CN105703005A - 电解质和负极结构 - Google Patents

电解质和负极结构 Download PDF

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CN105703005A
CN105703005A CN201510910062.0A CN201510910062A CN105703005A CN 105703005 A CN105703005 A CN 105703005A CN 201510910062 A CN201510910062 A CN 201510910062A CN 105703005 A CN105703005 A CN 105703005A
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lithium
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F.刘
Q.肖
Y.卢
M.蔡
F.戴
L.杨
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GM Global Technology Operations LLC
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Abstract

本发明公开了电解质和负极结构。示例性电解质包含溶剂、锂盐和添加剂,所述添加剂选自巯基硅烷、巯基硅氧烷、及其组合。该电解质可以用于在电极表面上制造固体电解质界面(SEI)层的方法中。由所述方法可以形成负极结构。

Description

电解质和负极结构
相关申请的交叉引用
本申请要求于2014年12月10日提交的美国临时专利申请系列号62/090,181的权益,其经此引用以其全文并入本文。
技术领域
本发明涉及电解质和负极结构。具体而言,本发明涉及锂基电池的电解质、用于在电极表面上制造固体电解质界面(SEI)层的方法和由所述方法形成的负极结构。
背景技术
二次或可再充电的锂离子电池或锂硫电池通常用于许多固定和便携设备,例如在消费电子产品、汽车和航空航天工业中遇到的那些。由于多种原因,包括相对高的能量密度、与其它类型的可再充电电池相比时通常不出现任何记忆效应、相对低的内电阻以及不使用时的低自放电率,锂类电池已经得以普及。锂电池在其整个有效寿命中进行反复的功率循环的能力使其成为有吸引力和可靠的电源。
发明内容
示例性电解质包含溶剂、锂盐和添加剂,所述添加剂选自巯基硅烷、巯基硅氧烷、及其组合。该电解质可以用于在电极表面上制造固体电解质界面(SEI)层的方法中。由所述方法可以形成负极结构。
因此,本发明公开了以下技术方案:
方案1.电解质,其包含:
溶剂;
锂盐;和
添加剂,其选自巯基硅烷、巯基硅氧烷、及其组合。
方案2.如方案1所限定的电解质,其中所述巯基硅烷选自(3-巯基丙基)三甲氧基硅烷、(巯基甲基)甲基二乙氧基硅烷、(3-巯基丙基)甲基二甲氧基硅烷、(3-巯基丙基)三乙氧基硅烷、(11-巯基十一烷氧基)三甲基硅烷、及其组合。
方案3.如方案1所限定的电解质,其中所述巯基硅氧烷选自[4%至6%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、[13%至17%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、(巯基丙基)甲基硅氧烷均聚物、及其组合。
方案4.如方案1所限定的电解质,其中:
所述溶剂选自1,3-二氧戊环、二甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、四乙二醇二甲醚(TEGDME)、聚乙二醇二甲醚(PEGDME)、及其混合物;并且
