CN101669235B - 沉积的微体系结构电池和制造方法 - Google Patents
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Abstract
一种电池，其包括第一部分，所述第一部分包括其上形成有集电器和阳极电极材料的基底。第二部分形成于基底上，并包括集电器和阴极电极材料。所述第一部分接合于所述第二部分且在接合的所述第一部分和所述第二部分之间设置有隔离器，以将所述阳极电极材料与阴极电极材料隔开。电解质放置为与所述阳极电极材料、所述阴极电极材料以及所述隔离器接触。
Description
技术领域
本发明涉及能量储存***。更具体地，本发明涉及沉积的微体系结构电池***及其设计和制造方法。
背景技术
许多微机电***(MEMS)需要电能电源。在一些情况中，电力由偶联的电池或电池***提供。如果电池大，则丧失了MEMS器件的尺寸优势。电极材料、隔离器和电解质的物理限制决定了它们要分开制造，并随后将电池与MEMS器件偶联。
MEMS技术也已使完全可植入医疗器械的发展成为可能。然而，这些设备的电源可占这些***高达85％的重量和35％的体积。最小的商用电池在毫米(mm)范围内，并且利用锌或锂的化学。通常使用不锈钢壳来容纳流体电解质和气态反应副产物。
可植入***的进一步小型化需要与MEMS制造技术和与MEMS加工相容的材料和基底具有增强的相容性的新电池技术。电源的选择也将不仅依赖于电化学。在设计过程中，必须考虑形状因素、性能、寿命、化学品的毒性以及热生成率。这在可植入***中尤为如此。
发明内容
本发明的一些实施方案涉及微体系结构电池。这些电池可用于建造微观封装(microscopic footprint)，典型地约为1mm2，并能在制造时直接集成到MEMS器件中。微体系结构电池具有克服过去的MEMS能量与电力限制的潜力，并将能够广泛利用MEMS器件来建造用于环境或生物医学应用的无线传感器网络，这是因为可以建造与该***其它部件规模相同的电源。通过使用改进的制造工艺来沉积电池材料，可降低能量损耗并增加储存容量，使微电池能具有可与MEMS集成的尺寸且能满足其寿命需要。
附图说明
图1是根据本发明一个实施方案的包括偶联的微机械加工电池的微机电***的示意图。
图2是根据本发明一个实施方案的微机械加工电池的截面视图。
图3是多单个电池的微机械加工电池的示意图。
详细说明
MEMS器件可得益于可与MEMS器件一起制造或以与MEMS器件的制造相容的方式制造的薄膜微体系结构沉积电池。微电池可使用用于MEMS器件自身的工艺技术制造。以此方式，微电池可制造为具有不大于器件自身的封装尺寸，可在MEMS器件的加工过程中或使用与MEMS器件相同的工艺技术制造。微电池可直接偶联到MEMS器件，省去额外的工艺步骤。其它的微体系结构工艺可应用于基底以建造用于电解质的空隙、连接或微通道，所述工艺例如为激光加工、微钻孔、微切削或类似工艺。虽然关于适合与MEMS器件组合的电池结构描述了本发明的几个实施方案，但是该技术可放大到更大的尺寸。因此，本发明可用于设计和制造用于集成到规格大得多的应用的电池，这些应用包括更大的便携设备例如移动电话、个人数字助理(PDA)和膝上型电脑；平板光伏阵列和为各种设备(包括机动车辆)供电的大规格、高功率方型或卷绕型单电池，或为电网电能装置提供负载均衡。
图1示出MEMS器件10和偶联的微机械加工电池12。MEMS器件可包括玻璃硅基基底14，例如二氧化硅(SiO2)；在基底14上形成的换能器16和电路18，例如在基底14中形成的处理器。盖20可封闭电路18但露出换能器。本发明不限于MEMS器件的特定结构或其预期功能，包括MEMS器件是否为或是否包括换能器，或MEMS器件是否包括处理电路或类似结构。因此，MEMS器件实际上可以是具备电力需求的任意类型的MEMS器件。
微机械加工电池12偶联到MEMS器件10，且该微机械加工电池12可以例如利用聚合物粘合剂19(如两部分环氧树脂)粘接到MEMS器件10。
图2以截面图示出微电池，例如微体系结构电池12。在该实例中，基底已使用微型金刚石钻头加工以在电极之间形成适于容纳固体、凝胶或液体电解质的空隙。微体系结构电池12包括第一部分22和第二部分24以及位于两部分之间的隔离器26。所述两个部分分别限定阳极和阴极，因此至少在电极材料方面不同。所述两个部分可通过粘合剂(例如快速固化的环氧树脂)固定在一起，隔离器26设置在其间。隔离器26可以是由聚合物如
