CN101467030B - 氢传感器 - Google Patents
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Abstract
一种基于纳米颗粒的传感器,其中,以较高的密度接种较小的颗粒,于使用较大颗粒和较小密度播种的传感器相比能产生更快的响应时间。所述纳米颗粒可以包括钯纳米颗粒。该传感器可以用于氢燃料电池。
Description
本申请是美国专利申请第11/551630号的部分后续案,该申请要求美国临时申请第60/728980号和PCT申请PCT/US2006/030314的优先权,所有这些专利申请都通过引用结合于此。本申请是美国专利申请第10/854,420号的部分后续案,该申请要求美国临时申请第60/475,558号和PCT申请PCT/US2006/030314的优先权,该申请要求以下临时专利申请的优先权:60/728,353和60/728,980,这两个申请通过引用结合于此。本申请还要求美国临时申请第60/793,377的优先权,该临时申请通过引用结合于此。
背景技术
使用钯金属检测气态氢的传感器是一个两步过程,其中,双原子的氢分子在钯金属表面分裂成单原子氢,然后,单原子氢扩散到钯晶格中,造成钯晶格膨胀(最多至5%)和引发相变(见图1)。当钯的薄膜位于两个电触点之间时,薄膜在接触氢时会因相变而使电阻增加。电触点的接通时间(响应时间)通常不够迅速而不能进行商业应用,比如用于氢燃料电池。
附图简述
图1是钯发生相变的薄膜氢气传感器的图解;
图2说明氢气传感器中的电流变化;
图3是位于电阻基片上的氢传感器的示意图,箭头显示电流的方向,其中,电阻器代表基片;
图4说明一种两步的、在电阻基片上涂镀钯纳米颗粒的方法;
图5的表格说明本发明的实施方式的纳米颗粒的粒径和密度的变化;
图6(a)-6(d)列出显示本发明的实施方式的粒径和密度变化的代表性的扫描电子显微图像;
图7图示本发明的实施方式的传感器在60℃下对40,000ppm的氢气的响应曲线图;
图8说明传感器在60℃下对400ppm的氢气的响应曲线图;
图9是根据本发明的实施方式,直径(d)对于两个相邻的钯纳米颗粒的颗粒间距(1)的俯视示意图;
图10A图示说明根据本发明的实施方式的传感器元件;
图10B图示说明根据本发明的实施方式的具有钛制参考元件的传感器对;
图10C图示说明根据本发明的实施方式的与载体印刷电路板电线连接的传感器对;
图10D图示说明根据本发明的实施方式的实心模式的有源元件;
图10E图示说明根据本发明的实施方式的条纹模式的有源元件;
图11图示说明传感器的操作;
图12图示说明用于测试所述传感器的装置;
图13(a)-(b)说明氢传感器的电阻的变化;
图14(a)-(b)说明氢传感器的初始电阻;
图15图示说明传感器对温度和浓度的响应。
发明详述
一个有待解决的问题是找到用于快速氢气传感器的粒径和密度范围。本文公开的粒径和密度范围能在高氢气浓度下达到10秒或更短的响应时间。
美国专利第6,849,911中公开了另一种用于生产钯基氢传感器的方法,该方法通过电化学沉积技术在电阻基片上制造钯纳米颗粒网状物,该专利通过引用结合于此。当钯纳米颗粒在两个电触点之间的电阻基片上发生膨胀时,会使碰巧位于两个相邻的纳米颗粒下方的电阻基片中的微小电阻短路。根据大规模的统计,该基片的端到端电阻与氢气的量成比例下降。因此,该传感器测量氢气,而不只是检测它的存在。
(a)钯纳米颗粒网状物对薄膜或纳米金属丝(nanowire)(现有技术)
