CN101421865A - 空气电池及制造方法 - Google Patents
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Abstract
本发明揭示一种具有嵌入于液体电解质(12)中的锂箔阳极(11)的电池(10)，所述锂箔阳极(11)定位于两个类似构造的电池阴极半体(13)与(14)之间。每一阴极半体具有耦合到第一多孔金属衬底(17)的第一玻璃屏障(16)、耦合到第二多孔金属衬底(19)的第二玻璃屏障(18)、耦合到第三多孔金属衬底(21)的第三玻璃屏障(20)及锂空气阴极(22)。外围边缘密封剂层(25)包围所述电解质的外围边缘且将所述两个半体接合在一起。所述电池还包括耦合到所述阳极的阳极端子(27)及耦合到所述阴极的阴极端子(28)。
Description
相关申请交叉参考案
本申请案请求对2006年3月10提出申请的第60/781,399号临时专利申请案的权益。
技术领域
本发明大体来说涉及电池，且更特定来说涉及空气阴极类型的电池。
背景技术
锂空气电池由经由空气阴极电气化学耦合到大气氧的锂阳极组成。经由空气阴极引入到所述电池中的氧气体实质上是无限的阴极反应物源。这些电池具有非常高的比能及相对平坦的放电电压曲线。
提供比现有技术的那些电池容易制造的锂空气电池将是有益的。相应地，本发明的主要目的就是提供此种电池。
发明内容
在本发明的优选形式中，空气电池包含阳极、邻近所述阳极定位的液体电解质、邻近所述液体电解质定位的第一玻璃电解质层、接合到所述第一玻璃电解质层的第一多孔支撑衬底及定位于邻近所述第一多孔支撑衬底且与所述第一玻璃电解质层相对的空气阴极。
在本发明的另一优选形式中，一种制造空气电池的方法包含以下步骤：提供粘性空气阴极层、将第一多孔支撑衬底放置在所述粘性空气阴极层上从而允许所述粘性空气阴极层的一部分被吸入所述第一多孔支撑衬底内，在所述第一多孔支撑衬底上沉积第一玻璃屏障层、将阳极定位于邻近所述玻璃屏障层及将电解质定位于所述阳极与所述玻璃屏障层之间。
附图说明
图1是包含优选形式的本发明的原理的空气电池的透视图。
图2是图1的空气电池的部分分解图。
图3是图1的电池的制造工艺的示意图。
图4是图1的空气电池的一部分的剖面图。
图5是显示正被电镀的图1的空气电池的的一部分的剖面图。
图6是显示在电镀之后的图1的空气电池的一部分的剖面图。
图7是图1的空气电池的一部分的剖面图。
图8是图1的空气电池的一部分的剖面图。
具体实施方式
接下来参照图式，图式中显示包含优选形式的本发明的原理的电池或电气化学电池10。电池10包括嵌入于液体电解质12内的锂箔阳极11，所述锂箔阳极定位于两个类似构造的电池阴极半体13与14之间。每一阴极半体具有耦合到第一多孔金属衬底17的第一玻璃屏障16、耦合到第二多孔金属衬底19的第二玻璃屏障18、耦合到第三多孔金属衬底21的第三玻璃屏障20及锂空气阴极22。外围边缘密封剂层25包围电解质12的外围边缘且将两个半体13与14接合在一起。电池10还包括耦合到阳极11的阳极端子及耦合到阴极22的阴极端子28。在下文中更加详细地论述包含这些组件的材料。
接下来参照图3，为制造电池10，提供阴极材料40的浆。阴极材料40由聚合物粘结剂、碳及溶剂或悬浮液体的混合物组成。所述聚合物粘结剂可以是聚偏二氟乙烯(PVDF)，或另一选择为可以是通常用于电池工业中的许多其它适合的聚合物中的一者。举例来说，所述聚合物粘结剂可由在非溶剂液体悬浮液中作为纳米颗粒悬浮的PTFE或等效材料组成。所述碳优选地是乙炔黑碳材料，但可以是其它类型的适合的碳。阴极集电器可由例如具有小片形状的延伸物(其稍后将用作阴极端子28)的薄铝网等材料制成，首先将所述薄铝网放在铸造台39上。在所述集电器网的顶部上沉积或铸造阴极材料40的可选第一涂层且允许其固化。一旦干燥，从所述铸造表面剥离其中嵌入有所述集电器的阴极材料且将其翻转并放置在所述铸造台上，其中所述集电器的未经涂敷的侧朝上。然后，将阴极材料40的第二涂层施加到所述集电器的暴露表面上。可通过使用医生的刀片42来将所述涂层施加到所述集电器。所述阴极材料的优选厚度为10微米与5毫米之间，然而所述厚度取决于电池的所需特性。