所述锂盐选自双(三氟甲基磺酰)亚胺锂(LiN(CF3SO2)2或LiTFSI)、LiNO3、LiPF6、LiBF4、LiI、LiBr、LiSCN、LiClO4、LiAlCl4、LiB(C2O4)2(LiBOB)、LiB(C6H5)4、LiBF2(C2O4)(LiODFB)、LiN(SO2F)2(LiFSI)、LiPF3(C2F5)3(LiFAP)、LiPF4(CF3)2、LiPF4(C2O4)(LiFOP)、LiPF3(CF3)3、LiSO3CF3、LiAsF6、及其组合。
方案5.如方案1所限定的电解质,其中:
所述溶剂选自碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯、碳酸氟代亚乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、甲酸甲酯、乙酸甲酯、丙酸甲酯、γ-丁内酯、γ-戊内酯、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、及其组合;并且
所述锂盐选自双(三氟甲基磺酰)亚胺锂(LiN(CF3SO2)2或LiTFSI)、LiNO3、LiPF6、LiBF4、LiI、LiBr、LiSCN、LiClO4、LiAlCl4、LiB(C2O4)2(LiBOB)、LiB(C6H5)4、LiBF2(C2O4)(LiODFB)、LiN(SO2F)2(LiFSI)、LiPF3(C2F5)3(LiFAP)、LiPF4(CF3)2、LiPF4(C2O4)(LiFOP)、LiPF3(CF3)3、LiSO3CF3、LiAsF6、及其组合。
方案6.如方案1所限定的电解质,其中所述添加剂以电解质总重量%的约1重量%至约10重量%的量存在。
方案7.负极结构,其包含:
包含活性材料的负极;和
在所述负极的表面上形成的固体电解质界面(SEI)层,所述SEI层由巯基硅烷、巯基硅氧烷、及其组合形成。
方案8.如方案7所限定的负极结构,其中所述巯基硅烷选自(3-巯基丙基)三甲氧基硅烷、(巯基甲基)甲基二乙氧基硅烷、(3-巯基丙基)甲基二甲氧基硅烷、(3-巯基丙基)三乙氧基硅烷、(11-巯基十一烷氧基)三甲基硅烷、及其组合。
方案9.如方案7所限定的负极结构,其中所述巯基硅氧烷选自[4%至6%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、[13%至17%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、(巯基丙基)甲基硅氧烷均聚物、及其组合。
方案10.如方案7所限定的负极结构,其中所述活性材料选自石墨、硅基材料和锂基材料。
方案11.在电极表面上制造固体电解质界面(SEI)层的方法,所述方法包括:
使所述电极暴露于电解质,所述电解质包含:
溶剂;
锂盐;和
添加剂,其选自巯基硅烷、巯基硅氧烷、及其组合。
方案12.如方案11所限定的方法,其中在电化学电池中使所述电极暴露于电解质,并且其中所述方法还包括对所述电化学电池施加电压。
附图说明
本公开的实例的特性将通过参照下面的具体实施方式和附图而变得明显,其中同样的附图标记对应相似的(尽管可能并不相同的)组件。为了简洁起见,具有在之前已描述的功能的附图标记或特性可能连同或不连同它们出现于其中的其它附图一起描述。
图1是在LiOH存在时在负极上形成的固体电解质界面(SEI)层的示意性图解;
图2A至2C是图解包含对比例电解质和本文公开的电解质实施例的锂-锂对称电池的电压对时间(T,以小时计)的图;
图3是图解用(3-巯基丙基)三甲氧基硅烷涂布的铜工作电极的库伦效率(%)的图;以及
图4是图解在电解质中含有聚(巯基丙基)甲基硅氧烷的铜工作电极的库伦效率(%)的图。
具体实施方式