钯薄膜是一种连续的表面,原子间是正常的金属连接。钯薄膜对氢浓度增加的响应具有正的系数。即,电阻随着氢浓度的增加而增加(见图1)。与低电阻开关类似,钯纳米金属丝的电阻随着与氢接触的增加而减小(见图2)。当纳米颗粒膨胀并沿着金属丝整体长度相互接触时,所述开关接通。它对浓度梯度比较不敏感。当增加与氢的接触时,钯纳米颗粒网状物的电阻响应是电阻的逐渐降低(见图3)。
(b)电阻基片和钯‘纳米开关’的使用(现有技术:美国专利第6,849,911)
在电阻基片上使用纳米开关是已知的现有技术(见图3),这使得大部分纳米颗粒在接触氢之前是相互不接触的。一旦接触氢,颗粒的尺寸膨胀并开始相互接触,造成在颗粒所附着的电阻基片上发生电短路,逐步加强该基片的整体的端到端电阻的下降。由于颗粒形成无规则的网状物和任意的尺寸,所以,短路不会在特定的氢气浓度下发生,如同纳米金属丝的情况一样。然而,当所接触的氢浓度增加时,总体电阻逐渐下降。
(c)合适的电阻层的特性(现有技术:美国专利第6,849,911号}
对在其上形成纳米颗粒的电阻层提出一些要求。它应该是绝对温度稳定的,应该对环境因素不敏感,应该能经受纳米颗粒的形成。它还要产生某种‘非接触’电阻,这种电阻对于它所连接的电子设备来说是最佳的。对于传感器和电子仪器的情况,一个0.5mm×2.0mm的电阻表面产生的最佳电阻为1200至2200欧姆。
该最佳电阻值是由所需的操作电流、对附近电信号的基于阻抗的抗扰度(immunity)和该表面的电阻稳定性所确定的。如果使用比如钛表面,则较厚的表面膜改进其老化特性,但是电阻和可得信号减小。如果这种同样的膜太薄,则电噪声增加,并且对诸如氧化等影响的抵抗能力减小,钛在这些方面是众所周知的。上述物理结构的最佳电阻是90至150埃的钛产生。电阻膜材料的实际选择不会改变本发明的方式和方法。每一种材料都具有一些物理特性,通过使用本发明的一般方法可以对这些特性进行补偿。
(d)在电阻基片上制造纳米颗粒(美国专利申请第10/854,420号,该申请通过引用结合于此)。
通过电镀法在电阻基片上制造钯纳米颗粒。电镀浴含有溶解于水的0.1mM的PdCl2和0.1M的HCl。电镀纳米颗粒方法是成功操作传感器所必需的,所述传感器的窄距离窗口中,纳米颗粒相互之间具有特定的距离。
如果颗粒间的间隔较大,传感器对低浓度的响应变慢且不敏感。确实,传感器存在对于温度和浓度的最小阈值,在该阈值以下传感器不会运行。这是因为即使在颗粒最大程度地膨胀和增大时,颗粒之间间隔也太远而无法相互接触。
因此,需要同时控制基片上纳米颗粒的大小和晶种密度(seeding density)。本发明中,通过一个两步的电镀过程使钯纳米颗粒生长,该过程包括短时的成核脉冲(通常<10秒)和较长时的生长脉冲(<10分钟)。在该电化学制造过程中,控制成核与生长的参数以便制造在不同的氢浓度范围操作的传感器。通常,通过成核步骤(短脉冲)中的负荷量(charge)控制纳米颗粒的密度,而通过生长步骤(长脉冲)控制颗粒的大小。图4中显示一种典型的电镀曲线。该电镀过程采用恒电流法。电流参数依据基片的面积。
传感器的速度(称为响应时间)可以通过控制纳米颗粒的大小来控制。
因此,一个有待解决的问题是找到用于快速传感器的粒径和颗粒密度范围。本文公开的粒径和密度范围能在高氢浓度下达到10秒或更短的响应时间。
用于快速响应氢传感器的纳米颗粒的粒径和密度范围的鉴定
图5显示了一种基质,在电镀过程中其粒径和颗粒密度发生改变。研究了四种颗粒粒径和密度,以便鉴定响应时间最快的传感器。以下给出实验的变量:
实施例1:类型-较小粒径,低密度
可以看出,100-SL传感器的粒径约为50纳米,颗粒间距约为150纳米。图6a中显示SEM显微图像。减少成核时间以便提供低的颗粒密度。通过减小成核电流来降低颗粒间密度。