在阴极材料的第二涂层固化之前，在所述阴极材料层或阴极22上沉积第一多孔金属衬底或多孔金属界面层17。第一多孔金属衬底17优选地是在化学上不反应的金属，例如铝或镍，其具有12微米与300微米之间的厚度。金属衬底17具有经测量在100毫微米与25微米之间的孔。金属衬底17在粘性阴极材料层上“浮动”使得阴极材料40可通过毛细管作用吸入到多孔金属衬底17的孔中。我们相信，仅聚合物或可能所述聚合物及丙酮或聚合物及悬浮液体被吸入所述孔中，而碳可以或可不具有防止其被吸入所述孔中的颗粒大小。将经固化的阴极层22与多孔金属衬底17作为单个层从铸造台39移除。此可简单地以常规方式从台39剥离所述层来完成。
然后，在多孔金属衬底17的顶表面上沉积与阴极层22相对的玻璃屏障层(第一玻璃屏障16)。可制作第一玻璃屏障16以及下文所说明的其它玻璃屏障且其可以是LiPON(锂磷氧氮，LixPOyNz)。应了解，可通过沉积此类玻璃层的其它常规已知方法来产生第一玻璃屏障16，所述方法例如化学蒸汽沉积(CVD)、金属有机物化学蒸汽沉积(MOCVD)、RF溅镀或其它常规已知技术。
应注意，为进一步增强保护阳极11免受潮湿，所述电池可包括多层多孔金属衬底17、19及21及玻璃屏障层16、18及20，如其中每一阴极半体13及14包括三个此类组合层的优选实施例中所示。因此，所述优选实施例显示上面沉积有第二玻璃屏障18的第二多孔金属衬底19及上面沉积有第三玻璃屏障20的第三多孔金属衬底21，所述第二及第三玻璃屏障均以类似于第一玻璃屏障的方式沉积。所述多孔衬底与玻璃屏障的多个分层防止一个层中的针孔44传播穿过整个保护结构，即在所述工艺中形成的任何针孔44不可能互相对准而穿过多个层，如图8中所示。
然后，通过电镀工艺处理第一玻璃屏障16、第二玻璃屏障18及第三玻璃屏障20的顶表面以将在所述玻璃屏障中形成的任何针孔44钝化，如图5至9中的更加详细地显示。将每一玻璃屏障的顶表面暴露于电镀溶液46，所述电镀溶液可以是醚、氯化铝(AlCl3)及小百分比的氢化锂铝(LiAlH4)的溶液，同时向相关联的金属衬底施加电流。所述电镀工艺形成填充所述玻璃屏障中的针孔44的铝插塞47。铝插塞47还延伸到所述金属衬底的基本孔。因此，铝插塞47填充所述玻璃屏障中的针孔44。必须将这些铝插塞或其至少顶部部分钝化以防止电流穿过所述玻璃。可通过简单地在升高的温度下将铝插塞暴露到氧气氛来将其氧化而使其钝化。另一选择为，可通过用掺杂有硅的四甲基氢氧化铵(TMAH)(其在所述插塞上形成二氧化硅的薄层)对所述插塞进行处理来使其钝化。另一选择为，可在所述插塞到达玻璃屏障的顶表面之前停止所述插塞的形成，然而由于难以控制所述工艺及所得插塞的形成，因此我们相信所述插塞的二氧化硅涂层是更可靠的解决方案。
如图7中所示，将外围环氧树脂层49施加到第一玻璃屏障16与第二多孔金属衬底19之间的外围区域，使得所述屏障及所述衬底沿其外围边际接合在一起。同样，将外围环氧树脂层50或其它适合的接合材料施加到第二玻璃屏障18与第三多孔金属衬底21之间的外围区域，使得所述屏障及所述衬底沿其外围边际接合在一起。所述接合形成由所述第一、第二及第三金属衬底17、19及21及所述第一、第二及第三玻璃屏障16、18及20组成的多层结构。环氧树脂层49及50在相邻的玻璃屏障之间形成空间且金属衬底重叠在那里。用液体或(另一选择为)液体/聚合物电解质材料52填充这些新形成的空间及所述金属衬底的孔以提供屏障之间的离子导电性。此可通过将所述电解质材料注入穿过环氧树脂且然后密封由注入装置产生的洞来完成。所述电解质材料可以是液体电解质，例如碳酸丙烯及二亚甲基及六氟化锂磷。应了解，可将其它类型的电解质及沉积电解质的方法用作刚刚说明的方法的替代方案。
如图2中所示，电池10具有夹于两个类似构造的阴极半体13与14之间的安装在中间的阳极11，每一阴极半体包括三个经钝化的玻璃屏障16、18及20、三个金属衬底17、19及21及空气阴极22。在惰性气体环境中，通过将外围环氧树脂层25或其它适合的密封剂材料施加到第三玻璃屏障的朝内的顶表面的外围区域或边际周围来在阳极11的任一侧上将两个阴极半体13与14结合在一起。阳极11包括延伸穿过所述密封剂的阳极端子27。然后，将液体电解质12注入到两个电池部分13与14之间的空间内以确保阳极11与阴极22之间的离子导电性。然后，将阴极端子28安装到每一阴极22。
