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

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 Download PDF

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CN101702444A
CN101702444A CN200910174918A CN200910174918A CN101702444A CN 101702444 A CN101702444 A CN 101702444A CN 200910174918 A CN200910174918 A CN 200910174918A CN 200910174918 A CN200910174918 A CN 200910174918A CN 101702444 A CN101702444 A CN 101702444A
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lithium
anode
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S·J·维斯科
Y·S·尼蒙
B·D·卡茨
L·C·德永赫
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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

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
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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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244310A (zh) * 2011-05-19 2011-11-16 周建林 一种新型金属燃料电池
CN102479974A (zh) * 2010-11-29 2012-05-30 中国电子科技集团公司第十八研究所 一种金属锂电池用防腐蚀保护膜
CN102479940A (zh) * 2010-11-29 2012-05-30 中国电子科技集团公司第十八研究所 一种带有防腐蚀保护膜的金属锂电极的制备方法
CN102479938A (zh) * 2010-11-29 2012-05-30 中国电子科技集团公司第十八研究所 一种带有防腐蚀保护膜的金属锂电极
CN102479936A (zh) * 2010-11-29 2012-05-30 中国电子科技集团公司第十八研究所 一种金属锂电池用防腐蚀保护膜的制备方法
CN102655249A (zh) * 2011-03-03 2012-09-05 现代自动车株式会社 锂离子空气电池
CN102751550A (zh) * 2011-04-20 2012-10-24 三星电机株式会社 金属空气电池及其制备方法
CN103053065A (zh) * 2010-07-31 2013-04-17 大众汽车有限公司 具有高氧气饱和度的锂-空气电池
CN103367798A (zh) * 2012-04-02 2013-10-23 三星精密化学株式会社 用于锂离子二次电池的电解质和锂离子二次电池
CN104054209A (zh) * 2011-11-15 2014-09-17 高级聚合电池公司 水性电解质锂硫电池
TWI481102B (zh) * 2012-12-28 2015-04-11 Ind Tech Res Inst 受保護的活性金屬電極及具有此電極的元件
CN104681870A (zh) * 2013-12-03 2015-06-03 中国电子科技集团公司第十八研究所 微晶玻璃陶瓷电解质表面处理的方法
CN104681883A (zh) * 2013-12-03 2015-06-03 中国电子科技集团公司第十八研究所 高可靠水体系金属锂电池的制备方法
CN105633479A (zh) * 2016-03-11 2016-06-01 南京大学 一种全固态锂硫电池的制备方法
CN105762441A (zh) * 2016-02-29 2016-07-13 苏州大学张家港工业技术研究院 基于锂离子固体电解质的锂空气电池的制备方法
CN106104897A (zh) * 2014-03-27 2016-11-09 巴斯夫欧洲公司 凝胶电解质和电极
US9660265B2 (en) 2011-11-15 2017-05-23 Polyplus Battery Company Lithium sulfur batteries and electrolytes and sulfur cathodes thereof
CN107275097A (zh) * 2017-07-17 2017-10-20 深圳中科瑞能实业有限公司 金属导电材料用作钾离子混合超级电容器负极和钾离子混合超级电容器及其制备方法
US9812706B2 (en) 2012-12-28 2017-11-07 Industrial Technology Research Institute Protected active metal electrode and device with the electrode
CN109041402A (zh) * 2018-07-31 2018-12-18 宜昌后皇真空科技有限公司 一种产生多电荷态离子束的方法和用于该方法的装置
CN109643818A (zh) * 2016-09-02 2019-04-16 昭和电工株式会社 氧化还原流动二次电池及其电极
CN109818048A (zh) * 2019-03-04 2019-05-28 江西星盈科技有限公司 全固态锂金属电池及其制备工艺
CN109845020A (zh) * 2016-07-11 2019-06-04 得克萨斯州大学系统董事会 基于金属镀覆的电能储存单元
CN109950667A (zh) * 2017-12-21 2019-06-28 中南大学 一种锂氧气(空气)电池扩展夹层及其湿法纺丝制备过程
CN106063012B (zh) * 2014-02-19 2019-08-16 锡安能量公司 使用抑制电解质的离子导体的电极保护
CN110710024A (zh) * 2017-06-09 2020-01-17 罗伯特·博世有限公司 具有阳极保护层的电池单元

Families Citing this family (356)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6911280B1 (en) * 2001-12-21 2005-06-28 Polyplus Battery Company Chemical protection of a lithium surface
US20080057386A1 (en) * 2002-10-15 2008-03-06 Polyplus Battery Company Ionically conductive membranes for protection of active metal anodes and battery cells
US7282302B2 (en) 2002-10-15 2007-10-16 Polyplus Battery Company Ionically conductive composites for protection of active metal anodes
US7645543B2 (en) 2002-10-15 2010-01-12 Polyplus Battery Company Active metal/aqueous electrochemical cells and systems
US7608178B2 (en) * 2003-11-10 2009-10-27 Polyplus Battery Company Active metal electrolyzer
US7491458B2 (en) 2003-11-10 2009-02-17 Polyplus Battery Company Active metal fuel cells
US7646171B2 (en) * 2004-01-06 2010-01-12 Sion Power Corporation Methods of charging lithium sulfur cells
US8828610B2 (en) 2004-01-06 2014-09-09 Sion Power Corporation Electrolytes for lithium sulfur cells
US7358012B2 (en) 2004-01-06 2008-04-15 Sion Power Corporation Electrolytes for lithium sulfur cells
US10297827B2 (en) 2004-01-06 2019-05-21 Sion Power Corporation Electrochemical cell, components thereof, and methods of making and using same
US9368775B2 (en) 2004-02-06 2016-06-14 Polyplus Battery Company Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers
US7282295B2 (en) 2004-02-06 2007-10-16 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US7691536B2 (en) * 2004-02-20 2010-04-06 Excellatron Solid State, Llc Lithium oxygen batteries and method of producing same
US10566669B2 (en) 2004-02-20 2020-02-18 Johnson Ip Holding, Llc Lithium oxygen batteries having a carbon cloth current collector and method of producing same
US20080070087A1 (en) * 2004-02-20 2008-03-20 Excellatron Solid State, Llc Non-volatile cathodes for lithium oxygen batteries and method of producing same
KR100914109B1 (ko) * 2004-05-14 2009-08-27 파나소닉 주식회사 리튬이온 2차전지
US20060078790A1 (en) * 2004-10-05 2006-04-13 Polyplus Battery Company Solid electrolytes based on lithium hafnium phosphate for active metal anode protection
US7670724B1 (en) * 2005-01-05 2010-03-02 The United States Of America As Represented By The Secretary Of The Army Alkali-hydroxide modified poly-vinylidene fluoride/polyethylene oxide lithium-air battery
US20060194115A1 (en) * 2005-02-14 2006-08-31 Polyplus Battery Company Intercalation anode protection for cells with dissolved lithium polysulfides
MX2008002074A (es) * 2005-08-09 2008-04-22 Polyplus Battery Co Inc Estructuras de sello flexible para anodos de metal activo protegidos.
US8404388B2 (en) 2005-08-09 2013-03-26 Polyplus Battery Company Compliant seal structures for protected active metal anodes
US8048570B2 (en) * 2005-08-09 2011-11-01 Polyplus Battery Company Compliant seal structures for protected active metal anodes
US8129052B2 (en) 2005-09-02 2012-03-06 Polyplus Battery Company Polymer adhesive seals for protected anode architectures
WO2007062220A2 (en) * 2005-11-23 2007-05-31 Polyplus Battery Company Li/air non-aqueous batteries
WO2007075867A2 (en) 2005-12-19 2007-07-05 Polyplus Battery Company Composite solid electrolyte for protection of active metal anodes
WO2007106742A2 (en) * 2006-03-10 2007-09-20 Excellatron Solid State Llc Air battery and manufacturing method
US20070259234A1 (en) * 2006-05-06 2007-11-08 David Chua Metal-air semi-fuel cell with an aqueous acid based cathode
CA2552282A1 (fr) 2006-07-18 2008-01-18 Hydro Quebec Materiau multi-couches a base de lithium vif, procedes de preparation et applications dans les generateurs electrochimiques
WO2008016990A2 (en) * 2006-08-02 2008-02-07 Ada Technologies, Inc. High performance ultracapacitors with carbon nanomaterials and ionic liquids
EP2087540A4 (en) * 2006-10-13 2014-01-22 Ceramatec Inc ADVANCED AIR-METAL BATTERY HAVING CERAMIC MEMBRANE ELECTROLYTE
DE102006054951A1 (de) * 2006-11-22 2008-05-29 Volkswagen Ag Ionische Flüssigkeiten sowie deren Verwendung
WO2008067409A2 (en) * 2006-11-28 2008-06-05 Polyplus Battery Company Protected lithium electrodes for electro-transport drug delivery
WO2008089110A1 (en) 2007-01-12 2008-07-24 Microazure Corporation Three-dimensional batteries and methods of manufacturing the same
EP2132806A4 (en) * 2007-03-30 2012-12-19 Univ Michigan MICROARCHITECTURATED BATTERY
US20090005824A1 (en) * 2007-06-29 2009-01-01 Polyplus Battery Company Electrotransport devices, methods and drug electrode assemblies
FR2920255B1 (fr) * 2007-08-24 2009-11-13 Commissariat Energie Atomique Generateur electrochimique au lithium fonctionnant avec un electrolyte aqueux.
US20100239893A1 (en) * 2007-09-05 2010-09-23 John Howard Gordon Sodium-sulfur battery with a substantially non-porous membrane and enhanced cathode utilization
WO2009032313A1 (en) 2007-09-05 2009-03-12 Ceramatec, Inc. Lithium-sulfur battery with a substantially non- porous membrane and enhanced cathode utilization
US20090069740A1 (en) * 2007-09-07 2009-03-12 Polyplus Battery Company Protected donor electrodes for electro-transport drug delivery
US8012621B2 (en) 2007-11-26 2011-09-06 Ceramatec, Inc. Nickel-metal hydride battery using alkali ion conducting separator
US9209445B2 (en) 2007-11-26 2015-12-08 Ceramatec, Inc. Nickel-metal hydride/hydrogen hybrid battery using alkali ion conducting separator
WO2009070600A2 (en) 2007-11-27 2009-06-04 Ceramatec, Inc. Substantially solid, flexible electrolyte for alkili-metal-ion batteries
CA2705270C (en) * 2007-11-27 2016-07-26 Ceramatec, Inc. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides
US9722275B2 (en) * 2007-12-14 2017-08-01 Nanotek Instruments, Inc. Anode protective layer compositions for lithium metal batteries
US20090189567A1 (en) * 2008-01-30 2009-07-30 Joshi Ashok V Zinc Anode Battery Using Alkali Ion Conducting Separator
US10320033B2 (en) 2008-01-30 2019-06-11 Enlighten Innovations Inc. Alkali metal ion battery using alkali metal conductive ceramic separator
US8236446B2 (en) * 2008-03-26 2012-08-07 Ada Technologies, Inc. High performance batteries with carbon nanomaterials and ionic liquids
US8187752B2 (en) 2008-04-16 2012-05-29 Envia Systems, Inc. High energy lithium ion secondary batteries
US8277691B2 (en) * 2008-05-05 2012-10-02 Ada Technologies, Inc. High performance carbon nanocomposites for ultracapacitors
JP5678297B2 (ja) * 2008-06-10 2015-02-25 友寄 壹 リチウムイオン電池の製法及びリチウム電池の製法
MX2010013888A (es) 2008-06-16 2011-05-03 Polyplus Battery Co Inc Celdas para baterias del litio/aire acuosas.
