CN101702444A - 具有非水中间层构造的受保护的活性金属电极和电池组电池结构 - Google Patents
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Abstract
本发明名称为“具有非水中间层构造的受保护的活性金属电极和电池组电池结构”。活性金属和具有离子导电保护构造的活性金属嵌入电极结构和电池组电池,该离子导电保护构造包括活性金属(例如锂)导电不透水层,该不透水层通过用非水电解质(阳极电解液)浸渍的多孔隔膜与电极(阳极)分开。这种保护构造防止了活性金属与不透水层另一(阴极)侧上环境的不利反应,该环境可包括含水或非水液体电解质(阴极电解液)和/或各种电化学活性材料,包括液体、固体和气体氧化剂。还提供了安全性添加剂和有利于制造的设计。
Description
本申请是基于申请日为2004年10月8日、申请号为200480042697.3、发明名称为“具有非水中间层构造的受保护的活性金属电极和电池组电池结构”的申请所提交的分案申请
技术领域
本发明一般涉及活性金属电化学装置。更特别地,本发明涉及活性金属(例如碱金属,如锂)、活性金属嵌入(例如锂-碳、碳)和活性金属合金(例如锂-锡)合金或合金化金属(例如锡)电化学(例如电极)结构和电池组电池。电极结构具有离子导电保护构造,该保护构造包括活性金属(例如锂)导电不透水层,其被用非水电解质浸渍的多孔隔膜与电极(阳极)隔开。这种保护结构防止了活性金属与不透水层的另一(阴极)侧上环境的有害反应,环境可包括含水、空气或有机液体电解质和/或电化学活性材料。
背景技术
碱金属如锂的低当量使它们作为电池电极部件尤其有吸引力。锂能提供比传统电池标准-镍和镉更大的每体积的能量。不幸的是,可再充电锂金属电池在市场上还没有成功。
可再充电锂金属电池的失败很大程度上归因于电池循环问题。在反复的充电和放电循环中,锂“枝晶”通过电解质从锂金属电极逐渐生长出来,并最终接触正极。这导致电池内部短路,使电池在较少的几次循环后就不能再使用。在循环的同时,锂电极还可能生长出会从负极上移开的“海绵状”沉积物,并因此降低了电池容量。
为了解决锂在液体电解质体系中差的循环性能,一些研究人员提出对锂负极面向电解质的侧涂敷“保护层”。这种保护层必须能传导锂离子,但同时防止锂电极表面和主体电解质之间的接触。许多应用保护层的技术都没有成功。
一些预期的锂金属保护层都在原位通过锂金属和接触锂的电池电解质中的化合物之间的反应来形成。这些原位薄膜中的大部分都是通过组装电池后的控制化学反应来生长。通常,这种薄膜具有允许部分电解质渗透到裸锂金属表面上的多孔形态。因此,它们不能充分地保护锂电极。
还考虑了各种预先成形的锂保护层。例如,美国专利5314765(1994年5月24日签发给Bates)描述了制造包含一薄层溅射的氧氮磷锂(“LiPON”)或相关材料的锂电极的外部技术。LiPON为一种玻璃态单离子导体(传导锂离子),其已被研究作为固态锂微电池的可能电解质,固态锂微电池被制造在硅上并用于功率集成电路(参见美国专利5597660、5567210、5338625和5512147,全部签发给Bates等)。
本申请人实验室中的工作已开发了在活性金属电池电极中使用玻璃态或非晶态保护层如LiPON的技术。(参见例如美国专利6025094,02/15/00签发,6402795,06/11/02签发,6214061,04/10/01签发,和6413284,07/02/02签发,全部转让给PolyPlus Battery公司)。
在含水环境中使用锂阳极的现有努力依靠强碱性条件的使用如浓KOH水溶液的使用来减缓Li电极的腐蚀,或依靠在Li电极上使用聚合物涂层来阻止水扩散到Li电极表面上。但是,在所有情况下,都存在大量的碱金属电极与水的反应。对此,现有技术教导与Li-金属阳极一起使用含水阴极或电解质是不可能的,因为水的击穿电压为约1.2V,Li/水电池可具有约3.0V的电压。锂金属和水溶液之间的直接接触导致强烈的寄生化学反应和没有任何有用目的的锂电极的腐蚀。因此,锂金属电池领域中的研究焦点直接在有效的非水(大部分为有机)电解质体系的开发上。
发明内容
本发明一般涉及活性金属电化学装置。更特别地,本发明涉及活性金属(例如碱金属,如锂)、活性金属嵌入(例如锂-碳、碳)和活性金属合金(例如锂-锡)合金或合金化金属(例如锡)电化学(例如电极)结构和电池组电池。电极结构具有离子导电的保护构造,该保护构造包括活性金属(例如锂)离子导电基本不透水层,其被用非水电解质(阳极电解液)浸渍的多孔隔膜与电极(阳极)隔开。这种保护构造防止了活性金属与不透水层的另一(阴极)侧上环境的有害反应,环境可包括含水、空气或有机液体电解质(阴极电解液)和/或电化学活性材料。
保护构造的隔膜层(中间层)防止阳极的活性金属(例如锂)和活性金属离子导电基本不透水层之间的有害反应。因此,该构造有效地隔离(分离)了阳极/阳极电解液与溶剂、电解质处理和/或阴极环境,包括通常对Li或其它活性金属强腐蚀的这种环境,并且同时允许离子传递进入和离开这些可能腐蚀的环境。
本发明的电池和电池结构的各种实施方案包括活性金属、活性金属离子、活性金属合金化金属和活性金属嵌入阳极材料,这些材料被具有非水阳极电解液的离子导电保护构造所保护。这些阳极可在电池组电池中与各种可能的阴极体系结合,阴极体系包括水、空气、金属氢化物和金属氧化物阴极和相关的阴极电解液体系,尤其是含水阴极电解液体系。
对于保护构造的基本不透水层(例如玻璃或玻璃-陶瓷膜)破裂或以其它方式破碎并允许侵蚀性阴极电解液进入和接近锂电极的情况,还可向本发明的结构和电池内引入安全性添加剂。非水中间层结构可掺入当与反应性阴极电解液接触时会引起锂表面上形成不透水聚合物的凝胶/聚合剂。例如,阳极电解液可包括在水中不溶或很少溶解的聚合物的单体,例如二氧戊环(Diox)/聚二氧戊环(polydioxaloane),阴极电解液可包括单体用聚合引发剂,例如质子酸。
另外,本发明的结构和电池可采用任何合适的形式。有利于制造的一种有利形式为管状形式。
在一个方面,本发明涉及电化学电池结构。该结构包括由活性金属、活性金属离子、活性金属合金、活性金属合金化金属或活性金属嵌入材料组成的阳极。阳极在它的表面上具有离子导电保护构造。该构造包括具有非水阳极电解液并与活性金属化学相容且接触阳极的活性金属离子导电隔膜层,和与隔膜层和含水环境化学相容且接触隔膜层的基本不透水离子导电层。隔膜层可为用有机阳极电解液浸渍的半透膜,例如用液体或凝胶相阳极电解液浸渍的微孔聚合物。这种电化学(电极)结构可与阴极体系包括含水阴极体系配对形成根据本发明的电池组电池。