锂基电池通常通过在负极(有时称阳极)和正极(有时称阴极)之间可逆地传递锂离子来运行。负极和正极位于用适于传导锂离子的电解质溶液浸泡的多孔聚合物隔膜的相对两侧。在充电过程中,锂离子嵌入/插入到负极中,并且在放电过程中,锂离子从负极中抽出。各个电极还与各自的集流体相关联,所述集流体通过能使电流在负极与正极之间传递的可断开的外电路连接。锂基电池的实例包括锂硫电池(即包含硫基正极)、锂离子电池(即包含锂基正极)和锂-锂电池(即包含锂基正极和负极)。
本文公开的负极的实例具有在其表面上形成的固体电解质界面(SEI)层。该SEI层由存在于电解质溶液中的添加剂形成。由于添加剂存在于电解质溶液中,SEI层可以在电化学电池中原位形成。如在本文中所使用的,电化学电池可以指锂硫电池、锂离子电池或半电池,或者具有工作电极和对电极/参比电极的Li-Li对称电池(即锂-锂电池)。在本文中称为非原位技术的其它技术也可以用于形成SEI层。由于它们在电化学电池外进行,这些技术被认为是非原位的。
本文公开的添加剂与负极材料(例如锂、硅和石墨)具有强相互作用。据信,一种或多种添加剂与电极之间的化学反应甚至可以在没有施加电压的情况下发生。
添加剂的实例包括巯基硅烷、巯基硅氧烷、及其组合。巯基硅烷的一些具体的实例包括(3-巯基丙基)三甲氧基硅烷(3-MPS)、(巯基甲基)甲基二乙氧基硅烷、(3-巯基丙基)甲基二甲氧基硅烷、(3-巯基丙基)三乙氧基硅烷、(11-巯基十一烷氧基)三甲基硅烷、及其组合。巯基硅氧烷的一些具体的实例包括[4%至6%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、[13%至17%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、(巯基丙基)甲基硅氧烷均聚物、及其组合。
在电解质中包含一种或多种添加剂。可以以任何合适的量包含添加剂。作为一个实例,可以以电解质总重量%的约1重量%至约10重量%的量包含添加剂。
电解质还包含溶剂和锂盐。电解质溶剂的选择可以取决于是否要原位形成SEI层,并且如果要使其原位形成,则将使用电化学电池的类型。当要在锂硫电池或Li-Li对称电池中原位形成SEI层时,电解质溶剂可以选自1,3-二氧戊环(DOL)、二甲氧基乙烷(DME)、四氢呋喃、2-甲基四氢呋喃、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、四乙二醇二甲醚(TEGDME)、聚乙二醇二甲醚(PEGDME)和其混合物。当要在锂离子电池或Li-Li对称电池中原位形成SEI层时,电解质溶剂可以选自环状碳酸酯(碳酸亚乙酯(EC)、碳酸亚丙酯、碳酸亚丁酯、碳酸氟代亚乙酯)、直链碳酸酯(碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC))、脂族羧酸酯(甲酸甲酯、乙酸甲酯、丙酸甲酯)、γ-内酯(γ-丁内酯、γ-戊内酯)、链结构醚(1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷)、环状醚(四氢呋喃、2-甲基四氢呋喃)和其混合物。当要非原位形成SEI层时,可以使用任何前述的电解质溶剂。
锂盐的实例包括LiClO4、LiAlCl4、LiI、LiBr、LiSCN、LiBF4、LiB(C6H5)4、LiAsF6、LiN(FSO2)2(LIFSI)、LiN(CF3SO2)2(LITFSI或双(三氟甲基磺酰)亚胺锂)、LiPF6、LiB(C2O4)2(LiBOB)、LiBF2(C2O4)(LiODFB)、LiPF3(C2F5)3(LiFAP)、LiPF4(CF3)2、LiPF4(C2O4)(LiFOP)、LiPF3(CF3)3、LiSO3CF3、LiNO3和其混合物。在一个实例中,在电解质中盐的浓度为约1mol/L。
在其上形成SEI的电极通常在任意的锂硫电池、锂离子电池或Li-Li对称电池中用作负极。负极可以包含活性材料、粘合剂材料和导电填料,或者可以仅包含锂金属(例如,在Li-Li对称电池中)。