形成的膜或其它具有纳米尺寸孔的聚合物膜，并且可以为约25微米(μm)厚，低至100nm。
可利用所述两部分中的一个或两个中形成的微流体通道28(以虚线示出，因为在引入电解质之后这些通道即被密封)引入电解质。在一个优选实施方案中，延迟电解质的引入，直到MEMS器件投入运行，以增加器件的搁置寿命以及可用寿命。
每个部分22和24可通过将电极材料30沉积到基底32上来形成。有利的是，合适的集电器结构34也在电极沉积过程中或作为后续过程沉积在基底32上。集电器34可形成为包括导电搭接头36，以允许待偶联到MEMS器件10的电池的输出。电极活性材料的沉积可通过激光加工(例如Nd-YAG激光器或其它类型的激光器)与脉冲激光沉积(PLD)、电子束沉积(EBD)、化学气相沉积(CVD)、物理气相沉积(PVD)、化学流体沉积(CFD)或电镀或以上任意组合的组合来实现。
在一个实例中，不限制微体系结构电池12的一般性质，可通过首先使用计算机辅助设计和印制技术形成掩模而制备用于阳极和阴极的基底32。可将光致抗蚀剂旋涂于空白基底母料上(如晶片材料)，并使用紫外(UV)暴光或其它方法固化。光致抗蚀剂可通过溶剂选择性地移除。然后可以使用蚀刻剂将基底蚀刻到期望的深度，所述蚀刻剂例如为氢氟酸(HF)，或者其它能均一且可控地移除材料的蚀刻剂。
作为湿法蚀刻的一个替代方案，可用激光烧蚀来蚀刻基底。激光烧蚀能够提供更少的加工步骤和更快的加工速度。然而，湿法蚀刻可提供对蚀刻深度和空腔几何深度更好的控制。
第一部分22(在该实例中为锌(Zn)阳极)可通过利用三个金属沉积步骤形成。用于粘合的镍(Ni)层(未示出)或其它金属或金属氧化物材料可沉积在蚀刻的基底上，然后沉积金(Au)或其它导电集电器(如集电器34)。然后沉积用于活性材料(如电极材料30)的锌层。在该实施方案中，经由气雾喷涂沉积悬浮于石油或其它蒸馏物中的Zn纳米颗粒来沉积锌(Zn)。
第二部分24(在该实例中为氧化银(AgO)阴极)可利用三个金属沉积步骤形成。将用于粘合的镍(Ni)层(未示出)或其它金属或金属氧化物材料沉积在蚀刻的基底上，然后沉积金(Au)或其它导电集电器(如集电器34)。然后沉积用于活性材料(如电极材料30)的银层。在设置银活性材料之后，将银氧化为氧化银。氧化过程通过将该结构浸在过氧化氢(H2O2)中直至银材料被充分氧化而实现。或者，金属的氧化可通过将膜在臭氧氛(O3)中暴露于UV射线而实现。为此目的，可利用其它氧化剂或气氛，利如在金属沉积过程中将基底膜暴露于氧(O2)。
可以使用任何适当的金属沉积技术。PVD较其它工艺可提供更快的厚(大于10μm)金属层沉积。作为一个替代方案，对于所述膜，如果所需的活性材料的厚度超过经由PVD或溅镀所能够实现的厚度，也可使用电镀。集电器的厚度通常小于活性材料的厚度，并可通过任何适当的技术形成。化学流体沉积提供低温加工的优势，并可减少加工步骤的数目。虽然可使用烧结来将银粉末沉积到基底上，但是由于所需的加工温度，该工艺可能是较不期望的。最终电极结构的表面光洁度强烈取决于基底的温度和所用的蒸发技术。PVD在较低的基底温度下进行，生成的基底具有较高孔隙度和更粗糙的表面光洁度。所沉积的膜可以是无定形的，并且可能需要后续加热以引起再结晶。对于采用液体电解质的电池电极而言，多孔结构是有益的，这是因为提供了活性表面区域和电解质可透过性，并同时保持电导率和机械完整性。
如果需要，可在晶片或其它基础结构上制备多个基底。在蚀刻之后，按需要完成金属沉积和氧化步骤，以获得合适的比能量功率特性和重量能量功率特性(energy and power characteristics)。各个基底可利用标准的切削技术从晶片分离。在阳极部分的切割过程中不应使用冷却水，以防止锌氧化。
亚毫米直径通道或孔28(例如，直径为约100μm)在基底32中形成，以允许将电解质例如氢氧化钾(KOH)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸亚丙酯(PC)或其它传导离子且为电中性的电解质引入已完成的微体系结构电池结构12中，同时将空气排出。作为一个替代方案，可使用凝胶型电解质，并且在所述部分的接合和密封过程中将其封闭在微电池结构中，或者可在之后利用形成于基底中的适于此目的的通路将其***。
可使用微机械钻孔或化学钻孔来形成孔28。任选的玻璃通道(未示出)可***到形成的洞中，并且利用快速固化的环氧树脂固定于其中。在引入电解质之后，可将玻璃通道(如果存在的话)可从封装切掉，并使用环氧树脂密封孔28。