实施例2:类型-较小粒径,正常密度
可以看出,100-SN传感器的粒径约为50纳米,颗粒间距约为30纳米。图6b中显示其SEM显微图像。使成核电流维持在接近控制参数以便提供正常的颗粒密度,在恒电流过程中,成核电流的实际值依据基片面积。
实施例3:类型-较小粒径,高密度
可以看出,100-SH传感器的粒径约为20纳米,颗粒间距约为1-2纳米。传感器对于400ppm H2的响应时间(t90)约为25秒。图6c中显示其SEM显微图像。通过缩短生长时间来减小粒径,通过增强成核电流来增加颗粒间密度。
实施例4:类型-正常粒径,正常密度
可以看出,100-NN传感器的粒径约为50纳米,颗粒间距约为30纳米。传感器对于40000ppm(4%)H2的响应时间(t90)约为35秒。图6d中显示其SEM显微图像。控制镀覆条件使成核与生长保持恒定以便提供正常的粒径和密度。
图7显示这四种传感器对40000ppmH2的响应,图8显示这四种传感器对400ppmH2的响应。小粒径、高密度类型(100-SH)的响应时间是10秒,而正常粒径、正常密度类型(100-NN)的响应时间大于30秒。根据两个相邻颗粒之间的中心到中心的距离计算颗粒间距(1)。粒径(d)与颗粒间距(1)的比率定义为任何给定的颗粒的直径除以相邻颗粒的中心到中心距离的比率,如图9中举例说明的。
100-SH型的粒径(d)与颗粒间距(1)的比率约为0.85至1.0,而100-NN型约为0.6至0.85。因此,纳米颗粒的粒径(d)与颗粒间距(1)的比率决定了传感器的速度。
因此,对纯钯传感器改变其粒径和颗粒密度以获得更快的响应时间。得到的结论是,具有较高颗粒密度和较小粒径的传感器(100-SH)改进了传感器的响应时间方面的性能。
图11显示氢传感器的原理。将钯或钯复合材料颗粒负载于基材上。在氢气气氛中,这些颗粒膨胀而相互接触,使电极之间的电性质发生改变。比如,在恒电流模式下,当传感器接触氢气时,电极之间的电阻减小。
可以通过净化的玻璃基片和在其上沉积的金属膜来制备氢传感器。之后,对其图案化并在其上沉积接触垫。通过将晶片切割成方形、电镀和将芯片切割成方形来制备传感器的检测部件。整个传感器元件的尺寸约为1cm×1cm,检测部件的尺寸小于0.5cm×0.5cm。将钯或钯-银复合颗粒负载于基材上。粒径可以是约100纳米。可以如表1中所示改变粒径和颗粒堆积密度。金属的组成是100%钯,或钯与银的比率为90:10。将这些颗粒排列成数条带,每一条带的带宽为10微米。
图12显示一种实验装置。将氢气传感器固定在由耐热玻璃管制成的玻璃小室中。将玻璃小室置于柱式加热炉中,将其温度控制在分析温度。在玻璃小室的入口处,放置一个尺寸更小的玻璃管(长3厘米,直径1.5厘米),以便改善传感器周围的气体交换。测试气体是用氩气稀释的4%、4000ppm和400ppm的氢气。氮气也可以用作惰性气体。用质量流量控制器提供这些气体。首先,向所述小室提供100cc/min的氮气,然后,用一个四通阀将气体改为50cc/min的测试气体。一段时间后,将气体改为氮气。用一个处理装置箱监测来自传感器的电信号并算出停留时间。
测试氢传感器的性能。图13显示氢传感器在4%的氢中于333K下的停留时间的变化。图13(a)显示绝对停留时间,图13(b)显示基于传感器的初始停留时间的相对停留时间。从氮气转换成氢气后,传感器的电阻快速减小,然后变得似乎接近恒定。在氢气中,相对停留时间的变化幅度为30%至90%,这取决于颗粒的状况。钯复合颗粒的图案会影响传感器的性能。具体地,在10秒的接触时间中,100-SH和100-SN的电阻几乎是一半。900秒(15分钟)后,氢气被转换为氮气。这时,传感器的电阻增加至初始值,但是增加的速度小于降低的速度。这些结果表明,氢气易于渗透至钯复合金属,而氢气从钯复合金属上脱附比渗透慢。