合适的活性材料的实例包括任何锂宿体活性材料,所述锂宿体活性材料在铜或其它集流体充当电化学电池的负极端子时能够充分进行锂的插入和脱插、或锂的合金化和去合金化、或锂的嵌入和脱嵌。锂宿体活性材料的实例包括石墨、硅基材料或锂基材料。石墨表现出有利的锂插入和脱插特性,其是相对非反应性的,并且能够以产生相对高的能量密度的量储存锂。可以用于制造负极的石墨的市售形式可以购自,例如TimcalGraphite&Carbon(Bodio,瑞士)、LonzaGroup(Basel,瑞士)或SuperiorGraphite(Chicago,IL)。硅基活性材料的实例包括晶态硅、无定形硅、二氧化硅、低价硅氧化物(SiOx,0<x<2)、硅合金(例如Si-Sn)等。这些硅活性材料可以是纳米尺寸至微米尺寸的粉末、粒子等形式。锂基材料的实例包括锂箔或钛酸锂。当使用锂箔时,可以不使用聚合物粘合剂或导电填料。
粘合剂材料可以用来在结构上使活性材料固定在一起。粘合剂材料的实例包括聚偏二氟乙烯(PVdF)、聚环氧乙烷(PEO)、三元乙丙(EPDM)橡胶、羧甲基纤维素(CMC)、丁苯橡胶(SBR)、丁苯橡胶-羧甲基纤维素(SBR-CMC)、聚丙烯酸(PAA)、交联的聚丙烯酸-聚乙烯亚胺、聚酰亚胺或任何其它合适的粘合剂材料。还有其它合适的粘合剂的实例包括聚乙烯醇(PVA)、海藻酸钠、或其它水溶性粘合剂。
导电填料材料可以是导电碳材料。导电碳材料可以是高表面积碳,例如乙炔黑。包含导电填料材料以确保电池中活性材料与负极侧集流体之间的电子传导。
负极可以包含总重量的最多90%(即90重量%)的活性材料。在一个实例中,负极包含约70重量%至约90重量%的活性材料、约5重量%至约15重量%的导电填料材料和约5重量%至约15重量%的粘合剂材料。如上所述,当使用锂箔时,负极包含100%的活性材料。
为了非原位地在负极上形成SEI层,可以制备本文公开的任何电解质的实例,可以购买或制备负极,并且接下来可以使负极暴露于电解质。当非原位地在负极上形成SEI层时,要理解的是,可以将锂盐排除在电解质外。使负极暴露于电解质可以通过浸涂或某些其它合适的涂布技术来完成。巯基硅烷和/或巯基硅氧烷的巯基官能团强烈地与负极相互作用(甚至不需要施加电压)以在其表面上形成SEI层。在这些实例中,可以使负极暴露于电解质以至足够使添加剂与负极表面之间发生化学反应的时间。作为一个实例,暴露时间可以为约2分钟至约24小时。
在图1中显示了经由非原位技术形成的负极结构10的一个实例。在图1的左侧显示了包括负极14和形成于其上的SEI层12的负极结构10。
可以使经由非原位技术形成并包含非锂活性材料(例如石墨或硅基材料)的负极结构10的实例暴露于预锂化技术从而锂化负极结构10并形成负极结构10'。在这些实例中,负极结构10可以用半电池预锂化。更具体地,用浸泡在用于形成SEI层12的相同电解质中的负极结构10来组装半电池。该半电池包含对电极(例如锂),并且对所述半电池施加电压电位。施加电压造成锂金属渗入负极结构10。更具体地,锂离子自锂金属溶出(或去镀)并通过与电解质溶液(其能传导锂离子)的电铸反应与石墨或硅基活性材料合金化。锂离子可以与活性材料合金化,由此锂化负极结构10。在预锂化过程中,电解质的分解产物(例如,如图1所示的LiOH)可以引起SEI层12的硅和氧原子结合在一起以形成另一形态的SEI层12'和另一形态的负极结构10'。
在预锂化完成后,拆卸该半电池并且可以用合适的溶剂(例如DME)洗涤预锂化的负极结构10'。预锂化的负极结构10'可以与负极侧集流体结合并用于本文公开的任何电化学电池/电池组的实例中。要理解的是,由于已经形成SEI层,本文公开的电化学电池/电池组的实例中使用的电解质可以包含或不包含添加剂。在这些实例中,所使用的电解质将取决于电化学电池/电池组的类型。
要理解的是,当使用锂作为活性材料时,可以不用预锂化负极结构10。
为了原位地(即在电化学电池中)在负极上形成SEI层,可以用负极、合适的正极、位于负极与正极之间的多孔聚合物隔膜和包含适于具体电池类型的溶剂的电解质的实例来组装电池。