US9099758B2 (en) 2008-06-20 2015-08-04 University Of Dayton Lithium-air cell incorporating lithium aluminum germanium phosphate cathode
US9178255B2 (en) * 2008-06-20 2015-11-03 University Of Dayton Lithium-air cells incorporating solid electrolytes having enhanced ionic transport and catalytic activity
US8323817B2 (en) * 2008-09-12 2012-12-04 Ceramatec, Inc. Alkali metal seawater battery
US9475998B2 (en) 2008-10-09 2016-10-25 Ceramatec, Inc. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides
US20100141211A1 (en) * 2008-11-04 2010-06-10 Rachid Yazami Hybrid electrochemical generator with a soluble anode
JP5354580B2 (ja) * 2009-01-28 2013-11-27 独立行政法人産業技術総合研究所 リチウム−空気電池
US20130244085A1 (en) * 2009-03-16 2013-09-19 Ceramatec, Inc Battery with non-porous alkali metal ion conductive honeycomb structure separator
US8673067B2 (en) * 2009-05-21 2014-03-18 Battelle Memorial Institute Immobilized fluid membranes for gas separation
FR2941091A1 (fr) * 2009-06-19 2010-07-16 Commissariat Energie Atomique Accumulateur de type lithium-air avec une anode comprenant un materiau d'insertion/desinsertion du lithium
US10056644B2 (en) 2009-07-24 2018-08-21 Zenlabs Energy, Inc. Lithium ion batteries with long cycling performance
WO2011020073A1 (en) * 2009-08-14 2011-02-17 Seeo, Inc High energy polymer battery
WO2011028251A2 (en) 2009-08-24 2011-03-10 Sion Power Corporation Release system for electrochemical cells
WO2011031455A2 (en) * 2009-08-25 2011-03-17 Polyplus Battery Company Implantable electrode assembly, implantable electrochemical power cells and implantable medical device assemblies
US8481187B2 (en) 2009-09-10 2013-07-09 Battelle Memorial Institute High-energy metal air batteries
US20110059364A1 (en) * 2009-09-10 2011-03-10 Battelle Memorial Institute Air electrodes for high-energy metal air batteries and methods of making the same
FR2950737B1 (fr) * 2009-09-30 2012-01-20 Electricite De France Compartiment negatif rigide pour batterie metal-air et procede de fabrication de celui-ci
FR2951714B1 (fr) * 2009-10-27 2013-05-24 Electricite De France Dispositif electrochimique a electrolyte solide conducteur d'ions alcalins et a electrolyte aqueux
JP2011096492A (ja) * 2009-10-29 2011-05-12 Sony Corp リチウム空気電池
US8236452B2 (en) * 2009-11-02 2012-08-07 Nanotek Instruments, Inc. Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
EP2497133B1 (en) 2009-11-05 2018-12-26 Field Upgrading USA, Inc. Solid-state sodium-based secondary cell having a sodium ion conductive ceramic separator
US9159995B2 (en) * 2009-11-19 2015-10-13 Technion Research & Development Foundation Limited Silicon-air batteries
US8993177B2 (en) 2009-12-04 2015-03-31 Envia Systems, Inc. Lithium ion battery with high voltage electrolytes and additives
US8592092B2 (en) 2009-12-09 2013-11-26 Toyota Jidosha Kabushiki Kaisha Battery
DE102009057718A1 (de) * 2009-12-10 2011-06-16 Siemens Aktiengesellschaft Batterie und Verfahren zum Betreiben einer Batterie
JP5408265B2 (ja) * 2009-12-24 2014-02-05 トヨタ自動車株式会社 空気電池システム
US8962188B2 (en) 2010-01-07 2015-02-24 Nanotek Instruments, Inc. Anode compositions for lithium secondary batteries
DE102010051964A1 (de) 2010-01-14 2011-07-21 Volkswagen AG, 38440 Lithium-Luftbatterie mit sauerstoffübertragendem Elektrolyt
US20110177401A1 (en) * 2010-01-21 2011-07-21 Owen Crowther Lithium-air cell protective membranes comprising polytetrafluoroethylene coated fiberglass cloth
US20120276457A1 (en) 2010-01-22 2012-11-01 Toyota Jidosha Kabushiki Kaisha Negative electrode structure for aqueous electrolyte batteries and aqueous electrolyte battery comprising the negative electrode structure
US8765306B2 (en) 2010-03-26 2014-07-01 Envia Systems, Inc. High voltage battery formation protocols and control of charging and discharging for desirable long term cycling performance
US8481195B1 (en) * 2010-04-14 2013-07-09 Hrl Laboratories, Llc Lithium battery structures
WO2011133982A1 (en) * 2010-04-23 2011-10-27 Liox Power, Inc. Soluble oxygen evolving catalysts for rechargeable metal-air batteries
US20110274989A1 (en) * 2010-04-30 2011-11-10 Massachusetts Institute Of Technology Catalysts for oxygen reduction and evolution in metal-air electrochemical cells
JP5545728B2 (ja) * 2010-05-07 2014-07-09 国立大学法人三重大学 リチウム二次電池及びリチウム二次電池用の複合負極
EP2569819B1 (en) 2010-05-12 2018-03-21 Arizona Board of Regents, acting for and on behalf of Arizona State University Metal-air cell with performance enhancing additive
JP5168318B2 (ja) 2010-05-25 2013-03-21 トヨタ自動車株式会社 水系電解液電池及び水系電解液電池の製造方法
US20130078535A1 (en) * 2010-06-04 2013-03-28 Masanobu Aizawa Metal-air battery
US8735003B2 (en) 2010-06-16 2014-05-27 Alliance For Sustainable Energy, Llc Lithium-ion batteries having conformal solid electrolyte layers
US8758914B2 (en) 2010-06-18 2014-06-24 Polyplus Battery Company Li-Ion/polysulfide flow battery
KR20120011322A (ko) * 2010-07-28 2012-02-07 삼성전자주식회사 리튬 공기 전지
US9083062B2 (en) 2010-08-02 2015-07-14 Envia Systems, Inc. Battery packs for vehicles and high capacity pouch secondary batteries for incorporation into compact battery packs
US8771855B2 (en) 2010-08-11 2014-07-08 Ceramatec, Inc. Alkali metal aqueous battery
JP5163709B2 (ja) * 2010-08-17 2013-03-13 トヨタ自動車株式会社 金属空気電池用液状空気極、及び当該液状空気極を備える金属空気電池
WO2012025543A1 (en) 2010-08-24 2012-03-01 Basf Se Electrolyte materials for use in electrochemical cells
US20130189592A1 (en) * 2010-09-09 2013-07-25 Farshid ROUMI Part solid, part fluid and flow electrochemical cells including metal-air and li-air battery systems
CN103098263B (zh) 2010-09-09 2016-01-20 加州理工学院 电化学能量存储系统和方法
US9843027B1 (en) 2010-09-14 2017-12-12 Enovix Corporation Battery cell having package anode plate in contact with a plurality of dies
KR20120036589A (ko) * 2010-10-08 2012-04-18 삼성전자주식회사 리튬 이온 전도체, 이의 제조방법 및 이를 포함하는 리튬 공기 전지
US20120094193A1 (en) * 2010-10-19 2012-04-19 Robert Bosch Gmbh High specific-energy li/o2-co2 battery
US9166222B2 (en) 2010-11-02 2015-10-20 Envia Systems, Inc. Lithium ion batteries with supplemental lithium
KR101256641B1 (ko) 2010-11-02 2013-04-18 삼성에스디아이 주식회사 리튬 이차전지용 양극 활물질 및 이의 제조방법
JP6041809B2 (ja) 2010-12-01 2016-12-14 セラマテック・インク 中温作動ナトリウム電池
US8758947B2 (en) 2011-01-11 2014-06-24 Battelle Memorial Institute Graphene-based battery electrodes having continuous flow paths
DE102011120959A1 (de) 2011-02-19 2012-08-23 Volkswagen Ag Metall-Schwefel-Batteriesystem
WO2012146525A1 (en) * 2011-04-26 2012-11-01 Solvay Sa Lithium air battery cell
US9093717B2 (en) 2011-05-20 2015-07-28 Board Of Trustees Of Michigan State University Methods of making and using oxide ceramic solids and products and devices related thereto
US8735002B2 (en) 2011-09-07 2014-05-27 Sion Power Corporation Lithium sulfur electrochemical cell including insoluble nitrogen-containing compound
US8760118B2 (en) 2011-06-02 2014-06-24 Robert Bosch Gmbh System and method for charging and discharging a Li-ion battery
JP5691875B2 (ja) * 2011-06-20 2015-04-01 アイシン精機株式会社 水系リチウム−空気二次電池
JP6270718B2 (ja) 2011-07-11 2018-01-31 カリフォルニア インスティチュート オブ テクノロジー 電気化学システム用のセパレータシステムおよび電気化学セル
US9379368B2 (en) 2011-07-11 2016-06-28 California Institute Of Technology Electrochemical systems with electronically conductive layers
CA2877487A1 (en) 2011-07-12 2013-01-17 Board Of Trustees Of Michigan State University Porous sol gels and methods and structures related thereto
JP5674040B2 (ja) * 2011-07-25 2015-02-18 独立行政法人産業技術総合研究所 電気的充電と酸化剤による化学的酸化の双方により再生可能なリチウムセミレドックスフロー電池。
US9159990B2 (en) 2011-08-19 2015-10-13 Envia Systems, Inc. High capacity lithium ion battery formation protocol and corresponding batteries
WO2013028574A2 (en) 2011-08-19 2013-02-28 Polyplus Battery Company Aqueous lithium air batteries
US9306195B2 (en) 2011-09-29 2016-04-05 General Electric Company Electrochemical cells
US9525197B2 (en) 2011-10-10 2016-12-20 Toyota Motor Europe Nv/Sa Stable non-aqueous electrolyte promoting ideal reaction process in rechargeable lithium-air batteries
KR101851564B1 (ko) * 2011-10-27 2018-04-25 삼성전자주식회사 리튬 공기 전지용 전해질 및 이를 포함한 리튬 공기전지
CN102400135B (zh) * 2011-11-05 2013-03-20 太原理工大学 一种镁铝合金板的涂层热压增强方法
US8828573B2 (en) 2011-11-15 2014-09-09 Polyplus Battery Company Electrode structures for aqueous electrolyte lithium sulfur batteries