本发明的结构和结合本发明结构的电池组电池可具有各种构造(包括棱柱状和圆柱状)和组成,包括活性金属离子、合金和嵌入阳极,含水的、水、空气、金属氢化物和金属氧化物阴极,和含水的、有机或离子液体阴极电解液;增强电池安全性和/或性能的电解质(阳极电解液和/或阴极电解液)组和物;和制造技术。
在下文的详细描述中进一步描述和列举本发明的这些和其它特征。
附图说明
图1为结合了根据本发明的离子导电保护中间层构造的电化学结构电池的示意图。
图2为结合了根据本发明的离子导电保护中间层构造的电池组电池的示意图。
图3A-C图示了根据本发明的使用管状保护阳极设计的电池组电池的实施方案。
图4-7为图示结合了本发明的离子导电保护中间层构造的各种电池的性能的数据图。
图8图示了在用于产生图7所示数据的含水电解质中试验各种Li箔厚度的试验电池。
图9为结合了具有不同厚度的本发明离子导电保护中间层构造的阳极的电池比能推测曲线、Li厚度为3.3mm的保护阳极的电池重量比能值和电池结构图示以及计算用的参数。
图10图示了根据本发明一种实施方案的Li/水电池和燃料电池用氢发生器。
具体实施方式
现在将对本发明的具体实施方案详细说明。具体实施方案的例子图示在附图中。尽管结合这些具体实施方案描述了本发明,但应认识到并不打算限制本发明到这种具体实施方案。相反,旨在覆盖如附加权利要求所限定的本发明的精神和范围内包括的替代方案、改进和等价物。在下面的描述中,为了提供对本发明的彻底了解而阐述了大量具体细节。没有部分或全部这些具体细节也可实施本发明。在其它情况下,为了不会不必要地使本发明模糊,没有详细描述众所周知的过程操作。
当在本说明书和附加权利要求中结合“包括”、“一种方法包括”、“一种装置包括”或类似语言使用时,单数形式“一”和“该”包括复数引用,除非文中另外明确指明。除非另外定义,本文使用的全部技术和科学术语具有与本发明所属技术领域的普通技术人员常规理解相同的含义。
引言
活性金属在环境空气条件下反应性高,并在用作电极时能从阻挡层受益。它们通常为碱金属如(例如锂、钠或钾)、碱土金属(例如钙或镁),和/或某些过渡金属(例如锌),和/或这些中两种或多种的合金。可使用以下活性金属:碱金属(例如Li、Na、K)、碱土金属(例如Ca、Mg、Ba)或与Ca、Mg、Sn、Ag、Zn、Bi、Al、Cd、Ga、In的二元或三元碱金属合金。优选的合金包括锂铝合金、锂硅合金、锂锡合金、锂银合金和钠铅合金(例如Na4Pb)。优选的活性金属电极由锂构成。
碱金属如锂的低当量使它们作为电池电极成分尤其有吸引力。锂能提供比传统电池标准-镍和镉更大的单位体积能量。但是,锂金属或结合锂的、电势接近锂金属电势(例如在约1伏内)的化合物,如锂合金和锂-离子(锂嵌入)阳极材料,对许多潜在的有吸引力的电解质和阴极材料有高的反应性。本发明描述了使用非水电解质中间层构造来隔离活性金属(例如碱金属,如锂)、活性金属合金或活性金属离子电极(通常是电池组电池的阳极)与周围环境和/或电池的阴极侧。该构造包括具有非水阳极电解液(即在阳极周围的电解质)的活性金属离子导电隔膜层,该隔膜层与活性金属化学相容并接触阳极,还包括与隔膜层和含水环境化学相容并接触隔膜层的基本不透水离子导电层。非水电解质中间层构造有效地隔离(分离)了阳极与周围环境和/或阴极,包括阴极电解液(即在阴极周围的电解质)环境,包括通常对Li或其它活性金属强腐蚀的这种环境,并且同时允许离子传递进入和离开这些可能腐蚀的环境。按照这种方式,允许电化学装置如电池组电池的其它部件用这种构造制成就有大的灵活度。阳极按照这种方式与电池组或其它电化学电池的其它部件的隔离允许与阳极结合使用几乎任何溶剂、电解质和/或阴极材料。而且,可进行电解质或阴极侧溶剂体系的优化,而不会影响阳极稳定性或性能。
有许多能从在具有活性金属(例如碱金属,例如锂)的电池阴极侧或电池组电池中的活性金属嵌入(例如锂合金或锂-离子)阳极上使用水溶液、空气和其它材料中受益的应用,水溶液包括水和水基电解质,其它材料对锂和其它活性金属有反应性,包括有机溶剂/电解质和离子液体。
使用嵌锂电极材料如锂-碳和锂合金阳极而不是锂金属用于阳极还可提供有益的电池特性。首先,允许实现延长的电池循环寿命而没有形成可从Li表面生长到膜表面引起膜损坏的锂金属枝晶的风险。而且,在本发明的一些实施方案中,使用锂-碳和锂合金阳极代替锂金属阳极可显著提高电池安全性,因为这避免了循环过程中强反应性“海绵状”锂的形成。
本发明描述了受保护的活性金属、合金或嵌入电极,其使非常高能量密度的锂电池成为可能,如使用以其它方式与例如锂金属起不利反应的含水电解质或其它电解质的那些。这些高能量电池对的例子有锂-空气、锂-水、锂-金属氢化物、锂-金属氧化物,和这些的锂合金和锂-离子变体。本发明的电池可在它们的电解液(阳极电解液和阴极电解液)中掺入其它组分以增强电池安全性,并可具有各种构造,包括平面状和管状/圆柱状。
非水中间层构造
本发明的非水中间层构造设在电化学电池结构中,该结构具有阳极和在阳极第一表面上的离子导电保护构造,阳极由选自活性金属、活性金属离子、活性金属合金、活性金属合金化和活性金属嵌入材料中的材料构成。该构造由具有非水阳极电解液的活性金属离子导电隔膜层和基本不透水的离子导电层构成,隔膜层与活性金属化学相容并接触阳极,离子导电层与隔膜层和含水环境化学相容并接触隔膜层。隔膜层可包括半透膜,例如用有机阳极电解液浸渍的微孔聚合物,微孔聚合物如可从Celgard,Inc.Charlotte,North Carolina得到。
本发明的保护构造结合了活性金属离子导电玻璃或玻璃-陶瓷(例如锂离子导电玻璃-陶瓷(LIC-GC))的基本不透水层,其具有高的活性金属离子导电性和对能与锂金属强烈反应的侵蚀性电解质例如含水电解质的稳定性。合适的材料为基本不透水的、离子导电的且与含水电解质或以其它方式与例如锂金属不利反应的其它电解质(阴极电解液)和/或阴极材料化学相容。这种玻璃或玻璃-陶瓷材料基本无间隙、不可溶胀且本质上是离子导电的。也就是说,它们由于它们本身的离子导电性质而不依赖于液体电解质或其它试剂的存在。它们还具有高的离子电导率,至少10-7S/cm,通常至少10-6S/cm,例如至少10-5S/cm-10-4S/cm,并高至10-3S/cm或更高,从而多层保护结构的总离子电导率为至少10-7S/cm,并高至10-3S/cm或更高。该层的厚度优选为约0.1-1000微米,或者当该层的离子电导率为约10-7S/cm时,为约0.25-1微米,或当层的离子电导率在约10-4和约10-3S/cm之间时,为约10-1000微米,优选在1和500微米之间,更优选在10和100微米之间,例如20微米。