对于锂硫电池/电化学电池,可以使用任何负极的实例(例如含锂基、硅基或石墨活性材料的电极14)。
锂硫电池的正极包含任何能够与充当锂硫电化学电池正极端子的铝或另一合适的集流体充分进行锂的合金化和去合金化的硫基活性材料。硫基活性材料的一个实例是硫-碳复合材料。在一个实例中,正极中S对C的重量比为1:9至8:1。锂硫电池中的正极可以包含任何前述粘合剂材料和导电填料。
多孔聚合物隔膜可以由例如聚烯烃形成。该聚烯烃可以是均聚物(由单一单体成分得到)或杂聚物(由多于一种单体成分得到),并且可以是直链或支链的。如果使用由两种单体成分得到的杂聚物,该聚烯烃可以呈现包括嵌段共聚物或无规共聚物的链排列的任意共聚物链排列。如果该聚烯烃是由多于两种单体成分得到的杂聚物,这也同样适用。作为实例,该聚烯烃可以是聚乙烯(PE)、聚丙烯(PP)、PE和PP的共混物、或者PE和/或PP的多层结构化多孔膜。市售的多孔隔膜16包括单层聚丙烯膜,例如来自Celgard,LLC(Charlotte,NC)的CELGARD2400和CELGARD2500。要理解的是,多孔隔膜可以是经涂布或经处理的,或者未涂布或未处理的。例如,多孔隔膜可以是经涂布的或未涂布的,或可以包括或不包括在其上的任何表面活性剂处理。
在另外的实例中,多孔隔膜可以由其它聚合物形成,该聚合物选自聚对苯二甲酸乙二醇酯(PET)、聚偏二氟乙烯(PVdF)、聚酰胺(Nylon)、聚氨酯、聚碳酸酯、聚酯、聚醚醚酮(PEEK)、聚醚砜(PES)、聚酰亚胺(PI)、聚酰胺-酰亚胺、聚醚、聚甲醛(例如缩醛(acetal))、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯(polyethylenenaphthenate)、聚丁烯、聚烯烃共聚物、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚苯乙烯共聚物、聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、聚硅氧烷聚合物(例如聚二甲基硅氧烷(PDMS))、聚苯并咪唑(PBI)、聚苯并噁唑(PBO)、聚亚苯基类(例如PARMAXTM(MississippiPolymerTechnologies,Inc.,BaySaintLouis,Mississippi))、聚亚芳基醚酮、聚全氟环丁烷、聚四氟乙烯(PTFE)、聚偏二氟乙烯共聚物和三元共聚物、聚偏二氯乙烯、聚氟乙烯、液晶聚合物(例如VECTRANTM(HoechstAG,德国)和ZENITE?(DuPont,Wilmington,DE))、聚芳酰胺、聚苯醚和/或其组合。据信,可用于多孔隔膜的液晶聚合物的另一实例是聚(对羟基苯甲酸)。在又一实例中,多孔隔膜可以选自聚烯烃(例如PE和/或PP)与一种或多种上文所列的其它聚合物的组合。
该多孔隔膜可以是单层或可以是由干法或湿法制造的多层(例如双层、三层等)层叠件。该多孔隔膜用作电绝缘体(防止发生短路)、机械载体和防止两个电极之间的物理接触的阻隔物。多孔隔膜还确保了锂离子穿过填充其孔隙的电解质溶液的通道。
负极、正极和多孔隔膜用本文公开的电解质浸泡,所述电解质包含添加剂、锂盐、和适于锂硫电池的溶剂。
锂硫电池/电化学电池还包括外电路和负载。向锂硫电化学电池施加负载闭合了外电路并连通负极和正极。闭合的外电路能够跨锂硫电化学电池施加工作电压。
当负极初始暴露于电解质时,添加剂可以开始反应以在负极表面上形成SEI层。还可以对电化学电池/电池组施加电压电位从而预锂化负极并促进SEI层的形成。在施加电压的过程中,锂金属渗入负极,并且电解质中的添加剂与负极表面反应以在其上形成SEI层(例如12或12')。
对于锂离子电池/电化学电池,可以使用任何负极的实例(例如含锂基、硅基或石墨活性材料的电极14)。