US8828574B2 (en) 2011-11-15 2014-09-09 Polyplus Battery Company Electrolyte compositions for aqueous electrolyte lithium sulfur batteries
EP2792015B1 (en) 2011-11-22 2017-06-28 Robert Bosch GmbH High specific-energy li/02-co2 battery
JP2013114966A (ja) * 2011-11-30 2013-06-10 Idemitsu Kosan Co Ltd 電解質シート
US10355305B2 (en) 2012-01-16 2019-07-16 Enlighten Innovations Inc. Alkali metal intercalation material as an electrode in an electrolytic cell
EP2807698B1 (en) * 2012-01-24 2018-01-10 Enovix Corporation Ionically permeable structures for energy storage devices
EP2828923B1 (en) 2012-03-19 2018-05-02 Toyota Motor Europe NV/SA Three-dimensional carbon foam-supported electrode for metal-air batteries
WO2013154623A1 (en) * 2012-04-10 2013-10-17 California Institute Of Technology Novel separators for electrochemical systems
US11145857B2 (en) 2012-04-11 2021-10-12 Ionic Materials, Inc. High capacity polymer cathode and high energy density rechargeable cell comprising the cathode
US11152657B2 (en) 2012-04-11 2021-10-19 Ionic Materials, Inc. Alkaline metal-air battery cathode
US10559827B2 (en) 2013-12-03 2020-02-11 Ionic Materials, Inc. Electrochemical cell having solid ionically conducting polymer material
US11319411B2 (en) 2012-04-11 2022-05-03 Ionic Materials, Inc. Solid ionically conducting polymer material
US11251455B2 (en) 2012-04-11 2022-02-15 Ionic Materials, Inc. Solid ionically conducting polymer material
US9819053B1 (en) 2012-04-11 2017-11-14 Ionic Materials, Inc. Solid electrolyte high energy battery
FR2990064B1 (fr) * 2012-04-25 2014-05-23 Commissariat Energie Atomique Accumulateur electrochimique au lithium du type lithium-air
US8932771B2 (en) 2012-05-03 2015-01-13 Polyplus Battery Company Cathode architectures for alkali metal / oxygen batteries
US9780358B2 (en) 2012-05-04 2017-10-03 Zenlabs Energy, Inc. Battery designs with high capacity anode materials and cathode materials
US10553871B2 (en) 2012-05-04 2020-02-04 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
DE102012208316A1 (de) * 2012-05-18 2013-11-21 Robert Bosch Gmbh Lithium-Elektrode für eine Lithium-Ionen-Batterie und Verfahren zum Herstellen einer solchen
US20150171469A1 (en) * 2012-06-19 2015-06-18 E.I. Du Pont De Nemours And Company Additives with ionomer articles, methods for making and methods for using
WO2014004531A2 (en) * 2012-06-25 2014-01-03 Robert Bosch Gmbh Metal/oxygen battery with electrochemical oxygen compression
JP5598503B2 (ja) * 2012-07-02 2014-10-01 トヨタ自動車株式会社 空気電池用イオン性液体、当該イオン性液体を含有するリチウム空気電池用電解液及び空気電池
US20140017571A1 (en) * 2012-07-16 2014-01-16 Nthdegree Technologies Worldwide Inc. Printable Ionic Gel Separation Layer for Energy Storage Devices
US9548511B2 (en) 2012-07-18 2017-01-17 Nthdegree Technologies Worldwide Inc. Diatomaceous energy storage devices
US9083010B2 (en) 2012-07-18 2015-07-14 Nthdegree Technologies Worldwide Inc. Diatomaceous energy storage devices
CN108417401A (zh) 2012-07-18 2018-08-17 印制能源技术有限公司 硅藻土能量储存装置
US10396365B2 (en) 2012-07-18 2019-08-27 Printed Energy Pty Ltd Diatomaceous energy storage devices
US20140075745A1 (en) 2012-08-01 2014-03-20 Sharp Laboratories Of America, Inc. High Capacity Alkali/Oxidant Battery
US9397345B2 (en) 2012-08-06 2016-07-19 The Curators Of The University Of Missouri Cathodes for lithium-air battery cells with acid electrolytes
CN104584293A (zh) * 2012-08-14 2015-04-29 英派尔科技开发有限公司 柔性透明空气-金属电池
JP6416765B2 (ja) 2012-08-16 2018-10-31 エノビクス・コーポレイションEnovix Corporation 3次元電池のための電極構造体
US10854929B2 (en) 2012-09-06 2020-12-01 Field Upgrading Usa, Inc. Sodium-halogen secondary cell
US20140080013A1 (en) * 2012-09-17 2014-03-20 Battelle Memorial Institute Metal-air battery
US9520598B2 (en) 2012-10-10 2016-12-13 Nthdegree Technologies Worldwide Inc. Printed energy storage device
US9397341B2 (en) 2012-10-10 2016-07-19 Nthdegree Technologies Worldwide Inc. Printed energy storage device
FR2996780B1 (fr) * 2012-10-16 2014-12-19 Univ Claude Bernard Lyon Procede et dispositif de production d'energie
US9577289B2 (en) 2012-12-17 2017-02-21 Sion Power Corporation Lithium-ion electrochemical cell, components thereof, and methods of making and using same
KR102038624B1 (ko) * 2012-12-21 2019-10-31 삼성전자주식회사 보호 음극, 이를 포함하는 리튬 공기 전지, 및 리튬 이온 전도성 보호막의 제조방법
US9362546B1 (en) 2013-01-07 2016-06-07 Quantumscape Corporation Thin film lithium conducting powder material deposition from flux
US10388975B2 (en) 2013-01-31 2019-08-20 Board Of Trustees Of Michigan State University Template-based methods of making and using ceramic solids
US10164231B2 (en) 2013-02-05 2018-12-25 Hrl Laboratories, Llc Separators for lithium-sulfur batteries
US9627691B2 (en) 2013-02-07 2017-04-18 Ada Technologies, Inc. Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same
WO2014130725A1 (en) * 2013-02-21 2014-08-28 Robert Bosch Gmbh Lithium battery with composite solid electrolyte
KR102031349B1 (ko) 2013-02-21 2019-10-14 삼성전자주식회사 양극, 이를 포함하는 리튬공기전지, 및 양극의 제조방법
ES2817901T3 (es) * 2013-03-04 2021-04-08 Enlighten Innovations Inc Material de intercalación de metal alcalino como electrodo en una celda electrolítica
WO2014140198A1 (en) 2013-03-15 2014-09-18 Basf Se Protected electrode structures
US9728768B2 (en) 2013-03-15 2017-08-08 Sion Power Corporation Protected electrode structures and methods
US9991490B2 (en) 2013-03-15 2018-06-05 Enovix Corporation Separators for three-dimensional batteries
WO2014153536A1 (en) * 2013-03-21 2014-09-25 Sila Nanotechnologies Inc. Electrochemical energy storage devices and components
CN103214183B (zh) * 2013-03-28 2016-12-28 华南理工大学 一种下转换玻璃基片及其制备方法和在CdTe太阳能电池中的应用
CN104124463A (zh) * 2013-04-26 2014-10-29 中国科学院大连化学物理研究所 氢氯燃料电池用离子液体-聚合物复合膜及其制备和应用
GB2514821A (en) 2013-06-06 2014-12-10 Leclanch S A Electrochemical cells with glass containing separators
US9905860B2 (en) 2013-06-28 2018-02-27 Polyplus Battery Company Water activated battery system having enhanced start-up behavior
WO2015003123A1 (en) * 2013-07-03 2015-01-08 Sion Power Corporation Ceramic/polymer matrix for electrode protection in electrochemical cells, including rechargeable lithium batteries
US20150014184A1 (en) * 2013-07-10 2015-01-15 Lawence Ralph Swonger Producing lithium
CN105379000B (zh) 2013-07-17 2019-08-27 印制能源技术有限公司 能量储存装置
WO2015013207A1 (en) * 2013-07-22 2015-01-29 Battell Memorial Institute Polymer electrolytes for dendrite-free energy storage devices having high coulombic efficiency
KR102126278B1 (ko) * 2013-08-05 2020-06-24 에스케이이노베이션 주식회사 리튬 에어 배터리
WO2015021373A1 (en) 2013-08-08 2015-02-12 Sion Power Corporation Self-healing electrode protection in electrochemical cells
US11476494B2 (en) 2013-08-16 2022-10-18 Zenlabs Energy, Inc. Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics
US20160204476A1 (en) * 2013-09-02 2016-07-14 W.L. Gore & Associates, Co., Ltd. Protective film, separator and secondary battery using the same
KR102155696B1 (ko) 2013-09-13 2020-09-15 삼성전자주식회사 복합막, 그 제조방법 및 이를 포함한 리튬 공기 전지
EP3055268B1 (en) 2013-10-07 2021-09-01 QuantumScape Battery, Inc. Bilayers and trilayers comprising lithium-stuffed garnet films and a method for sintering a thin an free standing lithium-stuffed garnet film
US10714724B2 (en) 2013-11-18 2020-07-14 California Institute Of Technology Membranes for electrochemical cells
WO2015074065A1 (en) 2013-11-18 2015-05-21 California Institute Of Technology Electrochemical separators with inserted conductive layers
WO2015079689A1 (en) * 2013-11-27 2015-06-04 Sharp Kabushiki Kaisha High capacity alkali/oxidant battery
KR20150061605A (ko) 2013-11-27 2015-06-04 국립대학법인 울산과학기술대학교 산학협력단 이차 전지 및 이차 전지 시스템
KR102168066B1 (ko) 2013-12-03 2020-10-20 아이오닉 머터리얼스, 인코퍼레이션 이온 전도성 고체 폴리머 물질 및 응용
JP6217974B2 (ja) * 2013-12-11 2017-10-25 トヨタ自動車株式会社 非水電解質二次電池
US9640332B2 (en) * 2013-12-20 2017-05-02 Intel Corporation Hybrid electrochemical capacitor
KR20170038104A (ko) * 2014-01-02 2017-04-05 피너지 엘티디. 하이브리드 금속 공기 시스템 및 방법
US9997813B2 (en) 2014-02-18 2018-06-12 Sk Innovation Co., Ltd. Lithium air battery
WO2015126885A1 (en) 2014-02-19 2015-08-27 Basf Se Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor
US10490796B2 (en) 2014-02-19 2019-11-26 Sion Power Corporation Electrode protection using electrolyte-inhibiting ion conductor
WO2015141952A1 (ko) * 2014-03-19 2015-09-24 (주)오렌지파워 리튬 설퍼 전지