合适的基本不透水锂离子导电层的合适例子包括玻璃态或非晶态金属离子导体,如磷基玻璃、氧化物基玻璃、磷-氧氮化物基玻璃、硫(sulpher)基玻璃、氧化物/硫化物基玻璃、硒化物基玻璃、镓基玻璃、锗基玻璃或方硼石玻璃(如D.P.Button等在Solid State Ionics,9-10卷,第1部分,585-592(1983年12月)中描述的);陶瓷活性金属离子导体,如锂B-氧化铝、钠β-氧化铝、Li超离子导体(LISICON)、Na超离子导体(NASICON)等;或玻璃-陶瓷活性金属离子导体。具体例子包括LiPON、Li3PO4.Li2S.SiS2、Li2S.GeS2.Ga2S3、Li2O·11Al2O3、Na2O·11Al2O3、(Na,Li)1+xTi2-xAlx(PO4)3(0.6≤x≤0.9)和结晶学相关结构,Na3Zr2Si2PO12、Li3Zr2Si2PO12、Na5ZrP3O12、Na5TiP3O12、Na3Fe2P3O12、Na4NbP3O12、Li5ZrP3O12、Li5TiP3O12、Li3Fe2P3O12和Li4NbP3O12,和它们的组合,任选地被烧结或熔化。合适的陶瓷离子活性金属离子导体描述在例如Adachi等的美国专利4985317中,本文全文引入作为参考并用于各种目的。
用于保护构造的基本不透水层的尤其合适的玻璃-陶瓷材料为具有以下组成并包含由Li1+x(M,Al,Ga)x(Ge1-yTiy)2-x(PO4)3和/或Li1+x+yQxTi2-xSiyP3-yO12构成的主晶相的锂离子导电玻璃-陶瓷:
其中Li1+x(M,Al,Ga)x(Ge1-yTiy)2-x(PO4)3中X≤0.8和0≤Y≤1.0,M为选自Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm和Yb的元素,Li1+x+yQxTi2-xSiyP3-yO12中0<X≤0.4和0<Y≤0.6,Q为Al或Ga。通过将原料熔化成熔体、将熔体浇铸成玻璃并对玻璃进行热处理得到玻璃-陶瓷。这种材料可从日本OHARA公司得到,并进一步描述在美国专利5702995、6030909、6315881和6485622中,本文引入作为参考。
这种锂离子导电基本不透水层和它们的制造技术以及在电池组电池中的结合描述在美国临时专利申请No.60/418899中,该专利于2002年10月15日提交,题目为IONICALLY CONDUCTIVE COMPOSITES FORPROTECTION OF ANODES AND ELECTROLYTES,它的相应美国专利申请为No.10/686189(Attorney Docket No.PLUSP027),2003年10月14日提交,题目为IONICALLY CONDUCTIVE COMPOSITES FORPROTECTION OF ACTIVE METAL ANODES,美国专利申请No.10/731771(Attorney Docket No.PLUSP027X1),2003年12月5日提交,题目为IONICALLY CONDUCTIVE COMPOSITES FORPROTECTION OF ACTIVE METAL ANODES,和美国专利申请No.10/772228(Attorney Docket No.PLUSP039),2004年2月3日提交,题目为IONICALLY CONDUCTIVE MEMBRANES FORPROTECTION OF ACTIVE METAL ANODES AND BATTERYCELLS。本文出于各种目的全文引入这些申请作为参考。
在锂(或其它活性金属或活性金属嵌入)电池中使用这些强导电玻璃和玻璃-陶瓷时的临界限制在于它们对锂金属或电势接近锂金属电势(例如在约1伏内)的结合锂的化合物的反应性。本发明的非水电解质中间层隔离锂(例如)电极与玻璃或玻璃-陶瓷膜反应。非水中间层可具有半透膜,如Celgard微孔隔膜,来防止锂电极机械接触到玻璃或玻璃-陶瓷膜上。用带有溶剂的有机液体电解质(阳极电解液)浸渍该膜,溶剂如碳酸乙二酯(EC)、碳酸丙二酯(PC)、1,2-二甲氧基乙烷(DME)、1,3-二氧戊环(DIOX),或各种醚、甘醇二甲醚、内酯、砜、环丁砜、或它们的混合物。它可能还或替代地具有聚合物电解质、凝胶型电解质或这些的组合。重要的标准在于锂电极在非水阳极电解液中稳定,非水阳极电解液对Li+离子充分传导,锂电极不直接接触玻璃或玻璃-陶瓷膜,并且整个装置允许锂离子穿过玻璃或玻璃-陶瓷膜。
参考图1,图示和描述了本发明的一个具体实施方案。图1显示了电化学电池结构100的不成比例的图,电化学电池结构100具有活性金属、活性金属离子、活性金属合金化金属或活性金属嵌入材料阳极102和离子导电保护构造104。保护构造104具有在阳极102的表面上带有非水阳极电解液(有时还称为转移电解质)的活性金属离子导电隔膜层106和接触隔膜层106的基本不透水离子导电层108。隔膜层106与活性金属化学相容,基本不透水层108与隔膜层106和含水环境化学相容。结构100可任选地包括集电器110,集电器110由不会与活性金属形成合金或嵌入活性金属的合适导电金属组成。当活性金属为锂时,合适的集电器材料为铜。集电器110还可用于密封阳极与周围环境隔离以防止活性金属与周围空气或湿气的不利反应。
隔膜层106由用有机阳极电解液浸渍的半透膜构成。例如,该半透膜可为微孔聚合物,如可从Celgard,Inc得到的。有机阳极电解液可为液相或凝胶相。例如,阳极电解液可包括选自有机碳酸酯、醚、内酯、砜等中的溶剂和它们的组合,如EC、PC、DEC、DMC、EMC、1,2-DME或高级甘醇二甲醚、THF、2MeTHF、环丁砜和它们的组合。1,3-二氧戊环还可用作阳极电解液溶剂,尤其是但不必然是用于增强结合该结构的电池的安全性时,如下文进一步描述。当阳极电极液处于凝胶相时,可加入胶凝剂如聚偏氟乙烯(PVdF)化合物、六氟丙烯-亚乙烯氟化物共聚物(PVdf-HFP)、聚丙烯腈化合物、交联聚醚化合物、聚氧化烯化合物、聚氧化乙烯化合物和组合等以使溶剂形成凝胶。当然,合适的阳极电解液还包括活性金属盐,如在锂的情况下,例如LiPF6、LiBF4、LiAsF6、LiSO3CF3或LiN(SO2C2F5)2。合适的隔膜层的一个例子是溶解在碳酸丙二酯中的1MLiPF6,并浸渍在Celgard微孔聚合物膜中。