锂离子电池的正极包含能与充当锂离子电化学电池正极端子的铝或另一合适的集流体充分进行锂的嵌入和脱嵌的任何锂基活性物质。适于该正极的实例的一类常见的已知锂基活性材料包括层状锂过渡金属氧化物。例如,锂基活性材料可以是尖晶石锂锰氧化物(LiMn2O4)、锂钴氧化物(LiCoO2)、锰-镍氧化物尖晶石[Li(Mn1.5Ni0.5)O2]、或层状镍-锰-钴氧化物(具有通式xLi2MnO3·(1-x)LiMO2,其中M由任意比率的Ni、Mn和/或Co组成)。层状镍-锰-钴氧化物的具体的实例包括(xLi2MnO3·(1?x)Li(Ni1/3Mn1/3Co1/3)O2)。其它合适的锂基活性材料包括[Li(Ni1/3Mn1/3Co1/3)O2]、LiNiO2、Li2MSiO4(M由任意比率的Co、Fe和/或Mn组成)、Lix+yMn2-yO4(LMO,0<x<1并且0<y<0.1)或锂铁多阴离子氧化物,例如磷酸铁锂(LiFePO4)或氟磷酸铁锂(Li2FePO4F)。还可以使用其它另外的锂基活性材料,例如LiNi1- xCo1-yMx+yO2或LiMn1.5-xNi0.5-yMx+yO4(M由任意比率的Al、Ti、Cr和/或Mg组成)、稳定化的锂锰氧化物尖晶石(LixMn2-yMyO4,其中M由任意比率的Al、Ti、Cr和/或Mg组成)、锂镍钴铝氧化物(例如LiNi0.8Co0.15Al0.05O2或NCA)、铝稳定化的锂锰氧化物尖晶石(例如LixAl0.05Mn0.95O2)、锂钒氧化物(LiV2O5)、和任何其它高能镍-锰-钴材料(HE-NMC、NMC或LiNiMnCoO2)。“任意比率”是指任意元素可以以任意量存在。因此,在一些实例中,M可以是Al,含有或不含有Cr、Ti和/或Mg或者任何其它所列元素的组合。在另一实例中,可以在锂过渡金属基活性材料的任意实例的晶格中进行阴离子取代以稳定晶体结构。例如,可以用F原子取代任意O原子。
锂离子电化学电池/电池组中的正极可以包含任何前述的粘合剂材料和导电填料。
锂离子电化学电池/电池组还可以包含任何在先提供的多孔聚合物隔膜的实例。
负极、正极和多孔隔膜用本文公开的电解质浸泡,所述电解质包含添加剂、锂盐、和适于锂离子电池的溶剂。
锂离子电池/电化学电池还包括外电路和负载。向锂离子电化学电池施加负载闭合了外电路并连通负极和正极。闭合的外电路能够跨锂离子电化学电池施加工作电压。
当负极初始暴露于电解质时,添加剂可以开始反应以在负极表面上形成SEI层。还可以对电化学电池/电池组施加电压电位从而预锂化负极并促进SEI层的形成。在施加电压的过程中,锂金属渗入负极,并且电解质中的添加剂与负极表面反应以在其上形成SEI层(例如12或12')。
对于Li-Li对称电化学电池(即锂-锂电池),负极(或对电极)由锂金属形成。Li-Li对称电池的正极可以包括镀敷锂的铜工作电极(例如在铜上镀敷1mAhLi)。
锂-锂对称电化学电池还可以包含任何在先提供的多孔聚合物隔膜的实例。
负极、正极和多孔隔膜用本文公开的电解质浸泡,所述电解质包含添加剂、锂盐、和适于锂-锂对称电池的溶剂。
锂-锂对称电化学电池还包括外电路和负载。向锂-锂电化学电池施加负载闭合了外电路并连通负极和正极。闭合的外电路能够跨锂-锂对称电化学电池施加工作电压。
当负极初始暴露于电解质时,添加剂可以开始反应以在负极表面上形成SEI层。可以对负极施加电压(例如充电循环)以驱使电解质中的添加剂与负极之间发生反应。在施加电压之前和其过程中,锂金属渗入负极,并且电解质中的添加剂与高度反应性的锂金属负极表面反应以在其上形成SEI层(例如12或12')。
要理解的是,锂-锂对称电化学电池可以用作锂-锂电池。要理解的是,可以另外冲洗在锂-锂对称电化学电池中原位形成的负极结构(即具有在其上的SEI层的锂金属电极)并将其作为负极并入另一锂金属基电池中。
在本文公开的任何涉及原位形成SEI层的实例中,所施加的电压电位可以为约-2V至约3.0V。
本文公开的SEI层12、12'是保护性涂层,因为其保护负极14免于与电解质的附加反应。SEI层12、12'还表现出均匀性(在组成和厚度方面)以及对负极14的附着性。