US20150318530A1 (en) * 2014-05-01 2015-11-05 Sila Nanotechnologies, Inc. Aqueous electrochemical energy storage devices and components
KR102255300B1 (ko) 2014-05-16 2021-05-24 삼성전자주식회사 금속-공기 전지
EP2950380B1 (en) 2014-05-27 2017-04-12 Samsung Electronics Co., Ltd Electrolyte for lithium air battery and lithium air battery including the same
CN106415908B (zh) 2014-06-17 2019-02-12 美敦力公司 用于电池的半固体电解质
JP6361963B2 (ja) * 2014-06-20 2018-07-25 スズキ株式会社 リチウム空気電池の負極複合体、リチウム空気電池、およびリチウム空気電池モジュール
DE102014212139A1 (de) * 2014-06-25 2015-12-31 Robert Bosch Gmbh Anodenschutzschichtsystem mit Flüssigphasenschicht für eine Lithium-Zelle
US9780386B2 (en) 2014-08-08 2017-10-03 Samsung Electronics Co., Ltd. Composite for lithium air battery, method of preparing the composite, and lithium air battery employing positive electrode including the composite
KR102280684B1 (ko) 2014-08-27 2021-07-22 삼성전자주식회사 리튬공기전지 및 이의 제조방법
US10333173B2 (en) 2014-11-14 2019-06-25 Medtronic, Inc. Composite separator and electrolyte for solid state batteries
US10211481B2 (en) 2014-11-26 2019-02-19 Corning Incorporated Stabilized solid garnet electrolyte and methods thereof
US10593998B2 (en) 2014-11-26 2020-03-17 Corning Incorporated Phosphate-garnet solid electrolyte structure
US10147968B2 (en) 2014-12-02 2018-12-04 Polyplus Battery Company Standalone sulfide based lithium ion-conducting glass solid electrolyte and associated structures, cells and methods
US10601071B2 (en) 2014-12-02 2020-03-24 Polyplus Battery Company Methods of making and inspecting a web of vitreous lithium sulfide separator sheet and lithium electrode assemblies
US11749834B2 (en) 2014-12-02 2023-09-05 Polyplus Battery Company Methods of making lithium ion conducting sulfide glass
US10164289B2 (en) 2014-12-02 2018-12-25 Polyplus Battery Company Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods
EP3041066B1 (en) 2014-12-19 2017-11-29 Samsung Electronics Co., Ltd Composite membrane, preparation method thereof, anode structure including the composite membrane, and lithium secondary battery including the anode structure
US20160188716A1 (en) * 2014-12-24 2016-06-30 Quixey, Inc. Crowd-Sourced Crawling
US10262066B2 (en) * 2014-12-24 2019-04-16 Samsung Electronics Co., Ltd. Crowd-sourced native application crawling
US10615457B2 (en) 2015-02-25 2020-04-07 Ses Holdings Pte. Ltd. Electrolyte system for high voltage lithium ion battery
EP3353844B1 (en) 2015-03-27 2022-05-11 Mason K. Harrup All-inorganic solvents for electrolytes
CN107615521A (zh) 2015-03-30 2018-01-19 固态能源系统公司 电池应用中锂金属阳极的复合涂层体系和方法
EP3283449B8 (en) 2015-04-16 2021-05-05 QuantumScape Battery, Inc. Lithium stuffed garnet setter plates for solid electrolyte fabrication
KR102364843B1 (ko) * 2015-04-28 2022-02-18 삼성전자주식회사 전기 화학 전지, 이를 포함하는 전기 화학 전지 모듈 및 전기 화학 전지 제조방법
KR20230020563A (ko) 2015-05-14 2023-02-10 에노빅스 코오퍼레이션 에너지 저장 디바이스들에 대한 종방향 구속부들
KR102364845B1 (ko) * 2015-05-18 2022-02-18 삼성전자주식회사 리튬공기전지 및 이의 제조방법
CN108352565A (zh) * 2015-06-04 2018-07-31 离子材料公司 具有固体聚合物电解质的锂金属电池
KR102608943B1 (ko) 2015-06-04 2023-11-30 아이오닉 머터리얼스, 인코퍼레이션 고체 상태 바이폴라 배터리
US11342559B2 (en) 2015-06-08 2022-05-24 Ionic Materials, Inc. Battery with polyvalent metal anode
US11605819B2 (en) 2015-06-08 2023-03-14 Ionic Materials, Inc. Battery having aluminum anode and solid polymer electrolyte
WO2016200870A1 (en) * 2015-06-08 2016-12-15 The Regents Of The University Of Michigan Organic anolyte materials for flow batteries
WO2016205802A1 (en) * 2015-06-18 2016-12-22 University Of Southern California Lithium-ion mixed conductor membrane improves the performance of lithium-sulfur battery and other energy storage devices
US10347904B2 (en) 2015-06-19 2019-07-09 Solidenergy Systems, Llc Multi-layer polymer coated Li anode for high density Li metal battery
CN106328955B (zh) * 2015-06-25 2019-02-12 清华大学 锂空气电池正极及锂空气电池
KR102409386B1 (ko) 2015-07-08 2022-06-15 삼성전자주식회사 금속 공기 전지 시스템 및 그 작동 방법
EP3116058B1 (en) 2015-07-08 2019-12-04 Samsung Electronics Co., Ltd. Electrochemical battery and method of operating the same
WO2017066810A1 (en) 2015-10-13 2017-04-20 Arizona Board Of Regents On Behalf Of Arizona State University Chelating ionic liquids for magnesium battery electrolytes and systems
WO2017083822A1 (en) * 2015-11-13 2017-05-18 Massachusetts Institute Of Technology Methods and apparatus for controlling electrodeposition using surface charge properties
US10128551B2 (en) * 2015-11-20 2018-11-13 Samsung Electronics Co., Ltd. Electrolyte for lithium air battery and lithium air battery including the same
US9779882B2 (en) * 2015-11-23 2017-10-03 Nanotek Instruments, Inc. Method of producing supercapacitor electrodes and cells having high active mass loading
US10263305B2 (en) 2015-12-01 2019-04-16 Denso Corporation Magnesium oxygen battery
WO2017096258A1 (en) 2015-12-02 2017-06-08 California Institute Of Technology Three-dimensional ion transport networks and current collectors for electrochemical cells
CN105428724A (zh) * 2016-01-19 2016-03-23 范永禧 一种新型锂电池电解液及其制备方法
US9966630B2 (en) 2016-01-27 2018-05-08 Quantumscape Corporation Annealed garnet electrolyte separators
US10587005B2 (en) 2016-03-30 2020-03-10 Wildcat Discovery Technologies, Inc. Solid electrolyte compositions
US10734642B2 (en) 2016-03-30 2020-08-04 Global Graphene Group, Inc. Elastomer-encapsulated particles of high-capacity anode active materials for lithium batteries
WO2017197039A1 (en) 2016-05-10 2017-11-16 Polyplus Battery Company Solid-state laminate electrode assemblies and methods of making
EP3455898A4 (en) 2016-05-13 2019-12-18 Enovix Corporation DIMENSIONAL LIMITATIONS FOR THREE-DIMENSIONAL BATTERIES
US20170331092A1 (en) 2016-05-13 2017-11-16 Quantumscape Corporation Solid electrolyte separator bonding agent
US10418630B2 (en) 2016-07-14 2019-09-17 Ford Global Technologies, Llc Lithium-sulfur battery cell electrode
KR102626915B1 (ko) 2016-08-02 2024-01-18 삼성전자주식회사 복합막, 그 제조방법 및 이를 포함하는 리튬공기전지
US11158880B2 (en) 2016-08-05 2021-10-26 Quantumscape Battery, Inc. Translucent and transparent separators
JP6665729B2 (ja) * 2016-08-08 2020-03-13 スズキ株式会社 リチウム空気電池の正極構造
US11121422B2 (en) 2016-08-16 2021-09-14 Toyota Motor Europe Fluorinated ionic liquids with high oxygen solubility for metal-air batteries
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
DE102016011895A1 (de) 2016-10-05 2017-04-27 Daimler Ag Beschichteter Feststoffelektrolyt für Feststoffbatteriezelle
US11916200B2 (en) 2016-10-21 2024-02-27 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same
WO2018081808A1 (en) * 2016-10-31 2018-05-03 The Regents Of The University Of California Lithium and sodium superionic conductors
US10916762B2 (en) 2016-11-01 2021-02-09 Samsung Electronics Co., Ltd. Cathode for metal-air battery including spaces for accommodating metal oxides formed during discharge of metal-air battery and metal-air battery including the same
CN106410331A (zh) * 2016-11-07 2017-02-15 珠海格力电器股份有限公司 一种电池及运行该电池的方法
TWI819481B (zh) 2016-11-16 2023-10-21 美商易諾維公司 具有可壓縮陰極之三維電池
US10749201B2 (en) * 2017-01-11 2020-08-18 Xergy Inc. Regenerative fuel cell
WO2018140552A1 (en) 2017-01-26 2018-08-02 Ionic Materials, Inc. Alkaline battery cathode with solid polymer electrolyte
US11495792B2 (en) 2017-02-16 2022-11-08 Global Graphene Group, Inc. Method of manufacturing a lithium secondary battery having a protected high-capacity anode active material
US10211455B2 (en) 2017-02-20 2019-02-19 Nanotek Instruments, Inc. Lithium secondary batteries containing protected particles of anode active materials and method of manufacturing
US10084182B2 (en) 2017-02-23 2018-09-25 Nanotek Instruments, Inc. Alkali metal-sulfur secondary battery containing a protected sulfur cathode and manufacturing method
US10840502B2 (en) 2017-02-24 2020-11-17 Global Graphene Group, Inc. Polymer binder for lithium battery and method of manufacturing
US10985373B2 (en) 2017-02-27 2021-04-20 Global Graphene Group, Inc. Lithium battery cathode and method of manufacturing
US10411264B2 (en) 2017-02-27 2019-09-10 Global Graphene Group, Inc. Cathode active material layer for lithium secondary battery and method of manufacturing
CH713537A2 (it) * 2017-03-02 2018-09-14 Protonstar Sagl Sistema di accumulo energetico in una matrice di nichel.