所述构造工艺中的最后步骤是将电解质浸入阴极22中。可将所述电池放置在包含氧的适合环境中。电池的操作使得在放电时，电流在锂离子从锂金属阳极传导穿过所述电解质屏障系统并进入其在其中与来自电池环境的氧反应的阴极内时产生。所述电解质可由溶解于溶剂中的六氟化锂磷盐组成，例如采用通常用于电池工业中的碳酸丙烯(PC)的那些。由于基于碳酸丙烯的溶剂的挥发性性质及六氟化锂磷盐在潮湿环境中的不稳定性，使用此类型的电解质的电池在经密封封装内的纯氧环境下产生最佳性能。
另一选择为，可使用使用乙酰胺及三氟甲烷磺酰亚胺锂的锂盐的电池。通常，摩尔盐/乙酰胺比率是1比4。锂盐及乙酰胺两者在室温下均为固态。在将所述两种固体混合在一起之后，将其搅拌一整夜且然后将其温热在80摄氏度的温度下四个小时，从而形成非常清澈的溶液。所述离子液体的锂离子导电性是4*10-3S/cm。此类离子液体电解质具有极低的蒸汽压且因此在户外操作时不容易干燥。因此，此类型的电解质可用于靠来自周围空气的氧运转且不具有密封的封装的电池中。
作为刚刚说明的实施例的替代方案，所述阴极材料可由聚合物、碳、丙酮及所述聚合物的增塑剂(例如，二丁基阿德帕特(dibutyle adepate))的混合物组成。在此方法中，在已将多孔金属衬底接合到位之后移除所述增塑剂。可通过在将不会溶解所述接合聚合物的任一溶剂或其它适合溶剂(例如，甲醇)中冲洗所述阴极结构来从所述聚合物移除所述增塑剂。在此方法中，所述接合聚合物经配置以在形成聚合物/电解质凝胶系统时吸收大量的电解质。
在所述电池的替代实施例中，可在所述多孔金属衬底将担当玻璃电解质支撑层及阴极集电器的双重功能的情况下去除金属网阴极集电器。在此实施例中，阴极端子将被附装到所述金属衬底。
额外替代实施例将用多孔陶瓷或多孔聚合物材料替代多孔金属衬底17。适合的多孔陶瓷金属是由Watman(沃特曼)公司制造的Anodisc无机膜。此材料是具有高孔隙率(其中其孔延伸穿过所述膜)的阳极化铝。所述膜厚度为约60微米，其中孔直径为约200毫微米，但其它孔直径也可接受。另一方面，可使用通常用于制造电池的多孔亲水特富龙隔离材料。在这些情况下，如果实施经填塞的针孔特征，那么可在玻璃电解质层下方沉积薄金属层。此种子层将足够厚以提供用于镀敷工艺的电连续性，但也足够薄从而不会关闭或覆盖衬底的孔。
额外替代实施例将仅使用单个屏障层，所述屏障层是其衬底通过阴极聚合物接合材料直接接合到阴极的层。在此情况下，可实施所述针孔填塞选项，或另一选择为可不实施所述针孔填塞选项。
应了解，虽然在优选实施例中显示三个金属及玻璃层，但本发明可包括单层金属及玻璃。
应了解，术语玻璃屏障既定包括适合的陶瓷屏障。应了解，如本文中所使用，术语空气阴极等效于术语空气电极。
因此，可看出，现在提供在简单的工艺中制造的锂空气电池。当然，应了解，除在本文中具体叙述的那些修改以外，还可在不背离以上权利要求书中所论述的本发明的精神及范围的情况下对本文中所说明的具体优选实施例做出许多修改。
Claims (16)
1、一种空气电池，其包含：
阳极；
液体电解质，其邻近所述阳极定位；
第一玻璃电解质层，其邻近所述液体电解质定位；
第一多孔支撑衬底，其接合到所述第一玻璃电解质层；及
空气阴极，其邻近所述第一多孔支撑衬底定位并与所述第一玻璃电解质层相对。
2、如权利要求1所述的空气电池，其中所述第一多孔支撑衬底选自由多孔金属衬底、多孔陶瓷衬底及多孔聚合物衬底组成的群组。
3、如权利要求1所述的空气电池，其中所述空气阴极是由聚合物粘结剂、碳及溶剂或悬浮液体的混合物制成的阴极材料。
4、如权利要求1所述的空气电池，其进一步包含第二玻璃电解质层及接合到所述第二玻璃电解质层的第二多孔支撑衬底。
5、如权利要求4所述的空气电池，其进一步包含第三玻璃电解质层及接合到所述第三玻璃电解质层的第三多孔支撑衬底。
6、如权利要求1所述的空气电池，其中所述第一多孔支撑衬底的孔被钝化。
7、如权利要求6所述的空气电池，其中所述孔由具有电绝缘顶层的金属插塞钝化。