根据本发明的保护构造有大量优点。尤其是结合了这种构造的电池结构较容易制造。在一个例子中,锂金属被简单地靠着用有机液体或凝胶电解质浸渍的微孔隔膜放置,隔膜则靠近玻璃/玻璃陶瓷活性金属离子导体。
当使用玻璃-陶瓷时,实现了非水中间层的其它优点。当热处理上面引用的OHARA公司专利所描述类型的非晶态玻璃时,玻璃失透,导致玻璃-陶瓷的形成。但是,这种热处理可导致表面粗糙度的形成,这难以利用无机保护中间层如LiPON、Cu3N等的气相沉积来涂敷。液体(或凝胶)非水电解质中间层的使用能容易地通过常规液流覆盖这种粗糙表面,从而消除了对表面抛光等的需要。从这个意义上讲,可使用技术如“收缩”(Sony公司和Shott Glass所述(T.Kessler,H.Wegener,T.Togawa,M.Hayashi和T.Kakizaki,“Large Microsheet Glass for 40-in.ClassPALC Displays”,1997,FMC2-3,从Shott Glass网站:http://www.schott.com/english下载,本文引入作为参考))形成薄的玻璃层(20-100微米),并热处理这些玻璃形成玻璃-陶瓷。
电池组电池
非水中间层构造通常在电池组电池中被有效地采用。例如,图1的电化学结构100可与阴极体系120配对形成电池200,如图2所示。阴极体系120包括电子导电部件、离子导电部件和电化学活性部件。由于保护构造提供的隔离,阴极体系120可具有任何所需的组成,不受阳极或阳极电解液组成限制。特别地,阴极体系可引入在其它情况下与阳极活性金属强烈反应的组分,如含水材料,包括水、含水阴极电解液和空气,金属氢化物电极和金属氧化物电极。
在一种实施方案中,Celgard隔膜将靠着薄玻璃-陶瓷的一侧放置,然后是非水液体或凝胶电解质,再是锂电极。在玻璃陶瓷膜的另一侧,可使用侵蚀性溶剂,如含水电解质。按照这种方式,可构建例如廉价的Li/水或Li/空气电池。
根据本发明的电池能具有非常高的容量和比能。例如,容量大于5、大于10、大于100或甚至大于500mAh/cm2的电池都是可能的。如下面的实施例进一步所述,证实了Li阳极约3.35mm厚的本发明的Li/水试验电池具有约650mAh/cm2的容量。基于这种性能,推测显示出本发明Li/空气电池的非常高的比能。例如,对于具有3.3mm厚Li阳极、叠层厚度为6mm和面积为45cm2的Li/空气电池,未封装的比能为约3400Wh/l(4100Wh/kg),封装的比能为约1000Wh/l(1200Wh/kg),假定70%封装负荷。
阴极体系
如上所述,由于保护构造提供的隔离,根据本发明的电池组电池的阴极体系120可具有任何所需的组成,不受阳极或阳极电解液组成限制。特别地,阴极体系可引入在其它情况下与阳极活性金属强烈反应的组分,如含水材料,包括水、水溶液和空气,金属氢化物电极和金属氧化物电极。
本发明的电池组电池可包括而不限于水、水溶液、空气电极和金属氢化物电极,如题目为ACTIVE METAL/AQUEOUSELECTROCHEMICAL CELLS AND SYSTEMS的共同待审申请No.10/772157中所述,本文全文引入作为参考并用于各种目的,以及金属氧化物电极,例如在常规锂离子电池中所使用的。
通过本发明的保护中间层构造获得的阳极和阴极之间的有效隔离还能使阴极体系尤其是含水体系以及非水体系选择中的巨大灵活度成为可能。由于受保护阳极与阴极电解液完全分离,因而阴极电解液与阳极的相容性不再是问题,可使用对Li动力学上不稳定的溶剂和盐。
对于使用水作为电化学活性阴极材料的电池,多孔电子导电支撑结构可提供阴极体系的电子导电部件。含水电解质(阴极电解液)提供Li离子传递(导电性)的离子载体和与Li结合的阴离子。电化学活性组分(水)和离子导电组分(含水阴极电解液)将被混和成单一溶液,尽管它们在概念上是电池组电池的单独元件。本发明的Li/水电池组电池的合适阴极电解液包括任何具有合适离子电导率的含水电解质。合适的电解质可为酸性,例如强酸如HCl、H2SO4、H3PO4或弱酸如乙酸/醋酸锂;碱性,例如LiOH;中性,例如海水、LiCl、LiBr、LiI;或两性,例如NH4Cl、NH4Br等。
海水作为电解质的适宜性使具有非常高能量密度的用于海洋应用的电池组电池成为可能。使用前,电池结构由受保护阳极和多孔电子导电支撑结构(阴极的电子导电部件)组成。当需要时,通过将该电池浸没在能提供电化学活性和离子导电部件的海水中来完成电池。由于后一部件由环境中的海水提供,因此在它使用前不用作为电池组电池的一部分被运输(因而不需要包括在电池能量密度计算中)。这种电池被称为“开路”电池,因为不包含阴极侧上的反应产物。因此,这种电池为原电池。
根据本发明,二次Li/水电池也是可能的。如上所述,这种电池被称为“闭路”电池,因为在电池的阴极侧上包含阴极侧上的反应产物,其用于在对电池施加适宜的再充电电势时通过跨过保护膜移动Li离子返回来为阳极再充电。
如上文说明和下文进一步所述,在本发明的另一实施方案中,涂在多孔催化电子导电载体上的离聚物减少或消除了对电化学活性材料中离子导电性的需要。
在Li/水电池中发生的电化学反应为氧化还原反应,其中电化学活性阴极材料得到还原。在Li/水电池中,催化电子导电载体有利于氧化还原反应。如上所述,但不限制于此,在Li/水电池中,该电池反应被认为是:
Li+H2O=LiOH+1/2H2
阳极和阴极处的半电池反应被认为是:
阳极:Li=Li++e-
阴极:e-+H2O=OH-+1/2H2
因此,Li/水阴极的催化剂促进了到水的电子转移,产生氢和氢氧根离子。用于这种反应的常用廉价催化剂是镍金属;贵金属如Pt、Pd、Ru、Au等也起作用但较昂贵。
具有受保护Li阳极和含水电解质的电池也被认为在本发明的Li(或其它活性金属)/水电池的范围内,其中含水电解质由可溶解在水中的可用作活性阴极材料(电化学活性组分)的气态和/或固态氧化剂组成。使用作为比水更强的氧化剂的水溶性化合物在一些应用中与锂/水电池相比能显著增加电池能量,其中在电池放电反应中,在阴极表面处发生电化学氢析出。这种气态氧化剂的例子有O2、SO2和NO2。另外,金属亚硝酸盐尤其是NaNO2和KNO2和金属亚硫酸盐如Na2SO3和K2SO3都是比水强的氧化剂,并可容易地以大浓度溶解。可溶于水的另一类无机氧化剂为锂、钠和钾的过氧化物,以及过氧化氢H2O2。