图14显示传感器在333K下的初始电阻。在4%氢气的情况下,响应性的顺序为100-SH>100-SN、100-NN>90-NN、90-SN、100-SL。在400ppm氢的情况,顺序为100-SH>100-NN>90-NN、90-SN>100-SN>100-SL。无论氢气浓度是多少,100-SH的响应性是最高的,而100-SL的响应性是最低的。这意味着,高颗粒堆积密度产生高响应性。当颗粒堆积密度较高时,每一个颗粒在膨胀时几乎都很容易相互接触。金属的组成会影响传感器的响应性。在4%氢气的情况下,100-SN和100-NN的响应性分别显著高于90-SN和90-NN的响应性。在400ppm氢的情况下,100-NN的响应性高于90-NN的响应性,而90-SN的响应性则高于100-SN的响应性。
没有揭示90SN和100-SH的相对级别。然而,在整体上,加入银会抑制由氢气引起的脆裂,而且传感器的响应性会降低。下面,说明粒径的影响。在4%氢气的情况下,无论粒径是多少,100-SN和100-NN,90-SN和90-NN之间的响应性几乎一致。在400ppm氢气的情况下,响应性随着粒径的增加而增加。
在本粒径研究中,大粒径看来是高响应性所需要的。
以上,100-SN型传感器在任何情况下都显示出最高的响应性。接下来,具体评估温度和氢气浓度对100-SN型传感器的影响。
图15图示说明传感器对温度和氢浓度的响应。随着温度的增加,响应性显著地增加(图15(a))。
具体地,80℃时的响应性远远高于60℃时的响应性。在80℃下,10秒内电阻的相对差约是0.9。这种高响应性的原因是,温度增加可能使氢原子在钯复合金属中的扩散速度变得更快并导致金属快速膨胀,以提供高的传感器响应性。
图15(b)显示333K下传感器对氢浓度的响应。随着氢浓度的增加,电阻的变化幅度显著增大。通常,氢在钯金属中的扩散速度与氢气的分压差成正比。氢气的分压基本与氢的浓度成正比。在氢气压力高的区域,金属内部与金属表面的氢气分压差较高。氢浓度的影响可以用以上的原理来解释。
通过使用钯纳米颗粒开发了几种类型的氢传感器,并在宽的温度和氢浓度范围内对它们的性能进行评价。所述传感器通过电阻相对于钯膨胀的变化以及在氢气气氛下传感器的电阻下降来检测氢。无论粒径和颗粒堆积密度如何,这种氢传感器能检测浓度范围为400ppm至4%的氢。总体上说,由100%钯制成的传感器的响应性高于由90%钯-10%银的复合材料制成的传感器。而且,增加颗粒的堆积密度能提高传感器的响应。同时增加温度和氢浓度显著地提高传感器的响应性,这可能是因为,氢气在钯内的扩散速度随着温度和颗粒内部与外部之间的分压差而加快。
参考图10A,发现传感器上能方便地具有0.5mm×2mm(长/直径=4)的作用面积。也可以使用其它尺寸,但是这个尺寸是对电阻、作用面积和传感器稳定性的综合考虑得出的。在该作用面积的每一端可以是1mm×1mm的金结合片。
基片材料可以是钛,但是也可以用反应性较弱的钒来代替钛。本领域的技术人员将认识到,可以使用各种其它材料(包括有机材料),只要这些材料符合电阻率和操作的范围,并且配合传感器作为整体的材料兼容性问题。
钛是一种反应性很强的金属,人们必须清楚地了解它在传感器应用(诸如本发明的传感器)中的使用。参考图10B,为了弥补基于氧化的传感器的老化,可以将参考电阻元件加入传感器中。它可以与活性传感元件相同,但是可能没有镀钯。两种元件以大约相同的速度发生氧化,参考元件用于补偿剩余老化电阻的变化。