8、如权利要求1所述的空气电池，其中所述阳极为锂阳极。
9、一种制造空气电池的方法，其包含以下步骤：
(a)提供粘性空气阴极层；
(b)将第一多孔支撑衬底放置在所述粘性空气阴极层上以便允许所述粘性空气阴极层的一部分被吸入所述第一多孔支撑衬底中；
(c)在所述第一多孔支撑衬底上沉积第一玻璃屏障层；
(d)邻近所述玻璃屏障层定位阳极；及
(e)将电解质定位于所述阳极与所述玻璃屏障层之间。
10、如权利要求9所述的制造空气电池的方法，其中所述第一多孔支撑衬底选自由多孔金属衬底、多孔陶瓷衬底及多孔聚合物衬底组成的群组。
11、如权利要求9所述的制造空气电池的方法，其中所述空气阴极是由聚合物粘结剂、碳及溶剂或悬浮液体的混合物制成的阴极材料。
12、如权利要求9所述的制造空气电池的方法，其进一步包含将第二玻璃电解质层及接合到所述第二玻璃电解质层的第二多孔支撑衬底安装到所述第一玻璃电解质层的步骤。
13、如权利要求12所述的制造空气电池的方法，其进一步包含将第三玻璃电解质层及接合到所述第三玻璃电解质层的第三多孔支撑衬底安装到所述第二玻璃电解质层的步骤。
14、如权利要求9所述的制造空气电池的方法，其进一步包含将所述第一多孔支撑衬底的孔钝化的步骤。
15、如权利要求14所述的制造空气电池的方法，其中用具有电绝缘顶层的金属插塞将所述孔钝化的步骤。
16、如权利要求9所述的制造空气电池的方法，其中所述阳极为锂阳极。
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2007
- 2007-03-09 CN CN2007800135825A patent/CN101421865B/zh not_active Expired - Fee Related
- 2007-03-09 US US11/684,117 patent/US7731765B2/en not_active Expired - Fee Related
- 2007-03-09 WO PCT/US2007/063683 patent/WO2007106742A2/en active Application Filing
- 2007-03-09 JP JP2008558551A patent/JP2009529768A/ja active Pending
- 2007-03-09 KR KR1020087024826A patent/KR20080106574A/ko not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707241B (zh) * | 2009-11-27 | 2011-11-30 | 青岛生物能源与过程研究所 | 一种锂空气电池隔膜及制备方法 |
| CN102569822A (zh) * | 2010-12-07 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | 锂空气电池用防阻塞空气电极 |
| CN108242548A (zh) * | 2016-12-27 | 2018-07-03 | 现代自动车株式会社 | 用于具有改善容量的锂空气电池的阴极 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080106574A (ko) | 2008-12-08 |
| CN101421865B (zh) | 2012-09-26 |
| US20090325017A9 (en) | 2009-12-31 |
| WO2007106742A3 (en) | 2008-10-09 |
| JP2009529768A (ja) | 2009-08-20 |
| US7731765B2 (en) | 2010-06-08 |
| WO2007106742A2 (en) | 2007-09-20 |
| US20070212583A1 (en) | 2007-09-13 |
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