US11742475B2 (en) 2017-04-03 2023-08-29 Global Graphene Group, Inc. Encapsulated anode active material particles, lithium secondary batteries containing same, and method of manufacturing
US10483533B2 (en) 2017-04-10 2019-11-19 Global Graphene Group, Inc. Encapsulated cathode active material particles, lithium secondary batteries containing same, and method of manufacturing
US10916766B2 (en) 2017-04-10 2021-02-09 Global Graphene Group, Inc. Alkali metal-sulfur secondary battery containing a polymer-encapsulated sulfur cathode and manufacturing method
US10770721B2 (en) 2017-04-10 2020-09-08 Global Graphene Group, Inc. Lithium metal secondary battery containing anode-protecting polymer layer and manufacturing method
US10862129B2 (en) 2017-04-12 2020-12-08 Global Graphene Group, Inc. Lithium anode-protecting polymer layer for a lithium metal secondary battery and manufacturing method
KR102311682B1 (ko) 2017-06-02 2021-10-12 삼성전자주식회사 실란 화합물을 포함하는 복합 고체전해질 및 이를 포함하는 리튬전지
EP3642899B1 (en) 2017-06-23 2024-02-21 QuantumScape Battery, Inc. Lithium-stuffed garnet electrolytes with secondary phase inclusions
US10347937B2 (en) 2017-06-23 2019-07-09 Quantumscape Corporation Lithium-stuffed garnet electrolytes with secondary phase inclusions
US10629950B2 (en) 2017-07-07 2020-04-21 Polyplus Battery Company Encapsulated sulfide glass solid electrolytes and solid-state laminate electrode assemblies
US10868293B2 (en) 2017-07-07 2020-12-15 Polyplus Battery Company Treating sulfide glass surfaces and making solid state laminate electrode assemblies
KR102246632B1 (ko) * 2017-07-11 2021-04-30 주식회사 엘지화학 리튬 금속을 음극으로 하는 이차전지의 제조방법
US10862171B2 (en) 2017-07-19 2020-12-08 Polyplus Battery Company Solid-state laminate electrode assembly fabrication and making thin extruded lithium metal foils
US10964951B2 (en) 2017-08-14 2021-03-30 Global Graphene Group, Inc. Anode-protecting layer for a lithium metal secondary battery and manufacturing method
US10804537B2 (en) 2017-08-14 2020-10-13 Global Graphene Group, Inc. Protected particles of anode active materials, lithium secondary batteries containing same and method of manufacturing
US11170944B2 (en) * 2017-09-18 2021-11-09 KYOCERA AVX Components Corporation Ultracapacitor with a low leakage current
KR101888866B1 (ko) * 2017-10-27 2018-08-16 디자인정글(주) 저작권 보호를 통한 콘텐츠 유통 방법 및 그 시스템
US11600850B2 (en) 2017-11-06 2023-03-07 Quantumscape Battery, Inc. Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets
US11476522B2 (en) 2017-11-15 2022-10-18 Samsung Electronics Co., Ltd. Metal-air battery
US10256507B1 (en) 2017-11-15 2019-04-09 Enovix Corporation Constrained electrode assembly
TWI794331B (zh) 2017-11-15 2023-03-01 美商易諾維公司 電極總成及蓄電池組
US11149356B2 (en) 2017-12-19 2021-10-19 Battelle Energy Alliance, Llc Methods of forming metals using ionic liquids
US11094925B2 (en) 2017-12-22 2021-08-17 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
CN108183258B (zh) * 2018-01-03 2020-05-22 清陶(昆山)能源发展有限公司 一种聚丙烯酸酯类固态聚合物电解质以及制备方法及其在固态锂电池中的应用
US10601034B2 (en) 2018-02-21 2020-03-24 Global Graphene Group, Inc. Method of producing protected particles of anode active materials for lithium batteries
US10573894B2 (en) 2018-02-21 2020-02-25 Global Graphene Group, Inc. Protected particles of anode active materials for lithium batteries
US11721832B2 (en) 2018-02-23 2023-08-08 Global Graphene Group, Inc. Elastomer composite-encapsulated particles of anode active materials for lithium batteries
US10971722B2 (en) 2018-03-02 2021-04-06 Global Graphene Group, Inc. Method of manufacturing conducting elastomer composite-encapsulated particles of anode active materials for lithium batteries
US10964936B2 (en) 2018-03-02 2021-03-30 Global Graphene Group, Inc. Conducting elastomer composite-encapsulated particles of anode active materials for lithium batteries
US11005094B2 (en) 2018-03-07 2021-05-11 Global Graphene Group, Inc. Electrochemically stable elastomer-encapsulated particles of anode active materials for lithium batteries
US10818926B2 (en) 2018-03-07 2020-10-27 Global Graphene Group, Inc. Method of producing electrochemically stable elastomer-encapsulated particles of anode active materials for lithium batteries
US10971723B2 (en) 2018-04-16 2021-04-06 Global Graphene Group, Inc. Process for alkali metal-selenium secondary battery containing a cathode of encapsulated selenium particles
US11043694B2 (en) 2018-04-16 2021-06-22 Global Graphene Group, Inc. Alkali metal-selenium secondary battery containing a cathode of encapsulated selenium particles
EP3698420B1 (en) 2018-04-17 2021-03-03 Toyota Motor Europe Additives and methods to add additives in a rechargeable non-aqueous lithium-air battery
US11367927B2 (en) * 2018-05-14 2022-06-21 International Business Machines Corporation Separator for energy storage device
WO2019236371A2 (en) * 2018-05-29 2019-12-12 Nanotek Instruments, Inc. Fire-resistant lithium battery containing an electrode-protecting layer
US11121398B2 (en) 2018-06-15 2021-09-14 Global Graphene Group, Inc. Alkali metal-sulfur secondary battery containing cathode material particulates
US10978698B2 (en) 2018-06-15 2021-04-13 Global Graphene Group, Inc. Method of protecting sulfur cathode materials for alkali metal-sulfur secondary battery
US10985365B2 (en) 2018-06-18 2021-04-20 Global Graphene Group, Inc. Lithium-sulfur battery containing two anode-protecting layers
US10862157B2 (en) 2018-06-18 2020-12-08 Global Graphene Group, Inc. Alkali metal-sulfur secondary battery containing a conductive electrode-protecting layer
US10978744B2 (en) 2018-06-18 2021-04-13 Global Graphene Group, Inc. Method of protecting anode of a lithium-sulfur battery
US10985376B2 (en) 2018-06-18 2021-04-20 Global Graphene Group, Inc. Lithium-sulfur battery containing an electrode-protecting layer
US10957912B2 (en) 2018-06-18 2021-03-23 Global Graphene Group, Inc. Method of extending cycle-life of a lithium-sulfur battery
US10854927B2 (en) 2018-06-18 2020-12-01 Global Graphene Group, Inc. Method of improving cycle-life of alkali metal-sulfur secondary battery
US10727531B2 (en) 2018-06-21 2020-07-28 Global Graphene Group, Inc. Lithium metal secondary battery featuring an anode-protecting layer
US10784509B2 (en) 2018-06-21 2020-09-22 Global Graphene Group, Inc. Lithium metal secondary battery containing two anode-protecting layers
US11276852B2 (en) 2018-06-21 2022-03-15 Global Graphene Group, Inc. Lithium metal secondary battery containing an elastic anode-protecting layer
US10777810B2 (en) 2018-06-21 2020-09-15 Global Graphene Group, Inc. Lithium metal secondary battery containing a protected lithium anode
US10734646B2 (en) 2018-06-21 2020-08-04 Global Graphene Group, Inc. Lithium metal secondary battery containing an electrochemically stable anode-protecting layer
US10873088B2 (en) 2018-06-25 2020-12-22 Global Graphene Group, Inc. Lithium-selenium battery containing an electrode-protecting layer and method of improving cycle-life
US10770748B2 (en) 2018-06-25 2020-09-08 Global Graphene Group, Inc. Lithium-selenium battery containing an electrode-protecting layer and method for improving cycle-life
AU2019295778A1 (en) * 2018-06-28 2021-02-04 Alpha-En Corporation Producing lithium film using circulation of organic electrolyte
US11211639B2 (en) 2018-08-06 2021-12-28 Enovix Corporation Electrode assembly manufacture and device
US11043662B2 (en) 2018-08-22 2021-06-22 Global Graphene Group, Inc. Electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries
US11239460B2 (en) 2018-08-22 2022-02-01 Global Graphene Group, Inc. Method of producing electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries
US10886528B2 (en) 2018-08-24 2021-01-05 Global Graphene Group, Inc. Protected particles of cathode active materials for lithium batteries
US11223049B2 (en) 2018-08-24 2022-01-11 Global Graphene Group, Inc. Method of producing protected particles of cathode active materials for lithium batteries
KR102626920B1 (ko) 2018-09-14 2024-01-18 삼성전자주식회사 금속-공기 전지
US11453772B2 (en) 2018-09-30 2022-09-27 Robert Bosch Gmbh Polymer compositions based on PXE
US10971724B2 (en) 2018-10-15 2021-04-06 Global Graphene Group, Inc. Method of producing electrochemically stable anode particulates for lithium secondary batteries
US10629899B1 (en) 2018-10-15 2020-04-21 Global Graphene Group, Inc. Production method for electrochemically stable anode particulates for lithium secondary batteries
US10971725B2 (en) 2019-01-24 2021-04-06 Global Graphene Group, Inc. Lithium metal secondary battery containing elastic polymer foam as an anode-protecting layer
US11791450B2 (en) 2019-01-24 2023-10-17 Global Graphene Group, Inc. Method of improving cycle life of a rechargeable lithium metal battery
WO2020182292A1 (en) 2019-03-11 2020-09-17 Toyota Motor Europe Stable electrolyte based on a fluorinated ionic liquid and its use in high current rate lithium-air batteries
US11784318B2 (en) 2019-04-01 2023-10-10 Toyota Motor Europe 3D ordered nanomesh for metal-air battery
ES2902432T3 (es) * 2019-04-02 2022-03-28 Airbus Operations Gmbh Paneles para la cabina de una aeronave
US11728510B2 (en) 2019-05-24 2023-08-15 Samsung Electronics Co., Ltd. Solid conductor, preparation method thereof, solid electrolyte including the solid conductor, and electrochemical device including the solid conductor
CN110120309B (zh) * 2019-05-24 2021-06-29 中国科学院理化技术研究所 一种水系电解液及其应用
CN112151920A (zh) * 2019-06-28 2020-12-29 北京卫蓝新能源科技有限公司 一种固态锂空气电池
US11342548B2 (en) * 2019-06-28 2022-05-24 Research Foundation Of The City University Of New York Zinc electrodes with high capacity utilizations
CN112216871B (zh) * 2019-07-10 2022-04-15 比亚迪股份有限公司 一种锂离子电池电解液及其制备方法、锂离子电池和电池模组
US11837695B2 (en) 2019-08-05 2023-12-05 Samsung Electronics Co., Ltd. Oxide, method of preparing the same, solid electrolyte including the oxide, and electrochemical device including the oxide
WO2021081394A1 (en) * 2019-10-24 2021-04-29 Urban Electric Power Inc. Dual electrolyte approach for high voltage batteries
CN110911685B (zh) * 2019-11-28 2021-09-14 宁德新能源科技有限公司 用于负极的组合物和包含该组合物的保护膜、负极和装置
WO2021119310A1 (en) 2019-12-10 2021-06-17 Alpha-En Corporation Pre-lithiated electrode
US11631889B2 (en) 2020-01-15 2023-04-18 Polyplus Battery Company Methods and materials for protection of sulfide glass solid electrolytes
WO2021148836A1 (en) 2020-01-20 2021-07-29 Toyota Motor Europe Naphthalene based lithium compounds, a process for their preparation, their use as solid organic catalyst, and their use in rechargeable non-aqueous lithium-air battery cells