使用过氧化氢作为氧化剂尤其有利。在根据本发明的电池组电池中有至少两种使用过氧化氢的方法。首先,阴极表面上过氧化氢的化学分解导致氧气的产生,氧气可用作活性阴极材料。其次,或许更有效的方法,基于阴极表面上过氧化氢的直接电还原。原理上,过氧化氢可从碱性或酸性溶液被还原。对于利用酸性溶液的过氧化氢还原的电池,可获得最高的能量密度。在这种情况下,与Li/水对的E0=3.05V相比,具有Li阳极的电池产生E0=4.82V(标准条件)。但是,由于两种酸和过氧化氢对未保护Li的非常高的反应性,这种电池实际上只对于诸如根据本发明这类的受保护Li阳极才能实现。
对于使用空气作为电化学活性阴极材料的电池,这些电池的空气电化学活性组分包括为电化学反应提供水的水分。电池具有与阳极电连接以允许电子转移来还原空气阴极活性材料的电子导电支撑结构。电子导电支撑结构通常是多孔的,以允许流体(空气)流动且有催化性或用催化剂处理来催化阴极活性材料的还原。具有合适离子电导率的含水电解质或离聚物也与电子导电支撑结构接触,以允许电子导电支撑结构内的离子传递来完成氧化还原反应。
空气阴极体系包括电子导电部件(例如多孔电子导体)、具有至少一种含水成分的离子导电部件和作为电化学活性部件的空气。它可为任何合适的空气电极,包括在金属(例如Zn)/空气电池或低温(例如PEM)燃料电池中常用的那些。在金属/空气电池尤其是Zn/空气电池中使用的空气阴极描述在许多出处中,包括“Handbook of Batteries”(Linden和T.B.Reddy,McGraw-Hill,NY,第三版),并通常由几层组成,包括空气扩散膜、疏水Teflon层、催化剂层和金属电子导电部件/集电器,如Ni筛。催化剂层还包括可为水性和/或离聚的离子导电组分/电解质。典型的含水电解质由溶解在水中的KOH组成。典型的离聚电解质由水合(水)Li离子导电聚合物如全氟磺酸聚合物薄膜(例如du Pont NAFION)组成。空气扩散膜调节空气(氧气)流。疏水层阻止电池的电解质渗透到空气扩散膜内。该层通常包含碳和Teflon颗粒。催化剂层通常包含高表面积碳和加速氧气还原的催化剂。在大多数商业阴极中,使用金属氧化物如MnO2作为氧气还原的催化剂。替代的催化剂包括金属大环如钴酞菁,和高分散贵金属如铂和铂/钌合金。由于空气电极结构与活性金属电极化学隔离,因此空气电极的化学组成不受与阳极活性材料可能的反应性的限制。这允许使用通常会侵蚀未受保护金属电极的材料设计更高性能的空气电极。
根据本发明的另一类型的结合了受保护阳极和阴极体系的活性金属/含水电池组电池为锂(或其它活性金属)/金属氢化物电池。例如,用本文描述的非水中间层构造保护的锂阳极可在适合作为锂/金属氢化物电池中电解质的水溶液中被放电和充电。合适的电解质提供源或质子。例子包括卤化物酸或酸式盐,包括氯化物或溴化物酸或盐例如HCl、HBr、NH4Cl或NH4Br的水溶液。
除了上述含水、空气等体系外,利用结合了常规Li-离子电池阴极和电解质的阴极体系可得到提高的性能,阴极如金属氧化物阴极(例如LixCoO2、LixNiO2、LixMn2O4和LiFePO4)和烷基碳酸酯的二元、三元或多组分混合物,或它们与作为Li金属盐(例如LiPF6、LiAsF6或LiBF4)的溶剂的醚的混合物;或Li金属电池阴极(例如元素硫或聚硫化物)和电解质,该电解质由有机碳酸酯、醚、甘醇二甲醚、内酯、砜、环丁砜和它们的组合,如EC、PC、DEC、DMC、EMC、1,2-DME、THF、2MeTHF和它们的组合构成,如例如美国专利6376123中所述,本文引入作为参考。
此外,阴极电解液溶液可只由低粘度溶剂组成,如醚,像1,2-二甲氧基乙烷(DME)、四氢呋喃(THF)、2-甲基四氢呋喃、1,3-二氧戊环(DIOX)、4-甲基二氧戊环(4-MeDIOX)或有机碳酸酯如碳酸二甲酯(DMC)、碳酸乙基甲酯(EMC)、碳酸二乙酯(DEC)或它们的混合物。另外,可使用超低粘度的酯溶剂或助溶剂如甲酸甲酯和乙酸甲酯,它们对未保护的Li有非常高的反应性。本领域的那些技术人员都知道,离子导电率和扩散速度与粘度成反比,以至于在全部其它情况等同时,当溶剂粘度降低时电池性能提高。这种阴极电解液溶剂体系的使用显著提高了电池性能,尤其是在低温下的放电和充电特性。
在本发明的阴极电解液中还可使用离子液体。离子液体为熔点在100度以下、经常甚至低于室温的有机盐。最常用的离子液体为咪唑鎓和吡啶鎓衍生物,而且膦鎓或四烷基铵化合物也是已知的。离子液体具有理想的高离子电导率、高热稳定性、无可测量的蒸汽压和不易燃性属性。代表性的离子液体有1-乙基-3-甲基咪唑鎓甲苯磺酸盐(EMIM-Ts)、1-丁基-3-甲基咪唑鎓辛基硫酸盐(BMIM-OctSO4)、1-乙基-3-甲基咪唑鎓六氟磷酸盐和1-己基-3-甲基咪唑鎓四氟硼酸盐。尽管对用于电化学应用如电容器和电池的离子液体有很大兴趣,但它们对金属锂和锂化碳是不稳定的。但是,本发明中所述的受保护锂阳极与直接化学反应隔离,因此使用离子液体的锂金属电池可作为本发明的一种实施方案。这种电池应在高温下特别稳定。
安全性添加剂
作为安全措施,非水中间层构造可结合在与反应性电解质(例如水)接触时能导致阳极(例如锂)表面上不透水聚合物形成的凝胶/聚合剂。这种安全措施用于保护构造的基本不透水层(例如玻璃或玻璃-陶瓷膜)破裂或以其它方式损坏并允许侵蚀性阴极电解液进入和到达锂电极从而增加了Li阳极和含水阴极电解液之间强烈反应可能性的情形。
通过在阳极电解液中提供不溶于或很少溶于水的聚合物单体例如二氧戊环(Diox)(例如数量为约5-20体积%)和在阴极电解液中提供单体用聚合引发剂例如质子酸来防止这种反应。Diox基阳极电解液可由有机碳酸酯(EC、PC、DEC、DMC、EMC)、醚(1,2-DME、THF、2MeTHF、1,3-二氧戊环和其它一些)和它们的混合物组成。包括二氧戊环作为主要溶剂(例如50-100体积%)和Li盐尤其是LiAsF6、LiBF4、LiSO3CF3、LiN(SO2C2F5)2的阳极电解液尤其有吸引力。Diox为Li表面的良好钝化剂,在Diox基电解质中已经获得Li金属的良好循环数据(参见例如美国专利5506068)。除了它与Li金属的相容性外,与上述离子盐结合的Diox形成强导电电解质。相应的含水阴极电解液包含能产生不溶于水或只少量溶于水的Diox聚合产物(聚二氧戊环)的Diox聚合引发剂。