在前面的实例中，各个基底在组装成电池结构之前是分开的。可在分开之前组装多个电池。在金属沉积步骤完成之后，可以在一个或两个晶片上设置粘合剂，例如一种或更多种干粘合剂片或丝网印刷的湿粘合剂。然后可以将晶片以晶片-粘合剂-隔离器-粘合剂-晶片夹层的形式组合在一起，使粘合剂固化，然后将各个电池分开。
微机械加工电池的多次处理还允许制造多个单电池的微机械加工电池。在分开工艺过程中，可使多个单电池保持接合状态(参见图3中示出的电池的单电池12’)。在集电器34和导电搭接头36的形成过程中，导电搭接头可形成连接多个单电池(参见导电搭接头36’)以为多个单电池的微机械加工电池提供单一输出。
实际的电极、电解质和隔离器材料可针对应用进行选择，并可使用已知的优化技术进行改进。一种这样的优化技术由Albano等人在Design ofan Implantable Power Supply for an Intraocular Sensor，Using POWER(Power Optimization for Wireless Energy Requirements)和Cook等人在POWER(power optimization for wireless energy requirements)：AMATLAB based algorithm for design of hybrid energy systems(Journal ofPower Sources 159(2006)758-780)中进行了描述。
镍单电池化学具有射频可充电的优点。银单电池化学可增强可靠性并提供放电电流稳定性。薄膜技术(包括锂化学)在与MEMS器件组合时因在MEMS加工中可能需要高加工温度而具有潜在的加工困难。然而，一些单电池化学可能能够经受高达200℃的温度。
将微机械加工电池12接合到MEMS器件10的聚合物与硅的粘接可通过首先用蒸发的金涂覆两个部分而得到增强。等离子体增强化学气相沉积(PECVD)氮化硅膜也可增强粘接。已知金与硅可生成低共熔化合物，该化合物具有较其纯金属低得多的熔点。接合工艺中生成液体膜，该液体膜在冷却和固化之后将两个部分粘接起来。
根据本发明的电池的实施方案可具有以下特征的一个或更多个：
1)在制造MEMS器件的同时形成并与之集成；
2)小型、轻质，能够建造自动和远程的传感器网络；
3)表现出高的重量和体积能量和功率以及法拉第效率，优于电势满足(～27mWh/em2)的商业电池；
4)由于高精确制造，具有低内阻和低电力泄露；
5)薄膜沉积的电极；
6)可堆叠和/或层合的电极以获得更高的电压；
7)适于作为薄膜平板单电池、方型单电池堆、柱型单电池或螺旋卷绕型单电池的结构；
8)可修改成一次或二次电化学；
9)与固体薄膜电解质或电解质的液体或凝胶溶液相容；
10)能够气密性密封；
11)能降低成本地大量生产；
12)可放大到宏观电池尺寸。
虽然根据本文描述的实施方案的电池在MEMS器件中的应用是明显的，但是其技术完全可放大，并且大规模的沉积电池是可能和期望的。用于小电池的本发明技术的示范示出并证实了该方法。因此，本发明和本发明的实施方案提供：
A)用于尺寸显著减小和能量和功率性能显著提高的MEMS的优化电源设计和构造，其允许在器件制造的同时或制造完成之后进行集成；
B)一种基于薄膜沉积的制造技术，其允许制造小规模、低成本和可集成的CMOS***；
C)微电池堆、布置和多单电池结构的容量和寿命的表征；和
D)用于在刚性或柔性基底上形成微观电极膜以及通过向所述基底应用微体系结构化技术来形成液体、凝胶或固体电解质空隙的工艺。
虽然关于可用于故障保护器件的安装组件的几个优选实施方案描述了本发明，但是应理解，本发明不限于这些器件。其发明构思可应用于许多器件和结构。此外，尽管以组合方式显示并描述了各实施方案的特征，但是这些特征可单独地实施，每个这样的单独实施均在本发明的范围内。
尽管本公开容许各种修改方案和替换形式，但是以举例的方式在附图中和本文中描述的实施方案中示出某些实施方案。然而，应当理解，本公开无意于将本发明限制于描述的特定形式，相反，本发明意于覆盖由所附权利要求所定义的所有修改方案、替代方案和等同物。