DE112020006581T5 (de) 2020-01-20 2022-12-08 Marco Carboni Wiederaufladbare nicht-wässrige lithium-luft-batteriezelle mit einem festen organischen katalysator
US20230344014A1 (en) * 2020-04-13 2023-10-26 Urban Electric Power Inc. Metal-free high voltage battery
US11677097B2 (en) 2020-06-02 2023-06-13 Samsung Electronics Co., Ltd. Solid electrolyte, method of preparing the same, and electrochemical device including the same
US11575152B2 (en) 2020-06-29 2023-02-07 Samsung Electronics Co., Ltd. Oxide, preparation method thereof, solid electrolyte including the oxide, and electrochemical device including the oxide
KR20230121994A (ko) 2020-09-18 2023-08-22 에노빅스 코오퍼레이션 레이저 빔을 사용하여 웹에서 전극 구조의 집합체를 윤곽 형성하기 위한 방법
US11637291B2 (en) 2020-11-04 2023-04-25 Global Graphene Group, Inc. Lithium-protecting polymer layer for an anode-less lithium metal secondary battery and manufacturing method
KR20230122050A (ko) 2020-12-09 2023-08-22 에노빅스 코오퍼레이션 2차 배터리용 전극 조립체의 제조를 위한 방법 및 장치
KR20220100297A (ko) 2021-01-08 2022-07-15 삼성전자주식회사 고체이온전도체, 이를 포함하는 고체전해질 및 전기화학소자, 및 상기 고체이온전도체의 제조방법
US11677101B2 (en) 2021-01-12 2023-06-13 Global Graphene Group, Inc. High-elasticity polymer for lithium metal protection, lithium secondary battery and manufacturing method
US11868657B2 (en) 2021-02-08 2024-01-09 Samsung Electronics Co., Ltd. Memory controller, method of operating the memory controller, and electronic device including the memory controller
US11637329B2 (en) 2021-02-08 2023-04-25 Global Graphene Group, Inc. High-elasticity phosphazene polymer for lithium metal protection, lithium secondary battery and manufacturing method
US11893278B2 (en) 2021-02-08 2024-02-06 Samsung Electronics Co., Ltd. Memory controller and memory control method for generating commands based on a memory request
EP4195326A1 (en) 2021-12-13 2023-06-14 Toyota Jidosha Kabushiki Kaisha Binders for cathodes of lithium secondary battery cells
EP4210155A1 (en) 2022-01-07 2023-07-12 Toyota Jidosha Kabushiki Kaisha Low toxicity ether-based electrolyte composition and metal-air battery comprising the same
EP4261973A1 (en) 2022-04-13 2023-10-18 Toyota Jidosha Kabushiki Kaisha Self-standing solid electrolyte for solid lithium-air battery cells and method of preparation thereof
EP4290637A1 (en) 2022-06-07 2023-12-13 Toyota Jidosha Kabushiki Kaisha Metal m-air battery cell comprising an organic multi redox mediator compound as soluble organic catalyst

Family Cites Families (222)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2996562A (en) 1959-04-17 1961-08-15 Corson G & W H Electric-current producing cell and generation of current with same
US3528856A (en) 1966-08-29 1970-09-15 Energy Conversion Devices Inc Thermoelectric device and method of manufacture
US3607417A (en) * 1967-12-04 1971-09-21 Ionics Battery cell
US3615835A (en) 1969-01-16 1971-10-26 Energy Conversion Devices Inc Generation of dc voltage
US3625769A (en) 1969-03-21 1971-12-07 Gulton Ind Inc Fuel cell
CA962021A (en) 1970-05-21 1975-02-04 Robert W. Gore Porous products and process therefor
US3679540A (en) 1970-11-27 1972-07-25 Celanese Corp Reinforced microporous film
US3783026A (en) 1971-03-09 1974-01-01 Union Carbide Corp Air-depolarized cells utilizing a cyanate or thiocyanate-containing electrolyte
US3912536A (en) 1971-03-27 1975-10-14 Montedison Spa Negative electrode for solid electrolyte cells
US3703415A (en) 1971-06-01 1972-11-21 Gen Electric Primary sodium-water battery
JPS5717568Y2 (zh) 1973-12-06 1982-04-13
US4020247A (en) 1974-01-09 1977-04-26 The Secretary Of State For Defense In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Water activated primary batteries
US3966497A (en) 1974-09-16 1976-06-29 Esb Incorporated Seawater battery
JPS51119069A (en) 1975-03-20 1976-10-19 Nippon Oil Co Ltd Method of producing permeable film
US3976509A (en) 1975-04-04 1976-08-24 Lockheed Missiles & Space Company, Inc. Electrolyte compositions
US4007057A (en) 1975-12-29 1977-02-08 Lockheed Missiles & Space Company, Inc. Cell comprising an alkali metal and aqueous electrolyte
US4091182A (en) 1976-03-01 1978-05-23 General Electric Company Sealed lithium electrochemical cell with sodium beta-alumina electrolyte
US4162202A (en) 1976-03-08 1979-07-24 P. R. Mallory & Co. Inc. Means for improving contact between Li and the anode current collector
GB1554668A (en) 1977-02-23 1979-10-24 Secr Defence Water activated batteries
US4163084A (en) 1978-07-27 1979-07-31 Lockheed Missiles & Space Company, Inc. Electrochemically stable cathode
US4210707A (en) 1978-11-20 1980-07-01 General Electric Company Sealed lithium-type electrochemical cell
JPS6020517Y2 (ja) 1978-11-30 1985-06-19 日野自動車株式会社 自動車のための分割型天井内張り
DE2930056A1 (de) 1979-07-25 1981-02-12 Varta Batterie Galvanisches primaerelement
US4248682A (en) 1979-09-27 1981-02-03 Prototech Company Carbon-cloth-based electrocatalytic gas diffusion electrodes, assembly and electrochemical cells comprising the same
US4429000A (en) 1979-12-11 1984-01-31 Toray Industries, Inc. Moisture-permeable waterproof coated fabric and method of making the same
JPS573371Y2 (zh) 1979-12-25 1982-01-21
US4385101A (en) 1980-04-28 1983-05-24 Catanzarite Vincent Owen Electrochemical cell structure
US4269907A (en) 1980-05-05 1981-05-26 Lockheed Missiles & Space Company, Inc. Electrochemical cell
US4405416A (en) 1980-07-18 1983-09-20 Raistrick Ian D Molten salt lithium cells
DE3033438C2 (de) 1980-09-05 1986-08-21 Brown, Boveri & Cie Ag, 6800 Mannheim Elektrochemische Speicherzelle
JPS57103271A (en) * 1980-12-17 1982-06-26 Yuasa Battery Co Ltd Battery for submerged machine
JPS57103271U (zh) 1980-12-18 1982-06-25
JPS57172660U (zh) 1981-04-23 1982-10-30
US4402995A (en) 1982-01-28 1983-09-06 Ray-O-Vac Corporation Treatment of lithium anodes
JPS5931573A (ja) 1982-08-16 1984-02-20 Nippon Telegr & Teleph Corp <Ntt> リチウム電池用負極
US4539256A (en) 1982-09-09 1985-09-03 Minnesota Mining And Manufacturing Co. Microporous sheet material, method of making and articles made therewith
US4414293A (en) 1982-09-20 1983-11-08 The United States Of America As Represented By The United States Department Of Energy Parasitic corrosion resistant anode for use in metal/air or metal/O2 cells
DE3244824C2 (de) 1982-12-03 1985-10-24 Chamotte- u. Tonwerk Kurt Hagenburger, 6719 Hettenleidelheim Eingießvorrichtung zum Vergießen einer Metallschmelze sowie Verfahren zum Vergießen derselben
US4440836A (en) 1982-12-14 1984-04-03 Union Carbide Corporation Nonaqueous cell employing an anode having a boron-containing surface film
US4981672A (en) 1983-06-27 1991-01-01 Voltaix, Inc. Composite coating for electrochemical electrode and method
US4628420A (en) 1983-09-30 1986-12-09 Beverly Safford Water activated electric cell and survival lamp system
US4528248A (en) * 1984-07-30 1985-07-09 Lockheed Missiles & Space Company, Inc. Electrochemical cell and method
FR2592990B1 (fr) 1986-01-16 1994-10-21 Accumulateurs Fixes Dispositif de repartition d'electrolyte dans une pile amorcable
JPH0646578B2 (ja) 1986-04-14 1994-06-15 三洋電機株式会社 非水系二次電池
US4726989A (en) 1986-12-11 1988-02-23 Minnesota Mining And Manufacturing Microporous materials incorporating a nucleating agent and methods for making same
US5591315A (en) 1987-03-13 1997-01-07 The Standard Oil Company Solid-component membranes electrochemical reactor components electrochemical reactors use of membranes reactor components and reactor for oxidation reactions
JPS63198261U (zh) 1987-06-10 1988-12-20
US4828942A (en) 1987-08-27 1989-05-09 Massachusetts Institute Of Technology Polysulfide battery
US4833048A (en) 1988-03-31 1989-05-23 The United States Of America As Represented By The United States Department Of Energy Metal-sulfur type cell having improved positive electrode
US4916036A (en) 1988-10-20 1990-04-10 Dreisbach Electromotive, Inc. Continuous consumable anode
US4985317A (en) 1988-11-30 1991-01-15 Japan Synthetic Rubber Co., Ltd. Lithium ion-conductive solid electrolyte containing lithium titanium phosphate
US5108856A (en) 1989-03-13 1992-04-28 Westinghouse Electric Corp. Electrolyte compositions and methods
US4917974A (en) 1989-04-14 1990-04-17 The United States Of America As Represented By The Department Of Energy Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same
US5002843A (en) 1989-06-12 1991-03-26 Cieslak Wendy R Separator material for electrochemical cells
US5162175A (en) 1989-10-13 1992-11-10 Visco Steven J Cell for making secondary batteries
CA2036098A1 (en) 1990-02-13 1991-08-14 Syuichi Izuchi Manufacturing method for electrode and manufacturing method for electrode electrolyte composite
US5035963A (en) 1990-09-11 1991-07-30 The United States Of America As Represented By The Secretary Of The Army High temperature rechargeable molten salt battery
US5427873A (en) 1990-09-14 1995-06-27 Westinghouse Electric Corporation Lithium-water battery
US5525442A (en) 1990-09-14 1996-06-11 Westinghouse Electric Corporation Alkali metal battery
US5166011A (en) 1990-11-07 1992-11-24 Alupower, Inc. Process for forming an argentic oxide containing bipolar electrode and product produced thereby and deferred actuated battery assembly employing same
DE69111078T2 (de) 1990-11-28 1996-01-11 Moltech Invent Sa Elektrodenzusammenstellung und multimonopolare zellen für die aluminiumelektrogewinnung.
US5162172A (en) 1990-12-14 1992-11-10 Arch Development Corporation Bipolar battery
US5100523A (en) 1990-12-17 1992-03-31 Ford Motor Company Use of amorphous carbon to promote adhesion between electroactive polymer films and conductive substrates
JP2917066B2 (ja) * 1991-03-01 1999-07-12 株式会社フジミインコーポレーテッド 研磨剤組成物
JP2535748B2 (ja) 1991-03-04 1996-09-18 工業技術院長 リチウム回収方法
JP3305006B2 (ja) * 1991-07-05 2002-07-22 旭化成株式会社 有機電解液を用いる電池用セパレータ及びその製造方法
US5213908A (en) 1991-09-26 1993-05-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen
US5336384A (en) 1991-11-14 1994-08-09 The Dow Chemical Company Membrane-electrode structure for electrochemical cells
US5696201A (en) 1992-04-06 1997-12-09 Matec Holding Ag Sound and heat insulation having little odor
US5338625A (en) 1992-07-29 1994-08-16 Martin Marietta Energy Systems, Inc. Thin film battery and method for making same
CA2110097C (en) 1992-11-30 2002-07-09 Soichiro Kawakami Secondary battery
US5413881A (en) 1993-01-04 1995-05-09 Clark University Aluminum and sulfur electrochemical batteries and cells
US5409786A (en) 1993-02-05 1995-04-25 Eveready Battery Company, Inc. Inactive electrochemical cell having an ionically nonconductive polymeric composition activated by electrolyte salt solution
EP0614239A3 (en) 1993-03-01 1996-10-16 Tadiran Ltd Non-aqueous secondary battery with safety device.