如果膜损坏,则包含溶解的引发剂的阴极电解液与Diox基阳极电解液直接接触,并靠着Li阳极表面发生Diox的聚合。聚二氧戊环为Diox聚合的产物,具有高电阻,因而电池停止工作。另外,形成的聚二氧戊环层用作阻止Li表面和含水阴极电解液之间反应的阻挡层。Diox可被溶解在阴极电解液中的质子酸聚合。而且,水溶性的路易斯酸尤其是苯并苯甲酰(benbenzoyl)阳离子可用于此目的。
因此,通过使用二氧戊环(Diox)基阳极电解液和包含Diox聚合引发剂的阴极电解液可实现循环能力和安全性的提高。
活性金属离子和合金阳极
本发明涉及具有如上所述的由活性金属组成的阳极的电池和其它电化学结构。优选的活性金属电极由锂(Li)组成。用于这些结构和电池的合适阳极电解液如上所述。
本发明还涉及具有活性金属离子(例如锂-碳)或活性金属合金(例如Li-Sn)阳极的电化学结构。一些结构可最初具有不带电荷的活性金属离子嵌入材料(例如碳)或随后被活性金属或活性金属离子施以电荷的合金化金属(例如锡(Sn))。尽管本发明可适用于各种活性金属,但本文中主要结合锂作为例子来描述。
可使用常规Li-离子电池中常用的碳材料尤其是石油焦和中间相碳微球碳作为Li-离子含水电池组电池中的阳极材料。还可使用包括选自Ca、Mg、Sn、Ag、Zn、Bi、Al、Cd、Ga、In和Sb中的一种或几种金属、优选Al、Sn或Si的锂合金作为这种电池的阳极材料。在一种具体的实施方案中,阳极包括Li、Cu和Sn。
这种结构的阳极电解液可结合支撑盐,例如,溶解在常规Li-离子电池中常用的非水溶剂如EC、PC、DEC、DMC、EMC、MA、MF的二元或三元混合物中的LiPF6、LiBF4、LiAsF6、LiClO4、LiSO3CF3、LiN(CF3SO2)2或LiN(SO2C2F5)2。还可使用凝胶-聚合物电解质,例如包括一种上述盐、聚合物粘合剂如PVdF、PVdF-HFP共聚物、PAN或PEO、和增塑剂(溶剂)如EC、PC、DEC、DMC、EMC、THF、2MeTHF、1,2-DME及其混合物的电解液。
对于使用这些阳极的电池,可向保护构造另一侧上的电化学结构增加合适的阴极结构。该构造使使用大量特殊阴极如空气、水、金属氢化物或金属氧化物的Li-离子型电池成为可能。对于Li-离子含水电池组电池,例如,含水阴极电解液可为碱性、酸性或中性的,并包含Li阳离子。合适的含水阴极电解液的一个例子为2M LiCl,1M HCl。
在具有锂-碳锂合金阳极的电池的首次充电中,Li阳离子通过保护构造(包括阳极电解液)从阴极电解液传递到阳极表面,在那里如常规Li-离子电池中一样发生嵌入过程。在一种实施方案中,阳极在电池组装前在外部被化学或电化学锂化。
电池设计
根据本发明的电化学结构和电池组电池可具有任何合适的几何形状。例如,考虑本文提供的结构或电池部件的描述,通过按照容易适于本发明的已知电池组电池制造技术将结构或电池的各种部件(阳极、中间层、阴极等)的平面层堆叠获得平面几何形状。这些堆叠的层可被设计为棱柱状结构或电池。
或者,使用具有非水中间层构造的管状玻璃或玻璃-陶瓷电解质允许构建密封面积小的高表面积阳极。与密封长度随电池表面积增加的平板设计相反,管状结构利用端密封,其中可增加管的长度以提高表面积而密封面积不变。这允许构建应相应具有高功率密度的高表面积Li/水和Li/空气电池。
本发明的非水中间层构造的使用有利于构建。开端(有密封)或闭端玻璃或玻璃-陶瓷(即基本不透水活性金属离子导电固体电解质)管部分装有如上所述的非水有机电解质(阳极电解液或转移电解液),例如一般用在锂原电池中的电解质。将被一定类型的物理隔膜(例如半透聚合物膜,如Celgard,Tonin,聚丙烯网等)包围的具有集电器的锂金属棒插入到管内。使用简单的环氧树脂密封、玻璃-金属密封或其它合适的密封物理隔离开锂和环境。
然后将受保护阳极插入到圆柱状空气电极中制造圆柱状电池,如图3A所示。或可将阳极阵列插入到棱柱状空气电极内,如图3B所示。
通过用如本文上面所述的合适的含水、金属氢化物或金属氧化物阴极体系代替空气电极,还可使用这项技术构建Li/水、Li/金属氢化物或Li/金属氧化物电池。
除了使用锂金属棒或丝(在毛细管中)外,本发明还用于隔离开可再充电LiCx阳极和含水或其它腐蚀性环境。在这种情况下,在管状阳极中使用合适的阳极电解液(转移电解液)溶剂在锂化碳电极上形成钝化膜。这将允许使用大量特殊阴极如空气、水、金属氢化物或金属氧化物构建高表面积Li-离子型电池,例如如图3所示。
实施例
下面的实施例提供了说明根据本发明的Li金属和Li-离子含水电池组电池的有益性能的细节。提供这些实施例来例证和更清楚地说明本发明的内容,且决不打算是限制性的。
实施例1:Li/海水电池
进行一系列试验,其中使用OHARA公司的商业离子导电玻璃-陶瓷作为分开含水阴极电解液和非水阳极电解液的膜。电池结构为Li/非水电解质/玻璃-陶瓷/含水电解质/Pt。使用Chemetall Foote公司的厚度为125微米的锂箔作为阳极。玻璃-陶瓷板的厚度在0.3-0.48mm的范围内。使用两个O形环将玻璃-陶瓷板固定到电化学电池内,使得玻璃-陶瓷板从一侧暴露于含水环境和从另一侧暴露于非水环境。在这种情况下,含水电解质包括用Aquarium Systems,Inc的35ppt的“Instant Ocean”制备的人造海水。测定海水的电导率为4.5×10-2S/cm。放在玻璃-陶瓷另一侧上的微孔Celgard隔膜充满由溶解在碳酸亚丙酯中的1M LiPF6组成的非水电解质。非水电解质的装填体积为0.25ml/1cm2锂电极表面。当完成电池电路时,使用完全浸没在海水阴极电解液中的铂反电极促进氢还原。使用Ag/AgCl参比电极控制电池中Li阳极的电势。测量的值被重新计算成标准氢电极(SHE)标度的电势。观察到最接近地对应于水中Li/Li+和H2/H+之间热动力学电势差异的开路电势(OCP)为3.05伏(图4)。当电路闭合时,立即在Pt电极处观察到氢析出,其为电池中阳极和阴极电极反应的指示,2Li=2Li++2e-和2H++2e-=H2。图2中提供了放电速度为0.3mA/cm2时Li阳极溶解的电势-时间曲线。结果表明为具有稳定放电电压的工作电池。应强调,在使用直接接触海水的Li阳极的全部试验中,Li的利用率非常差,由于海水中极其高的Li腐蚀速度(超过19A/cm2),在类似于该实施例所用那些的低和中等电流密度下根本不能使用这类电池。
实施例2:Li/空气电池
电池结构类似于前面实施例中的结构,但Pt电极完全浸没在电解质中,这种试验电池具有为商业Zn/空气电池制造的空气电极。所用的含水电解质为1M LiOH。Li阳极和非水电解质与前面实施例中所述相同。