为了进一步说明本公开,本文给出了实施例。要理解的是,为了说明性的目的而提供这些实施例,并且不解释为限定本公开的范围。
实施例1
用锂箔负极和正极制备锂对称电池。对比例电池包含对比例电解质,其包含在EC/DMC(1:1体积比)中的1MLiPF6。实施例电池包含本文公开的电解质的实例,其包含在EC/DMC(1:1体积比)中的1MLiPF6和5%的3-MPS。对比例电池和实施例电池的测试条件为:室温;电流密度=0.39mA/cm2;充电和放电1小时,重复1000小时;以及截止电压=-2V至2V。图2A至2C图解了对比例电池(标记为“1”)和实施例电池(标记为“2”)的电压(V,Y轴)对时间(T,X轴,以小时计)。其结果表明,当与对比例电池相比时,包含实施例电解质的实施例电池表现出稳定得多的随时间推移的性能。
实施例2
为了说明可以非原位地涂布电极,制备了包含在DOL/DME(1:1体积比)中的0.1%的3-MPS的实施例电解质。随后用浸涂法将铜电极浸入电解质中。使铜电极与3-MPS反应2小时。
3-MPS涂布的铜电极随后在包含锂对电极/参比电极的实施例电化学电池中用作工作电极。实施例电池中的电解质包含在DOL/DME(1:1体积比)中的0.5MLiTFSI和0.4MLiNO3
对比例电化学电池包含未涂布的铜工作电极和锂对电极/参比电极。对比例电池中的电解质包含在DOL/DME(1:1体积比)中的0.5MLiTFSI和0.4MLiNO3(不含任何3-MPS)。
对比例电池和实施例电池的测试条件为:室温;电流=200μA;面积=1.23cm2;电荷=1mAh;以及100%放电深度(DOD)。库伦效率结果以百分数示于图3中。在图3中,Y轴(标记为%)代表库伦效率(百分数)并且X轴(标记为“#”)代表循环次数。如图3中说明的,在整个循环过程中,具有本文公开的SEI层的实施例电池(标记为“3”)的库伦效率i)稍高于对比例电池(标记为“4”)的库伦效率并且ii)通过几次循环后性能优于对比例电池。
实施例3
用铜工作电极和锂对电极/参比电极配置实施例电化学电池。电解质包含在DOL/DME(1:1体积比)中的0.4MLiTFSI和0.6MLiNO3以及2%的聚(巯基丙基)甲基硅氧烷。
对比例电化学电池也包含铜工作电极和锂对电极/参比电极。对比例电池中的电解质包含在DOL/DME(1:1体积比)中的0.4MLiTFSI和0.6MLiNO3(不含任何聚(巯基丙基)甲基硅氧烷)。
对比例电池和实施例电池的测试条件为:室温;电流=200μA;面积=1.23cm2;电荷=1mAh;以及100%放电深度(DOD)。库伦效率结果以百分数示于图4中。在图4中,Y轴(标记为%)代表库伦效率(百分数)并且X轴(标记为“#”)代表循环次数。如图5中说明的,在整个循环过程中,在电解质中含巯基硅氧烷添加剂的实施例电池(标记为“5”)的库伦效率通常比对比例电池(标记为“6”)的库伦效率更高且更稳定。
要理解的是,本文提供的范围包括了所述范围和所述范围内的任意值或子范围。例如,1:9至8:1的范围应当被解释为不仅包括明确列出的1:9至8:1的界限,还包括个别的值,例如1:2、7:1等,以及子范围,例如约1:3至6:3(即2:1)等。此外,当使用“约”来描述一个值时,这表示涵盖了自所述值的少量偏差(最多+/-10%)。
在整个说明书中提到的“一个实例”、“另一个实例”、“实例”等,是指与该实例相关联描述的具体要素(例如特征、结构和/或特性)被包括在本文描述的至少一个实例中,并且可以存在或不存在于其它的实例中。另外,要理解的是,针对任何实例描述的要素可以以任何合适的方式结合到多个实例中,除非上下文中明确地另有规定。
在描述和要求保护本文中公开的实例时,单数形式“一个”、“一种”和“所述/该”包括复数对象,除非上下文中明确地另有规定。