US5342710A (en) 1993-03-30 1994-08-30 Valence Technology, Inc. Lakyer for stabilization of lithium anode
US5387479A (en) 1993-06-16 1995-02-07 Valence Technology, Inc. Electrodes for rechargeable lithium batteries
US5314765A (en) 1993-10-14 1994-05-24 Martin Marietta Energy Systems, Inc. Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method
US5569520A (en) 1994-01-12 1996-10-29 Martin Marietta Energy Systems, Inc. Rechargeable lithium battery for use in applications requiring a low to high power output
US5961672A (en) 1994-02-16 1999-10-05 Moltech Corporation Stabilized anode for lithium-polymer batteries
ES2080686B1 (es) 1994-02-16 1996-10-16 S E De Carburos Metalicos S A Proceso y equipo de depuracion electrolitica en aguas residuales contaminadas utilizando catodos de oxigeno.
US5648187A (en) 1994-02-16 1997-07-15 Moltech Corporation Stabilized anode for lithium-polymer batteries
IL109845A (en) 1994-06-01 1998-08-16 Tadiran Ltd Rechargeable electrochemical cell
US5516598A (en) 1994-07-28 1996-05-14 Polyplus Battery Company, Inc. Secondary cell using organosulfur/metal charge transfer materials as positive electrode
US5571600A (en) 1994-11-07 1996-11-05 Clark University Sulfur/aluminum electrochemical batteries
US6030720A (en) 1994-11-23 2000-02-29 Polyplus Battery Co., Inc. Liquid electrolyte lithium-sulfur batteries
US5582623A (en) 1994-11-23 1996-12-10 Polyplus Battery Company, Inc. Methods of fabricating rechargeable positive electrodes
US6358643B1 (en) 1994-11-23 2002-03-19 Polyplus Battery Company Liquid electrolyte lithium-sulfur batteries
US5686201A (en) 1994-11-23 1997-11-11 Polyplus Battery Company, Inc. Rechargeable positive electrodes
US6017651A (en) 1994-11-23 2000-01-25 Polyplus Battery Company, Inc. Methods and reagents for enhancing the cycling efficiency of lithium polymer batteries
US5814420A (en) 1994-11-23 1998-09-29 Polyplus Battery Company, Inc. Rechargeable positive electrodes
US6376123B1 (en) 1994-11-23 2002-04-23 Polyplus Battery Company Rechargeable positive electrodes
US6025094A (en) 1994-11-23 2000-02-15 Polyplus Battery Company, Inc. Protective coatings for negative electrodes
US5523179A (en) 1994-11-23 1996-06-04 Polyplus Battery Company Rechargeable positive electrode
US5510209A (en) 1995-01-05 1996-04-23 Eic Laboratories, Inc. Solid polymer electrolyte-based oxygen batteries
US5792335A (en) 1995-03-13 1998-08-11 Magnesium Technology Limited Anodization of magnesium and magnesium based alloys
US6468688B2 (en) * 1995-05-03 2002-10-22 Pinnacle Vrb Limited High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions
US5652068A (en) 1995-11-14 1997-07-29 Northrop Grumman Corporation Metal-air battery with improved air supply
US5665481A (en) 1995-11-14 1997-09-09 Northrop Grumman Corporation Metal-air battery
US5702995A (en) 1995-11-15 1997-12-30 Kabushiki Kaisha Ohara Lithium ion conductive glass-ceramics
US6315881B1 (en) 1995-11-15 2001-11-13 Kabushiki Kaisha Ohara Electric cells and gas sensors using alkali ion conductive glass ceramic
US7211532B2 (en) 1995-11-15 2007-05-01 Kabushiki Kaisha Ohara Alkali ion conductive glass-ceramics and electric cells and gas sensors using the same
US6306509B2 (en) 1996-03-21 2001-10-23 Showa Denko K.K. Ion conductive laminate and production method and use thereof
JPH09320645A (ja) 1996-06-01 1997-12-12 Kazuo Okada 連続使用が可能な電池
JP4083224B2 (ja) 1996-06-14 2008-04-30 サイオン パワー コーポレイション 2次電池セルの電解質に有用な組成物
JPH1092444A (ja) 1996-09-13 1998-04-10 Japan Gore Tex Inc 電気化学反応装置用固体高分子電解質複合体及びそれを用いた電気化学反応装置
CN1204636C (zh) 1996-10-21 2005-06-01 日本电池株式会社 电池电极及其制造方法
DE69719386T2 (de) 1996-10-28 2004-04-01 Kabushiki Kaisha Ohara, Sagamihara Lithium-Ionen leitende Glaskeramiken und damit hergestellte elektrische Zellen und Glassensoren
US5981097A (en) 1996-12-23 1999-11-09 E.I. Du Pont De Nemours And Company Multiple layer membranes for fuel cells employing direct feed fuels
US6080290A (en) 1997-01-03 2000-06-27 Stuart Energy Systems Corporation Mono-polar electrochemical system with a double electrode plate
US5882812A (en) 1997-01-14 1999-03-16 Polyplus Battery Company, Inc. Overcharge protection systems for rechargeable batteries
IL120557A (en) 1997-03-31 2000-07-16 Licht Stuart Zinc sulfur battery
JPH10302794A (ja) 1997-04-30 1998-11-13 Matsushita Electric Ind Co Ltd リチウム二次電池
KR100378004B1 (ko) * 1997-06-10 2003-06-09 삼성에스디아이 주식회사 유리-고분자복합전해질및그제조방법
US6096447A (en) 1997-11-05 2000-08-01 Wilson Greatbatch Ltd. Phosphonate additives for nonaqueous electrolyte in alkali metal electrochemical cells
US6068950A (en) 1997-11-19 2000-05-30 Wilson Greatbatch Ltd. Organic phosphate additives for nonaqueous electrolyte in alkali metal electrochemical cells
US6402795B1 (en) 1998-02-18 2002-06-11 Polyplus Battery Company, Inc. Plating metal negative electrodes under protective coatings
JP3949303B2 (ja) 1998-03-20 2007-07-25 三星エスディアイ株式会社 リチウム二次電池負極用炭素材及びこれを用いたリチウム二次電池
IL124007A (en) * 1998-04-08 2001-08-26 Univ Ramot Long cycle-life alkali metal battery
US6214061B1 (en) 1998-05-01 2001-04-10 Polyplus Battery Company, Inc. Method for forming encapsulated lithium electrodes having glass protective layers
JP2002518796A (ja) * 1998-06-08 2002-06-25 モルテック・コーポレーション 安全保護用多官能反応性モノマーを含む非水電気化学セル
JP4745472B2 (ja) 1998-07-16 2011-08-10 株式会社オハラ リチウムイオン伝導性ガラスセラミックスおよびこれを用いた電池、ガスセンサー
JP3257516B2 (ja) * 1998-07-23 2002-02-18 日本電気株式会社 積層型電解質及びそれを用いた電池
US6210832B1 (en) 1998-09-01 2001-04-03 Polyplus Battery Company, Inc. Mixed ionic electronic conductor coatings for redox electrodes
US6200704B1 (en) 1998-09-01 2001-03-13 Polyplus Battery Company, Inc. High capacity/high discharge rate rechargeable positive electrode
US6955866B2 (en) 1998-09-03 2005-10-18 Polyplus Battery Company Coated lithium electrodes
US6198701B1 (en) 1998-09-03 2001-03-06 Polyplus Battery Company, Inc. Electrochemical timer
US6537701B1 (en) 1998-09-03 2003-03-25 Polyplus Battery Company, Inc. Coated lithium electrodes
US6110236A (en) 1998-09-11 2000-08-29 Polyplus Battery Company, Inc. Method of preparing electrodes having evenly distributed component mixtures
CA2347033A1 (en) * 1998-10-16 2000-04-27 Ballard Power Systems Inc. Ionomer impregnation of electrode substrates for improved fuel cell performance
US6203942B1 (en) 1998-10-22 2001-03-20 Wilson Greatbatch Ltd. Phosphate additives for nonaqueous electrolyte rechargeable electrochemical cells
US6146787A (en) 1998-11-11 2000-11-14 Bechtel Bwxt Idaho, Llc Solid polymer battery electrolyte and reactive metal-water battery
US6194098B1 (en) 1998-12-17 2001-02-27 Moltech Corporation Protective coating for separators for electrochemical cells
US6200701B1 (en) 1999-01-25 2001-03-13 Wilson Greatbatch Ltd. Phosphonate additives for nonaqueous electrolyte in rechargeable cells
US6495285B2 (en) 1999-01-25 2002-12-17 Wilson Greatbatch Ltd. Phosphonate additives for nonaqueous electrolyte in rechargeable electrochemical cells
US6225002B1 (en) 1999-02-05 2001-05-01 Polyplus Battery Company, Inc. Dioxolane as a proctector for lithium electrodes
US6358651B1 (en) 1999-02-26 2002-03-19 Reveo, Inc. Solid gel membrane separator in rechargeable electrochemical cells
US6228527B1 (en) 1999-03-02 2001-05-08 The United States Of America As Represented By The Secretary Of The Navy Magnesium solution phase catholyte seawater electrochemical system
JP3643289B2 (ja) 1999-04-30 2005-04-27 株式会社オハラ ガラスセラミックス複合電解質、及びリチウム二次電池
US6489055B1 (en) 1999-06-25 2002-12-03 Sanyo Electric Co., Ltd. Lithium secondary battery
DE19940069A1 (de) 1999-08-24 2001-03-08 Basf Ag Verfahren zur elektrochemischen Herstellung eines Alkalimetalls aus wäßriger Lösung
US6413285B1 (en) 1999-11-01 2002-07-02 Polyplus Battery Company Layered arrangements of lithium electrodes
US6413284B1 (en) 1999-11-01 2002-07-02 Polyplus Battery Company Encapsulated lithium alloy electrodes having barrier layers
US6733924B1 (en) 1999-11-23 2004-05-11 Moltech Corporation Lithium anodes for electrochemical cells
US7771870B2 (en) 2006-03-22 2010-08-10 Sion Power Corporation Electrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US7247408B2 (en) 1999-11-23 2007-07-24 Sion Power Corporation Lithium anodes for electrochemical cells
CN100344014C (zh) * 1999-11-23 2007-10-17 赛昂能源有限公司 电化电池的锂负极
US6797428B1 (en) 1999-11-23 2004-09-28 Moltech Corporation Lithium anodes for electrochemical cells
US6210732B1 (en) * 2000-02-03 2001-04-03 James A. Papanton Cooking oil additive and method of using
US6296958B1 (en) 2000-03-08 2001-10-02 Metallic Power, Inc. Refuelable electrochemical power source capable of being maintained in a substantially constant full condition and method of using the same
US6391069B1 (en) 2000-03-29 2002-05-21 Valence Technology (Nevada), Inc. Method of making bonded-electrode rechargeable electrochemical cells
JP2001313025A (ja) * 2000-04-28 2001-11-09 Mitsubishi Electric Corp 電 池
JP4608735B2 (ja) 2000-05-16 2011-01-12 ソニー株式会社 非水電解質二次電池の充電方法