观察到该电池的开路电势为3.2V。图5显示了放电速度为0.3mA/cm2时的放电电压-时间曲线。电池表现出2.8-2.9V的放电电压超过14小时。该结果表明,具有分开含水阴极电解液和非水阳极电解液的固体电解质膜的Li/空气电池可获得良好性能。
实施例3:Li-离子电池
在这些试验中,使用OHARA公司的商业离子导电玻璃-陶瓷作为分开含水阴极电解液和非水阳极电解液的膜。电池结构为碳/非水电解质/玻璃-陶瓷板/含水电解质/Pt。使用与锂离子电池中常用的碳电极类似的包括合成石墨的在铜衬底上的商业碳电极作为阳极。玻璃-陶瓷板的厚度为0.3mm。使用两个O形环将玻璃-陶瓷板固定到电化学电池内,使得玻璃-陶瓷板从一侧暴露于含水环境和从另一侧暴露于非水环境。含水电解质包括2M LiCl和1M HCl。放置在玻璃-陶瓷另一侧上的两层微孔Celgard隔膜充满非水电解质,非水电解质包括溶解在碳酸亚乙酯和碳酸二甲酯(体积比1∶1)的混合物中的1M LiPF6。在两层Celgard隔膜之间放置锂线参比电极以便控制循环过程中碳阳极的电势。使用完全浸没在2MLiCl、1M HCl溶液中的铂网作为电池阴极。使用放置在含水电解质中的Ag/AgCl参比电极控制碳电极的电势和跨过玻璃-陶瓷板的电压降,以及循环过程中Pt阴极的电势。观察到该电池的开路电压(OCV)为大约1伏。观察到与热动力学值紧密相对应的Li参比电极和Ag/AgCl参比电极之间的电压差为3.2伏。以0.1mA/cm2为电池充电直到碳电极对Li参比电极电势达到5mV,然后使用相同的截止电势以0.05mA/cm2充电。放电速度为0.1mA/cm2,碳阳极对Li参比电极的放电截止电势为1.8V。图6中的数据表明,具有嵌碳阳极和含Li阳离子的含水电解质的电池可以可逆地工作。这是在Li离子电池中使用水溶液代替固体锂化氧化物阴极作为Li离子源用于碳阳极充电的第一个已知例子。
实施例4:玻璃-陶瓷保护的厚Li阳极在含水电解质中的性能
设计测试用于在含水电解质中各种Li箔厚度的试验Li/水电池。图8所示的电池包含具有Cu衬底上活性面积为2.0cm2的受保护Li箔阳极的阳极室。厚度为约3.3-3.5mm的Li电极由Li金属棒制造。制造过程包括挤出和轧制Li棒,然后利用液压机静态挤压到得到的箔到Ni网集电器的表面上。使用具有聚丙烯主体的模用于挤压操作以避免与Li箔的化学反应。使用两个O形环将厚度为约50微米的玻璃-陶瓷膜固定到电化学电池内,使得玻璃-陶瓷膜从一侧暴露于含水环境(阴极电解液)和从另一侧暴露于非水环境(阳极电解液)。阳极电解液在阳极和玻璃-陶瓷膜表面之间提供液体中间层。
电池充满4M NH4Cl的含水阴极电解液,这允许阴极在电池贮存和放电过程中被缓冲。放置在玻璃-陶瓷膜另一侧上的微孔Celgard隔膜充满由溶解在碳酸亚丙酯中的1M LiClO4组成的非水阳极电解液。阳极室对着水溶液被密封,从而只有保护玻璃-陶瓷膜暴露于含水环境、参比电极和金属网反电极。由硼硅酸盐玻璃制成的电池体充满100ml阴极电解液。使用Ti网反电极作为阴极以促进Li阳极溶解过程中的氢析出(水还原)。使用紧邻保护玻璃膜表面放置的Ag/AgCl参比电极控制放电过程中Li阳极的电势。测量的值被重新计算成标准氢电极(SHE)标度的电势。电池备有释放阴极处产生的氢气的排气孔。
图7中显示了该电池的连续放电的电势-时间曲线。电池在大约2.7-2.9V的闭路电压下表现出几乎1400小时的非常长的放电。获得的放电容量值非常大,约650mAh/cm2。沿Li阳极/含水电解质界面移去超过3.35mm的Li,没有破坏50μm厚的保护玻璃-陶瓷膜。该实验中使用的Li箔的厚度在3.35-3.40mm的范围内。放电的Li阳极的事后分析证实,在电池放电结束时全部量的Li从Ni集电器上剥离。这证明受保护Li阳极放电的库仑效率接近100%。
使用获得的Li放电容量推测Li/空气棱柱电池的性能。在图9中,显示了具有变化的保护Li厚度的电池的比能推测和Li厚度为3.3mm的玻璃保护阳极的电池重量比能的值。该图还图示了电池构造和显示了计算用的参数。电池尺寸对应于名片的面积(约45cm2)和约6mm的厚度(包括3.3mm的Li阳极)。这产生非常大的90Wh的推测能力。可从图9看出,试验获得的玻璃-保护阳极的放电容量允许构建异常高性能特性的Li/空气电池。
另一实施方案-Li/水电池和用于燃料电池的氢发生器
使用根据本发明的活性金属电极上的保护构造允许构建上述具有可忽略腐蚀电流的活性金属/水电池。Li/水电池具有8450Wh/kg的非常高的理论能量密度。电池反应为Li+H2O=LiOH+1/2H2。尽管电池反应产生的氢一般是不再用的,但在本发明的这种实施方案中用于为环境温度燃料电池提供燃料。产生的氢可被直接输送到燃料电池或可用于为金属氢化物合金再充电以稍后用在燃料电池中。至少一个公司Millenium Cell《http: //www.millenniumcell.com/news/tech.html》利用硼氢化钠与水的反应产生氢。但是,该反应需要使用催化剂,并且由NaBH4和水的化学反应产生的能量作为热遗失。
NaBH4+2H2O→4H2+NaBO2
当与燃料电池反应H2+O2=H2O结合时,燃料电池反应被认为是:
NaBH4+2O2→2H2O+NaBO2
可由NaBH4反应物的当量计算这种体系的能量密度(38/4=9.5克/当量)。NaBH4的重量分析容量为2820mAh/g;由于电池电压为约1,因此该体系的比能为2820Wh/kg。如果基于最终产物NaBO2计算能量密度,则能量密度较低,约1620Wh/kg。
在Li/水电池的情况下,氢产生通过被认为由下面所述的电化学反应来进行:
Li+H2O=LiOH+1/2H2
在这种情况下,化学反应的能量被转化成3伏电池中的电能,然后在燃料电池中将氢转化成水,总反应被认为由下面所述:
Li+1/2H2O+1/4O2=LiOH
其中全部化学能在理论上都被转化成电能。在约3伏的电池电势下,基于锂阳极的能量密度为3830mAh/g,为11500Wh/kg(比NaBH4高4倍)。如果包括反应需要的水的重量,则能量密度为5030Wh/kg。如果能量密度基于放电产物LiOH的重量,则它为3500Wh/kg,或为NaBO2体系能量密度的两倍。这可与先前的概念相比,先前的概念中同样考虑了锂金属与水产生氢的反应。在那种情况下,能量密度被降低3倍,因为Li/H2O反应中的大部分能量作为热被损耗,并且能量密度基于实际上小于1的H2/O2对的电池电势(与Li/H2O的3相反)。在图10所示的本发明的这种实施方案中,通过Li/水电池上的负荷还可小心地控制氢的产生,Li/水电池由于保护膜而具有长的保存期限,并且离开电池的氢已经被增湿用于H2/空气燃料电池。
