CN104641503A - 具有过充电保护的1.5-3v锂电池 - Google Patents

具有过充电保护的1.5-3v锂电池 Download PDF

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CN104641503A
CN104641503A CN201380022100.8A CN201380022100A CN104641503A CN 104641503 A CN104641503 A CN 104641503A CN 201380022100 A CN201380022100 A CN 201380022100A CN 104641503 A CN104641503 A CN 104641503A
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rechargeable
electrolyte
lithium battery
lithium
aqueous lithium
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U·韦特尔曼
U·埃梅尔
I·切尔尼希
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Albemarle Germany GmbH
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Abstract

本发明涉及可再充电的非水性锂电池，其含有锂金属或锂合金作为活性阳极材料，含有相对Li/Li+具有1.5-3.4V之间范围内的氧化还原电势的活性阴极材料，和含有硫氰化锂(LiSCN)作为电解质组分。

Description

具有过充电保护的1.5-3V锂电池
锂离子电池(“LiB”)是目前单位能量密度最高的电池系统。它们由两种锂嵌入材料的组合构成，锂离子在不同的电势下可以可逆地嵌入和脱嵌。通常，阴极(正极物质)由锂金属氧化物组成，而阳极(负极活性物质)含有石墨材料。这时，阳极反应如下：
Li++e-+6C＜-＞LiC6
石墨材料的理论电容通过极限化学计量法由LiC6给出并等于372mAh/g。
已知电容较高的阳极材料，尤其是锂金属本身，在理论上具有3,860mAh/g的比电容。但是，不可以将锂金属阳极与“经典的”锂离子阴极材料(即，锂金属氧化物)结合使用，因为在这种情况下两个电极已经处于锂化状态。如果也要使用锂化的阳极材料，尤其是锂金属本身，则必须使用非锂化(或部分锂化)的阴极材料。这样的材料是例如：
当这些材料过充电时，可能出现不可逆的结构变化，这可能使阴极材料的作用能力受损或完全破坏。通常，锂嵌入电势不应超过约0.5-1.5V以上。此外，预防超过充电电势很重要，因为否则电解质组分，例如有机溶剂，在能量释放的情况下可能被氧化。锂离子电池中常用的碳酸酯尽管最高相对Li/Li+约4.4V是稳定的，然而它们不太适用于具有锂金属-或锂合金阳极的原电池。为了可以使用金属阳极，需要还原稳定的溶剂，一般是醚类。然而，这样的溶剂只最高到约3.6V(二甲氧基乙烷、二乙醚)是稳定的(K.Xu，Electrolytes：Overview inEncyclopedia of Electrochemical Power Sources，J.Garche(ed.)，Vol.5，p.51，Elsevier Amsterdam 2009)。
充电电势这样的限制可以用电子方法通过电池管理系统进行。后者成本相对过高，并在发生故障时可能带来危险的故障。
因而，希望固有的(化学的)保护系统来防止超过要求的充电终止电势。这样的系统通过所谓的氧化还原穿梭化合物提供。这样的化合物在超过确定的充电电势时被氧化。该氧化形式是稳定的，并可以通过迁移或扩散而向阳极移动，并在该处放电(还原)为起始形式。所还原的物质可以然后在阳极上再次被氧化，并如此反复。
对于上述阴极材料，至今还没有描述过可逆的氧化还原穿梭化合物。
本发明的目的是提供一种可再充电的、非水性锂电池，其含有可逆的氧化还原穿梭化合物，和在无锂阴极材料充电电势以上约0.5-1.5V和在醚类溶剂分解开始(约3.6V)以下可逆地被氧化。