JP4626013B2 (ja) * 2000-06-08 2011-02-02 住友電気工業株式会社 リチウム二次電池負極
KR100366346B1 (ko) * 2000-06-16 2002-12-31 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 그의 제조 방법
KR100473433B1 (ko) 2000-07-17 2005-03-08 마쯔시다덴기산교 가부시키가이샤 비수전해액 및 그것을 포함하는 비수전해액전지 및 전해콘덴서
US6465529B1 (en) * 2000-08-01 2002-10-15 Exxonmobil Research And Engineering Company Process for increasing cobalt catalyst hydrogenation activity via aqueous low temperature oxidation
EP1178554A3 (en) 2000-08-03 2003-06-25 Seijirau Suda Liquid fuel cell
JP3988374B2 (ja) 2000-10-06 2007-10-10 ソニー株式会社 非水電解液二次電池
US20020068220A1 (en) 2000-12-05 2002-06-06 Wyler Mark D. Electrochemical cell and negative electrode therefor
WO2002050933A2 (en) 2000-12-21 2002-06-27 Moltech Corporation Lithium anodes for electrochemical cells
US6511772B2 (en) 2001-01-17 2003-01-28 Wilson Greatbatch Ltd. Electrochemical cell having an electrode with a phosphate additive in the electrode active mixture
US6632573B1 (en) 2001-02-20 2003-10-14 Polyplus Battery Company Electrolytes with strong oxidizing additives for lithium/sulfur batteries
US6537698B2 (en) 2001-03-21 2003-03-25 Wilson Greatbatch Ltd. Electrochemical cell having an electrode with a phosphonate additive in the electrode active mixture
JP2002289266A (ja) * 2001-03-28 2002-10-04 Hitachi Maxell Ltd 空気極およびそれを正極として用いた空気電池
JP2002343437A (ja) * 2001-05-22 2002-11-29 Japan Storage Battery Co Ltd 非水電解質電池
CN1179432C (zh) 2001-05-31 2004-12-08 三星Sdi株式会社 锂电池的锂金属阳级保护层的形成方法
US7070632B1 (en) 2001-07-25 2006-07-04 Polyplus Battery Company Electrochemical device separator structures with barrier layer on non-swelling membrane
US6766817B2 (en) 2001-07-25 2004-07-27 Tubarc Technologies, Llc Fluid conduction utilizing a reversible unsaturated siphon with tubarc porosity action
US6991662B2 (en) 2001-09-10 2006-01-31 Polyplus Battery Company Encapsulated alloy electrodes
GB0123597D0 (en) * 2001-10-02 2001-11-21 Univ Belfast Friedal-crafts reactions
US20030082445A1 (en) 2001-10-25 2003-05-01 Smith W. Novis Battery pouch
KR100477744B1 (ko) 2001-10-31 2005-03-18 삼성에스디아이 주식회사 유기 전해액 및 이를 채용한 리튬 2차전지
JP4288400B2 (ja) * 2001-11-15 2009-07-01 日本電気株式会社 二次電池用電解液の製造方法および二次電池用電解液、二次電池の製造方法および二次電池
US6911280B1 (en) 2001-12-21 2005-06-28 Polyplus Battery Company Chemical protection of a lithium surface
GB2386126B (en) 2002-03-06 2006-03-08 Ceres Power Ltd Forming an impermeable sintered ceramic electrolyte layer on a metallic foil substrate for solid oxide fuel cell
CA2424725A1 (en) 2002-04-08 2003-10-08 David D. Rendina Renewable, energetic, nanodimensional dispersion
JP2003346862A (ja) * 2002-05-29 2003-12-05 Hitachi Maxell Ltd 燃料電池
ATE445234T1 (de) 2002-06-25 2009-10-15 Applied Intellectual Capital L Zink-luft-batterie mit säureelektrolyt
US7282302B2 (en) 2002-10-15 2007-10-16 Polyplus Battery Company Ionically conductive composites for protection of active metal anodes
BR0315274B1 (pt) 2002-10-15 2012-04-03 componente de dispositivo eletroquìmico, separador de bateria de compósito protetor, método para fabricar um componente de dispositivo eletroquìmico, célula de bateria, e, método para produzir a mesma.
US7645543B2 (en) 2002-10-15 2010-01-12 Polyplus Battery Company Active metal/aqueous electrochemical cells and systems
US20080057386A1 (en) 2002-10-15 2008-03-06 Polyplus Battery Company Ionically conductive membranes for protection of active metal anodes and battery cells
US7390591B2 (en) 2002-10-15 2008-06-24 Polyplus Battery Company Ionically conductive membranes for protection of active metal anodes and battery cells
KR100682883B1 (ko) 2002-11-27 2007-02-15 삼성전자주식회사 고체 전해질, 그의 제조방법 및 이를 채용한 리튬전지 및 박막전지
KR100590376B1 (ko) 2003-03-20 2006-06-19 마쯔시다덴기산교 가부시키가이샤 집합전지
US7070876B2 (en) 2003-03-24 2006-07-04 Ballard Power Systems, Inc. Membrane electrode assembly with integrated seal
US7211351B2 (en) 2003-10-16 2007-05-01 Cymbet Corporation Lithium/air batteries with LiPON as separator and protective barrier and method
US7608178B2 (en) * 2003-11-10 2009-10-27 Polyplus Battery Company Active metal electrolyzer
US7491458B2 (en) 2003-11-10 2009-02-17 Polyplus Battery Company Active metal fuel cells
US7282295B2 (en) 2004-02-06 2007-10-16 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US9368775B2 (en) 2004-02-06 2016-06-14 Polyplus Battery Company Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers
US7691536B2 (en) 2004-02-20 2010-04-06 Excellatron Solid State, Llc Lithium oxygen batteries and method of producing same
EP3322000A1 (en) * 2004-09-02 2018-05-16 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
US20060063051A1 (en) 2004-09-20 2006-03-23 Jang Bor Z Metal-air battery with ion-conducting inorganic glass electrolyte
US7947405B2 (en) 2004-09-29 2011-05-24 Giner Electrochemical Systems, Llc Solid polymer electrolyte composite membrane comprising porous ceramic support
US20060078790A1 (en) * 2004-10-05 2006-04-13 Polyplus Battery Company Solid electrolytes based on lithium hafnium phosphate for active metal anode protection
US7595019B2 (en) 2005-03-01 2009-09-29 Air Products And Chemicals, Inc. Method of making an ion transport membrane oxygen separation device
US8404388B2 (en) 2005-08-09 2013-03-26 Polyplus Battery Company Compliant seal structures for protected active metal anodes
US8129052B2 (en) 2005-09-02 2012-03-06 Polyplus Battery Company Polymer adhesive seals for protected anode architectures
US8048570B2 (en) 2005-08-09 2011-11-01 Polyplus Battery Company Compliant seal structures for protected active metal anodes
MX2008002074A (es) 2005-08-09 2008-04-22 Polyplus Battery Co Inc Estructuras de sello flexible para anodos de metal activo protegidos.
US9580320B2 (en) 2005-10-13 2017-02-28 Ohara Inc. Lithium ion conductive solid electrolyte and method for manufacturing the same
US7771880B2 (en) 2005-11-21 2010-08-10 University Of Dayton Solid composite electrolyte membrane and method of making
WO2007062220A2 (en) 2005-11-23 2007-05-31 Polyplus Battery Company Li/air non-aqueous batteries
WO2007075867A2 (en) 2005-12-19 2007-07-05 Polyplus Battery Company Composite solid electrolyte for protection of active metal anodes
US20070148533A1 (en) 2005-12-23 2007-06-28 Anglin David L Batteries
US20070231704A1 (en) 2006-03-30 2007-10-04 Ohara Inc. Lithium ion conductive solid electrolyte and production process thereof
US20070259234A1 (en) 2006-05-06 2007-11-08 David Chua Metal-air semi-fuel cell with an aqueous acid based cathode
EP1892780A3 (en) 2006-08-23 2010-11-10 Rovcal, Inc. Copper-manganese mixed oxide cathode material for use in alkaline cells having high capacity
US20080124433A1 (en) * 2006-11-27 2008-05-29 Synrad, Inc. Food processing using laser radiation
DE102007030604A1 (de) 2007-07-02 2009-01-08 Weppner, Werner, Prof. Dr. Ionenleiter mit Granatstruktur
JP5319943B2 (ja) 2008-03-19 2013-10-16 株式会社オハラ 電池
MX2010013888A (es) 2008-06-16 2011-05-03 Polyplus Battery Co Inc Celdas para baterias del litio/aire acuosas.
JP5502452B2 (ja) 2008-12-24 2014-05-28 日本ゴア株式会社 複合シートおよびその製造方法
US8986895B2 (en) 2009-02-04 2015-03-24 Kabushiki Kaisha Toyota Chuo Kenkyusho Garnet-type lithium ion-conducting oxide and all-solid-state lithium ion secondary battery containing the same
US20100203394A1 (en) 2009-02-06 2010-08-12 In Tae Bae Thin metal-air batteries
WO2010101794A1 (en) 2009-03-06 2010-09-10 Seeo, Inc High ionic conductivity electrolytes from block copolymers of grafted poly(siloxanes-co-ethylene oxide)
US8501351B2 (en) 2009-05-18 2013-08-06 Powergenix Systems, Inc. Pasted zinc electrode for rechargeable nickel-zinc batteries
JP5525388B2 (ja) 2009-09-03 2014-06-18 日本碍子株式会社 セラミックス材料及びその製造方法
US20110269007A1 (en) 2010-04-30 2011-11-03 Polyplus Battery Company High rate seawater activated lithium battery cells bi-polar protected electrodes and multi-cell stacks
CN103003356B (zh) 2010-05-19 2015-03-04 西奥公司 基于pxe的聚合物组合物
CN103493278B (zh) 2012-04-14 2018-01-26 西奥公司 小域大小多嵌段共聚物电解质

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN102655249B (zh) * 2011-03-03 2016-04-13 现代自动车株式会社 锂离子空气电池
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CN104054209A (zh) * 2011-11-15 2014-09-17 高级聚合电池公司 水性电解质锂硫电池
US9660265B2 (en) 2011-11-15 2017-05-23 Polyplus Battery Company Lithium sulfur batteries and electrolytes and sulfur cathodes thereof
CN103367798A (zh) * 2012-04-02 2013-10-23 三星精密化学株式会社 用于锂离子二次电池的电解质和锂离子二次电池
CN103367798B (zh) * 2012-04-02 2016-02-03 三星Sdi株式会社 用于锂离子二次电池的电解质和锂离子二次电池
US9029023B2 (en) 2012-04-02 2015-05-12 Samsung Fine Chemicals Co., Ltd Multi-layered structure electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same
US9812706B2 (en) 2012-12-28 2017-11-07 Industrial Technology Research Institute Protected active metal electrode and device with the electrode
TWI481102B (zh) * 2012-12-28 2015-04-11 Ind Tech Res Inst 受保護的活性金屬電極及具有此電極的元件
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