尽管已经详细描述了多个实例,但要理解的是,可以对所公开的实例加以修改。因此,前文的描述应被视为是非限制性的。

Claims (10)

1.电解质,其包含:
溶剂;
锂盐;和
添加剂,其选自巯基硅烷、巯基硅氧烷、及其组合。
2.如权利要求1所限定的电解质,其中所述巯基硅烷选自(3-巯基丙基)三甲氧基硅烷、(巯基甲基)甲基二乙氧基硅烷、(3-巯基丙基)甲基二甲氧基硅烷、(3-巯基丙基)三乙氧基硅烷、(11-巯基十一烷氧基)三甲基硅烷、及其组合。
3.如权利要求1所限定的电解质,其中所述巯基硅氧烷选自[4%至6%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、[13%至17%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、(巯基丙基)甲基硅氧烷均聚物、及其组合。
4.如权利要求1所限定的电解质,其中:
所述溶剂选自1,3-二氧戊环、二甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、四乙二醇二甲醚(TEGDME)、聚乙二醇二甲醚(PEGDME)、及其混合物;并且
所述锂盐选自双(三氟甲基磺酰)亚胺锂(LiN(CF3SO2)2或LiTFSI)、LiNO3、LiPF6、LiBF4、LiI、LiBr、LiSCN、LiClO4、LiAlCl4、LiB(C2O4)2(LiBOB)、LiB(C6H5)4、LiBF2(C2O4)(LiODFB)、LiN(SO2F)2(LiFSI)、LiPF3(C2F5)3(LiFAP)、LiPF4(CF3)2、LiPF4(C2O4)(LiFOP)、LiPF3(CF3)3、LiSO3CF3、LiAsF6、及其组合。
5.如权利要求1所限定的电解质,其中:
所述溶剂选自碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯、碳酸氟代亚乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、甲酸甲酯、乙酸甲酯、丙酸甲酯、γ-丁内酯、γ-戊内酯、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、及其组合;并且
所述锂盐选自双(三氟甲基磺酰)亚胺锂(LiN(CF3SO2)2或LiTFSI)、LiNO3、LiPF6、LiBF4、LiI、LiBr、LiSCN、LiClO4、LiAlCl4、LiB(C2O4)2(LiBOB)、LiB(C6H5)4、LiBF2(C2O4)(LiODFB)、LiN(SO2F)2(LiFSI)、LiPF3(C2F5)3(LiFAP)、LiPF4(CF3)2、LiPF4(C2O4)(LiFOP)、LiPF3(CF3)3、LiSO3CF3、LiAsF6、及其组合。
6.如权利要求1所限定的电解质,其中所述添加剂以电解质总重量%的约1重量%至约10重量%的量存在。
7.负极结构,其包含:
包含活性材料的负极;和
在所述负极的表面上形成的固体电解质界面(SEI)层,所述SEI层由巯基硅烷、巯基硅氧烷、及其组合形成。
8.如权利要求7所限定的负极结构,其中所述巯基硅烷选自(3-巯基丙基)三甲氧基硅烷、(巯基甲基)甲基二乙氧基硅烷、(3-巯基丙基)甲基二甲氧基硅烷、(3-巯基丙基)三乙氧基硅烷、(11-巯基十一烷氧基)三甲基硅烷、及其组合。
9.如权利要求7所限定的负极结构,其中所述巯基硅氧烷选自[4%至6%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、[13%至17%(巯基丙基)甲基硅氧烷]-二甲基硅氧烷共聚物、(巯基丙基)甲基硅氧烷均聚物、及其组合。
10.如权利要求7所限定的负极结构,其中所述活性材料选自石墨、硅基材料和锂基材料。
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