按照本发明，该目的通过可再充电的、非水性锂电池实现，该锂电池在充电状态下含有锂金属或锂合金作为活性阳极材料，含有相对Li/Li+具有1.5-3.4V范围内的氧化还原电势的活性阴极材料，并含有硫氰化锂(LiSCN)作为电解质组分。
优选含有粉末状锂金属或粉末状锂合金作为活性阳极材料。由粉末状颗粒制造的阳极可以通过挤压、辊压等机械地紧密化，或通过烧结而密实，以便获得宏观类似金属片的结构。但是紧密化的粉末阳极的特征在于复合材料结构，即，粉末状初级颗粒的相界可以通过高分辨率成像方法(例如扫描电子显微法)看出。应用粉末状或由粉末衍生的阳极层与均匀的金属片阳极相比具有单位(即按面积计算)的电流负载缩小的优点，以便减少树枝状生长(例如，见S.W.Kim，Metals and Materials(金属与材料)，6(2000)，345-349)。
作为锂合金使用二元的锂-第二金属-化合物，其中该第二金属优选选自Si、Sn、Al、Sb。
阴极材料选自CFX、过渡金属氧化物、过渡金属硫化物、过渡金属氟化物、过渡金属氟氧化物、有机氧化还原活性化合物以及硫和/或硒。
阴极材料优选选自CFX、MnO2、V2O5、V6O13、FeOF、FeF3、FeF2、S。
在该可再充电的、非水性锂电池中电解质在室温下处于液态、凝胶状或固态。该可再充电的、非水性锂电池优选含有质子惰性的有机溶剂作为电解质，该有机溶剂选自非环状或环状的醚、聚醚、腈、内酯、碳酸酯和/或离子液体。
该电解质优选含有至少一种质子惰性的有机溶剂，该有机溶剂选自四氢吡喃、四氢呋喃、1，2-二甲氧基乙烷、二乙二醇二甲基醚、乙腈、已二腈、丙二腈(Malodinitril)、戊二腈、γ-丁内酯和咪唑鎓盐。
该可再充电的、非水性锂电池的电解质优选可以含有LiSCN和至少另一种导电盐。
其它导电盐优选选自LiPF6、氟烷基磷酸锂、LiBF4、亚氨基盐、LiOSO2CF3、甲基化物盐、LiCIO4、螯合硼酸锂、氟代螯合硼酸锂、螯合磷酸锂、氟代螯合磷酸锂和/或卤化锂。
可再充电的、非水性锂电池的电解质可以含有如下的有机聚合物：聚氧化乙烯、聚丙烯腈、聚偏氟乙烯或其任意混合物。
在该可再充电的、非水性锂电池中LiSCN在电解质中的浓度为0.01至15重量％。
优选电解质中LiSCN的浓度为1至10重量％。
本发明还涉及可再充电的、非水性锂电池中应用的电解质，其中含有硫氰化锂作为电解质组分。
优选电解质中LiSCN的浓度为0.01至15重量％。
本发明尤其涉及LiSCN作为氧化还原穿梭化合物在可再充电的、非水性锂电池的电解质中的应用。
已经发现，LiSCN在对Li/Li+的电势超过约3.4V时被氧化，并在相邻的还原性分支(Ast)中被还原。该反应令人意外地是可逆的：在图1中示出三个周期来表明这一点。LiSCN的特殊的优点在于，它本身是一种容易离解的锂盐，并因而本身可以作为锂电解质使用。因而，原则上除了LiSCN以外不需要使用具有导电盐功能的其它锂盐。
该电解质可以以液态、凝胶状或固态存在。除了硫氰化锂以外可以以任何混合物的形式含有质子惰性的有机溶剂，例如碳酸酯(碳酸二甲酯、碳酸二乙酯、碳酸乙基甲基酯、碳酸亚丙酯、碳酸亚乙酯)，非环状或环状的醚(二丁基醚、四氢吡喃或四氢呋喃)，聚醚(1，2-二甲氧基乙烷或二乙二醇二甲基醚)，还有腈(乙腈、已二腈、丙二腈、戊二腈)以及内酯(γ-丁内酯)，离子液体(例如咪唑鎓盐)，其它锂盐(例如LiPF6、氟烷基磷酸锂、LiBF4、亚氨基盐(例如LiN(SO2CF3)2)、LiOSO2CF3、甲基化物盐(例如LiC(SO2CF3)3)、LiCIO4、螯合硼酸锂(例如LiBOB)、氟代螯合硼酸锂(例如LiC2O4BF2)、螯合磷酸锂(例如LiTOP)和氟代螯合磷酸锂(例如Li(C2O4)2PF2)、卤化锂(LiCI、LiBr、Lil))，添加剂(例如碳酸亚乙烯酯)和/或极性聚合物(例如聚氧化乙烯、聚丙烯腈、聚偏氟乙烯)。
LiSCN在电解质中的浓度为0.01至15％，特别优选1至10％。
图1表示具有在1MLiPF6/EC：DMC(1∶1重量)中的0.1M LiSCN的电解质和Pt-电极的循环伏安图，其中操作时的推进速度：100mV/s，扫描范围：相对Li/Li+3.0-4.0V。