为了使电场中基于氧化的老化作用达到最小,可以通过在氧气氛中对传感器升温而使其预氧化。比如,产生电阻钛膜时其厚度可以是100埃。氧化可以使其厚度减少至约80埃,比如以TiO2(一种绝缘体)代替20埃厚。
尽管氧化作用会无限地持续,但是随着氧化物增厚,氧化作用会逐渐变得慢得多,因为大的氧气分子需要比氧化过程开始时渗透得更深。
为了控制老化,可以使钛层增厚,以便通过使其预氧化的薄化过程来校正其厚度。因此,可以使用比如150埃的较厚的膜来代替比如90埃的较薄的膜。折衷的选择是提供较低的初始电阻。图10C图示说明安装在载有传感器的PC板上的传感器对。
参考图10B和10C,单个传感器可以包含两个元件,有源元件和参考元件。它们的大小和形状相同,不同之处在于,参考元件没有进行镀覆。例如可以使用0.5mm×2mm的电阻区,但是本领域的技术人员将认识到,可以使用其它的尺寸和几何形状,只要不改变本发明的方法。
参考图10D,传感器的有源元件的非金区(非结合片区)可以用一个20微米的掩模边界加以覆盖以防止被镀敷。这样就能防止电场效应在该元件边缘附近造成过分镀敷。
参考元件(图10B)在所有方面都与有源元件(图10B)相同,除了它没有镀钯以外。在镀敷步骤中,用于产生镀钯窗的光掩模可以简单地覆盖整个参考元件。
有源元件可以使用两种类型钯掩模,实心填充(solid-fill)型(图10D)或条纹型(图10E)。对于实心填充型元件,除了20微米的边界外,整个作用区域都镀钯。对于“条纹”型元件,可以在实心钛电阻片上形成各种宽度的钯线。正常的线宽和间距分别可以是10微米和10微米。
Claims (6)
1.一种传感器,包含能在氢气存在下膨胀的纳米颗粒,所述纳米颗粒包括钯纳米颗粒或钯-银复合颗粒,所述纳米颗粒的粒径小于50纳米,所述纳米颗粒以颗粒粒径与相邻颗粒的中心到中心距的平均比例为0.85至1.00的密度沉积在基片上。
2.如权利要求1所述的传感器,该传感器还包含两个位于所述基片端部的电极,用于感应通过基片和纳米颗粒的电流。
3.如权利要求2所述的传感器,其特征在于,所述基片是电阻性的。
4.如权利要求1所述的传感器,其特征在于,所述纳米颗粒的粒径为20-30纳米。
5.如权利要求1所述的传感器,其特征在于,所述传感器在0℃至100℃的温度下操作。
6.如权利要求1所述的传感器,其特征在于,所述传感器在60℃至90℃的温度下操作。
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Also Published As
Publication number | Publication date |
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US20070240491A1 (en) | 2007-10-18 |
JP2009534670A (ja) | 2009-09-24 |
CN101467030A (zh) | 2009-06-24 |
EP2064537A2 (en) | 2009-06-03 |
WO2007124408A2 (en) | 2007-11-01 |
WO2007124408A3 (en) | 2007-12-21 |
KR20090007443A (ko) | 2009-01-16 |
CA2649557A1 (en) | 2007-11-01 |
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