成电压。
除了草酸盐和醇盐之外，仲钨酸铵的水溶液也适合并优选用于生产钨涂层，而七钼酸(heptamolybdate)铵的水溶液，因能够遇热分解，适合并优选用于生产钼涂层。
适合生产钛涂层的是TiOSO4的水溶液，利用含水碱，例如用氨进行水解，或者用纯TiCl4，随后用水蒸气水解。
实施例1～7
采用一种按照DE-A 19 831 280，由铌低氧化物NbO2经镁蒸汽还原制取的高纯度铌粉末。该粉末的比BET表面积是3.02m2/g。将数量不等的样品浸泡在含表1所给数量的乙醇钽的乙醇溶液中。对比例样品以纯乙醇溶液处理。30min后，相应数量的样品通过过滤从各自溶液中分离出来并在环境空气中静置15min。
随后，将这些样品在95℃干燥45min，以80℃去离子水洗涤，然后再次干燥。
继而，样品在氩气氛下利用镁蒸汽在850℃～950℃(炉内温度梯度)进行还原。
图1显示按照表1的样品1的各种不同放大倍数SEM(扫描电子显微镜)照片。
关于钽、碳、氢和氧的分析数值以及样品的比表面面积均载于表1。
通常，将样品在3.14g/cm3的压缩密度下围绕铌导线压缩从而成为阳极丸，然后在1150℃烧结20min。烧结的阳极在0.1％浓度磷酸中成型至40V的形成电压。
电容器性质在以30％浓度硫酸作为阴极电解液、1.5V偏压条件下进行测定。
结果载于表1。
表1
| 样品 | 在乙醇中浸渍，Ta(OEt)5的浸渍量(wt％) | 粉末 | 电容器 | ||||||
| Tappm | Cppm | Hppm | Oppm | S.A.1)m2/g | CV/gμFV/g | CV/m2μ-FV/m2 | Ir/CVnA/μFV | ||
| 对比例 | 0 | 21 | 98 | 68 | 4 100 | 1,03 | 63 240 | 61 400 | 0,95 |
| 实施例1 | 1 | 1 640 | 103 | 67 | 3 900 | 0,93 | 69 200 | 74 400 | 1,08 |
| 实施例2 | 5 | 2 490 | 143 | 69 | 4 200 | 1,00 | 73 700 | 73 700 | 0,58 |
| 实施例3 | 10 | 13 900 | 224 | 78 | 5 209 | 1,15 | 81 100 | 70 500 | 0,77 |
| 实施例4 | 5(3-次) | 14 700 | 196 | 84 | 5 180 | 1,1 | 82 200 | 74 700 | 0,61 |
| 实施例5 | 20 | 27 200 | 275 | 112 | 5 528 | 1,55 | 91 700 | 59 200 | 0,67 |
| 实施例6 | 5(6-次) | 29 600 | 267 | 108 | 4 800 | 1,05 | 84 300 | 80 300 | 0,76 |
| 实施例7 | 5(8-次) | 42 300 | 248 | 121 | 4 430 | 0,98 | 83 900 | 85 600 | 0,69 |
1)BET
Claims (6)
1.一种包含铌阳极、氧化铌阻挡层、半导体阴极和电解质的电解电容器，其中氧化铌阻挡层包含至少一种选自元素铝、硅、钛、锆、钇和钽的金属。
2.权利要求1的电容器，其中该金属是钽。
3.一种由具有通过阳极氧化生成的阻挡层的烧结铌粉末组成的电容器阳极，其中该阻挡层包含金属铝、硅、钛、锆、钇和钽当中至少一种。
4.一种主要由具有包含金属铝、硅、钛、锆、钇和钽当中至少一种的表面涂层的铌组成的电容器粉末。
5.按照权利要求4的电容器粉末的生产方法，包括：将制成合金的或未制成合金的铌粉末浸泡在金属铝、硅、钛、锆、钇和钽当中至少一种的可水解或可分解化合物的溶液中，从溶液中分出该粉末，使附着的化合物水解或分解。
6.按照权利要求5的生产方法，还包括将水解物还原为金属。
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| Application Number | Priority Date | Filing Date | Title |
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| DE19953946A DE19953946A1 (de) | 1999-11-09 | 1999-11-09 | Kondensatorpulver |
| DE19953946.4 | 1999-11-09 |
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| US6416730B1 (en) | 1998-09-16 | 2002-07-09 | Cabot Corporation | Methods to partially reduce a niobium metal oxide oxygen reduced niobium oxides |
| US6322912B1 (en) | 1998-09-16 | 2001-11-27 | Cabot Corporation | Electrolytic capacitor anode of valve metal oxide |
| EP2221839B2 (en) † | 2000-08-10 | 2017-05-24 | Showa Denko K.K. | Niobium powder, sintered body and capacitor using the body |
| DE10044451C1 (de) * | 2000-09-08 | 2002-04-04 | Epcos Ag | Elektrode und Kondensator mit der Elektrode |
| JP2003213301A (ja) * | 2002-01-21 | 2003-07-30 | Kawatetsu Mining Co Ltd | ニオブ粉末及び固体電解コンデンサ |
| JP2004143477A (ja) * | 2002-10-22 | 2004-05-20 | Cabot Supermetal Kk | ニオブ粉末およびその製造方法、並びにそれを用いた固体電解コンデンサ |