还应理解，除非在本专利中使用语句“本文所用的术语“__”在此定义为指...”或类似的语句来清楚地定义术语，则无意于以明显或暗示的方式将该术语的含义限定为超过其清楚或通常的含义，并且该术语不应被解读为限定在基于本专利的任何部分中的任何陈述的范围内(除权利要求的语言外)。就本专利所附的权利要求中记载的任何术语来说，在本专利里指单一的含义，这只是为了清楚起见以不使读者困惑，并且无意于通过暗示或其它方式将该权利要求术语限定于单一的含义。除非用词语“意思是”和无任何结构记载的功能来定义权利要求的要素，则无意于基于35U.S.C.§112的第六段来解读任何权利要求要素的范围。
Claims (13)
1.一种电池，包括：
第一部分，所述第一部分包括第一基底，所述第一基底包括通过蚀刻所述第一基底的一部分形成的第一空腔、薄膜集电器和薄膜阳极电极材料，所述薄膜集电器和所述薄膜阳极电极材料设置在所述第一空腔内；
第二部分，所述第二部分包括第二基底，所述第二基底包括通过蚀刻所述第二基底的一部分形成的第二空腔、薄膜集电器和薄膜阴极电极材料，所述薄膜集电器和所述薄膜阴极电极材料设置在所述第二空腔内；
所述第二部分偶联到所述第一部分，以及
设置在所述第一部分和所述第二部分之间的隔离器以将所述阳极电极材料与所述阴极电极材料隔开。
2.权利要求1所述的电池，其中所述薄膜阳极电极材料和所述薄膜阴极电极材料包含高度多孔微结构。
3.权利要求1所述的电池，其还包括与所述阳极电极材料、所述阴极电极材料和所述隔离器接触的电解质。
4.权利要求1所述的电池，其中所述第一基底和第二基底各自包含玻璃，所述玻璃被蚀刻以提供所述第一空腔或第二空腔，用于在所述第一空腔或第二空腔上形成所述集电器和所述阳极或阴极电极材料。
5.权利要求4所述的电池，其中所述玻璃包含硅的氧化物。
6.权利要求1所述的电池，其中所述阳极电极材料包括选自锌、锂金属(Li)、石墨(C)、中间相碳微球(MCMB)或其它碳嵌入化合物的材料。
7.权利要求1所述的电池，其中所述阴极电极材料包括选自：氧化银、锂锰氧化物、锂铁磷酸盐、LiNixCoyAlzO2和LiNixCoyMnzO2的材料。
8.权利要求3所述的电池，其中所述电解质材料包括选自如下的材料：氢氧化钾(KOH)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸亚丙酯(PC)或其它传导离子且为电中性的电解质。
9.一种制造电池的方法，包括：
蚀刻第一基底的一部分以在所述第一基底内形成第一空腔；
在所述第一空腔中设置薄膜集电器材料和薄膜阳极电极材料；
蚀刻第二基底的一部分以在所述第二基底内形成第二空腔；
在所述第二空腔中设置薄膜集电器材料和薄膜阴极电极材料；和
在所述第一基底和所述第二基底之间提供隔离器以将所述薄膜阳极电极材料与所述薄膜阴极电极材料隔开。
10.权利要求9所述的方法，还包括：
在所述第一基底和所述第二基底中形成亚毫米直径通道；和
通过所述通道提供与所述阳极电极材料、所述阴极电极材料和所述隔离器接触的电解质。
11.权利要求9所述的方法，其中蚀刻所述第一基底的一部分和蚀刻所述第二基底的一部分包括使用或不使用掩模的蚀刻或通过应用激光的烧蚀。
12.权利要求9所述的方法，其中设置阳极和阴极材料包括使用等离子体气相沉积、化学流体沉积、电镀、烧结或溅镀。
13.权利要求9所述的方法，还包括接合所述第一基底和所述第二基底，其包括粘接所述第一基底与所述第二基底。
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| JP2010524158A (ja) | 2010-07-15 |
| US20130017433A1 (en) | 2013-01-17 |
| WO2008121972A2 (en) | 2008-10-09 |
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| WO2008121972A3 (en) | 2008-11-27 |
| EP2132806A4 (en) | 2012-12-19 |
| US20080248382A1 (en) | 2008-10-09 |
| US8603662B2 (en) | 2013-12-10 |
| JP5175333B2 (ja) | 2013-04-03 |
| EP2132806A2 (en) | 2009-12-16 |
| CN101669235A (zh) | 2010-03-10 |
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