结论
尽管为了清楚理解而较详细地描述了上述发明,但在本发明的范围内显然可实施某些变化和改进。特别地,尽管主要参照锂金属、合金或嵌入阳极描述了本发明,但阳极也可由任何活性金属尤其是其它碱金属如钠组成。应注意存在实施本发明的方法和组成的多种替代方式。因此,本发明的实施方案被认为是说明性的而不是限制性的,本发明不限于本文给出的细节。
本文引用的全部文献被出于各种目的引入作为参考。
Claims (28)
1.一种电化学电池结构,包括:
阳极,该阳极包括选自活性金属、活性金属离子、活性金属合金化金属和活性金属嵌入材料的材料;和
在阳极第一表面上的活性金属离子导电保护构造,该构造包括:
包括液相或凝胶相的非水电解液的活性金属离子导电隔膜层,该隔膜层与阳极化学相容并接触阳极,和
与隔膜层化学相容并接触隔膜层的基本不透水离子导电层,该基本不透水离子导电层包括选自玻璃态或非晶态活性金属离子导体、陶瓷活性金属离子导体和玻璃-陶瓷活性金属离子导体的材料。
2.权利要求1的结构,其中电解液处于液相。
3.权利要求1的结构,其中电解液处于凝胶相。
4.权利要求2的结构,其中液相电解液浸渍在半透聚合物膜。
5.权利要求1的结构,其中基本不透水层的材料为陶瓷活性金属离子导体。
6.权利要求1的结构,其中基本不透水层的材料为玻璃-陶瓷活性金属离子导体的材料。
7.权利要求1的结构,其中阳极的活性材料为锂。
8.权利要求1的结构,其中活性金属阳极材料为金属锂。
9.权利要求1的结构,其中活性金属阳极材料为锂合金。
10.权利要求1的结构,其中活性金属阳极材料为锂嵌入材料。
11.权利要求10的结构,其中锂嵌入材料为碳。
12.权利要求1的结构,其中活性金属阳极材料为钠。
13.一种电池组电池,包括:
在前权利要求任一项的电化学电池结构;和阴极体系,所述阴极体系包括电子导电部件、离子导电部件和电化学活性部件。
14.权利要求13的电池,其中离子导电部件为含水电解质。
15.权利要求13的电池,其中离子导电部件为非水电解质。
16.权利要求13的电池,其中电化学活性部件为水。
17.权利要求13的电池,其中电化学活性部件为空气。
18.权利要求13的电池,其中电化学活性部件为氧气。
19.权利要求18的电池,其中氧气溶解在离子导电部件中。
20.权利要求13的电池,其中电化学活性部件为硫或聚硫化物。
21.权利要求13的电池,其中离子导电部件和电化学活性部件为海水。
22.一种锂空气电池组电池,其包括权利要求13的电池组电池,其中活性金属阳极材料为锂,并且电化学活性部件为来自周围空气的氧气。
23.一种锂海水电池组电池,其包括权利要求13的电池组电池,其中活性金属阳极材料为锂,离子导电部件包括海水,并且电化学活性部件选自海水中存在的水和海水中溶解的氧气。
24.一种锂硫电池组电池,其包括权利要求13的电池组电池,其中活性金属阳极材料为锂,并且电化学活性部件为硫或聚硫化物。
25.一种制备权利要求13的电池组电池的方法,包括:
提供以下部件:
活性金属阳极;
阴极体系;和
权利要求1-12的离子导电保护构造,该离子导电保护构造在阳极第一表面上,以及
组装上述部件。
26.一种制备权利要求22的锂空气电池组电池的方法,包括:
提供以下部件:
锂阳极;和
阴极体系,以及
组装上述部件。
27.一种制备权利要求23的锂海水电池组电池的方法,包括:
提供以下部件:
锂阳极;和
阴极体系,以及
组装上述部件。
28.一种制备权利要求24的锂硫电池组电池的方法,包括:
提供以下部件:
锂阳极;和
阴极体系,以及
组装上述部件。
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US8828580B2 (en) | 2014-09-09 |
KR101117184B1 (ko) | 2012-06-25 |
EP1714349B1 (en) | 2015-07-15 |
US20150024251A1 (en) | 2015-01-22 |
CA2555637A1 (en) | 2005-09-09 |
WO2005083829A3 (en) | 2006-05-04 |
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JP2007524204A (ja) | 2007-08-23 |
JP2014222658A (ja) | 2014-11-27 |
AU2004316638A1 (en) | 2005-09-09 |
US8293398B2 (en) | 2012-10-23 |
US20160028063A1 (en) | 2016-01-28 |
CA2555637C (en) | 2012-12-11 |
US7829212B2 (en) | 2010-11-09 |
CN101702444B (zh) | 2012-10-03 |
US20130004852A1 (en) | 2013-01-03 |
US20110014522A1 (en) | 2011-01-20 |
WO2005083829A2 (en) | 2005-09-09 |
KR20070004670A (ko) | 2007-01-09 |
JP6141232B2 (ja) | 2017-06-07 |
US20050175894A1 (en) | 2005-08-11 |
US20080038641A1 (en) | 2008-02-14 |
AU2004316638B2 (en) | 2010-09-09 |
US7282295B2 (en) | 2007-10-16 |
EP1714349A2 (en) | 2006-10-25 |
US8501339B2 (en) | 2013-08-06 |
US20140057153A1 (en) | 2014-02-27 |
JP5624257B2 (ja) | 2014-11-12 |
BRPI0418500A (pt) | 2007-05-15 |
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