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| US7445679B2 (en) | 2003-05-16 | 2008-11-04 | Cabot Corporation | Controlled oxygen addition for metal material |
| US7515397B2 (en) | 2003-05-19 | 2009-04-07 | Cabot Corporation | Methods of making a niobium metal oxide and oxygen reduced niobium oxides |
| WO2005045860A1 (en) | 2003-11-10 | 2005-05-19 | Showa Denko K.K. | Niobium powder for capacitor, niobium sintered body and capacitor |
| US20080011124A1 (en) * | 2004-09-08 | 2008-01-17 | H.C. Starck Gmbh & Co. Kg | Deoxidation of Valve Metal Powders |
| WO2007020464A1 (en) * | 2005-08-19 | 2007-02-22 | Avx Limited | Solid state capacitors and method of manufacturing them |
| GB0517952D0 (en) * | 2005-09-02 | 2005-10-12 | Avx Ltd | Method of forming anode bodies for solid state capacitors |
| DE102005043829A1 (de) * | 2005-09-13 | 2007-04-05 | H.C. Starck Gmbh | Verfahren zur Herstellung von Elektrolytkondensatoren mit hoher Nennspannung |
| GB0622463D0 (en) * | 2006-11-10 | 2006-12-20 | Avx Ltd | Powder modification in the manufacture of solid state capacitor anodes |
| US7760487B2 (en) * | 2007-10-22 | 2010-07-20 | Avx Corporation | Doped ceramic powder for use in forming capacitor anodes |
| US7760488B2 (en) * | 2008-01-22 | 2010-07-20 | Avx Corporation | Sintered anode pellet treated with a surfactant for use in an electrolytic capacitor |
| US7768773B2 (en) * | 2008-01-22 | 2010-08-03 | Avx Corporation | Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor |
| US7852615B2 (en) * | 2008-01-22 | 2010-12-14 | Avx Corporation | Electrolytic capacitor anode treated with an organometallic compound |
| US8203827B2 (en) * | 2009-02-20 | 2012-06-19 | Avx Corporation | Anode for a solid electrolytic capacitor containing a non-metallic surface treatment |
| US9053860B2 (en) * | 2010-12-24 | 2015-06-09 | Showa Denko K.K. | Tungsten powder, anode body for capacitors, and electrolytic capacitor |
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| EP1230655B1 (de) | 2005-05-25 |
| IL149038A0 (en) | 2002-11-10 |
| KR20020065513A (ko) | 2002-08-13 |
| AU1389101A (en) | 2001-06-06 |
| IL149038A (en) | 2007-07-04 |
| SV2002000213A (es) | 2002-02-05 |
| CN1387667A (zh) | 2002-12-25 |
| AU770489B2 (en) | 2004-02-26 |
| CZ301939B6 (cs) | 2010-08-04 |
| KR100715408B1 (ko) | 2007-05-08 |
| US6821314B1 (en) | 2004-11-23 |
| BRPI0015400B1 (pt) | 2016-04-19 |
| CZ20021584A3 (cs) | 2002-07-17 |
| JP4999135B2 (ja) | 2012-08-15 |
| WO2001035428A1 (de) | 2001-05-17 |
| DE19953946A1 (de) | 2001-05-10 |
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| DE50010419D1 (de) | 2005-06-30 |
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