Claims (15)

1.可再充电的、非水性锂电池，其特征在于，其含有锂金属或锂合金作为活性阳极材料，含有相对Li/Li+具有1.5-3.4V之间范围内的氧化还原电势的活性阴极材料，和含有硫氰化锂(LiSCN)作为电解质组分。
2.按照权利要求1所述的可再充电的、非水性锂电池，其特征在于，含有粉末状锂金属或粉末状锂合金作为活性阳极材料，其可以以紧密化的形式存在。
3.按照权利要求1或2所述的可再充电的、非水性锂电池，其特征在于，所述阴极材料选自CFX、过渡金属氧化物、过渡金属硫化物、过渡金属氟化物、过渡金属氟氧化物、有机氧化还原活性化合物以及硫和/或硒。
4.按照权利要求3所述的可再充电的、非水性锂电池，其特征在于，所述阴极材料选自CFX、MnO2、V2O5、V6O13、FeOF、FeF3、FeF2、S。
5.按照权利要求1-4中任一项或多项所述的可再充电的、非水性锂电池，其特征在于，所述电解质在室温下以液态、凝胶状或固态存在。
6.按照权利要求5所述的可再充电的、非水性锂电池，其特征在于，所述电解质含有质子惰性的有机溶剂，该有机溶剂选自非环状或环状的醚、聚醚、腈、内酯、碳酸酯和/或离子液体。
7.按照权利要求6所述的可再充电的、非水性锂电池，其特征在于，所述电解质含有至少一种质子惰性的有机溶剂，该有机溶剂选自四氢吡喃、四氢呋喃、1，2-二甲氧基乙烷、二乙二醇二甲基醚、乙腈、己二腈、丙二腈、戊二腈、γ-丁内酯和咪唑鎓盐。
8.按照权利要求1-7中任一项或多项所述的可再充电的、非水性锂电池，其特征在于，所述电解质含有LiSCN和至少另一种导电盐。
9.按照权利要求1-8中任一项或多项所述的可再充电的、非水性锂电池，其特征在于，所述其它导电盐选自LiPF6、氟烷基磷酸锂、LiBF4、亚氨基盐、LiOSO2CF3、甲基化物盐、LiCIO4、螯合硼酸锂、氟代螯合硼酸锂、螯合磷酸锂、氟代螯合磷酸锂和/或卤化锂。
10.按照权利要求1-9中任一项或多项所述的可再充电的、非水性锂电池，其特征在于，所述电解质含有选自聚氧化乙烯、聚丙烯腈、聚偏氟乙烯或其任意混合物的有机聚合物。
11.按照权利要求1-10中任一项或多项所述的可再充电的、非水性锂电池，其特征在于，电解质中LiSCN的浓度为0.01-15重量％。
12.按照权利要求11所述的可再充电的、非水性锂电池，其特征在于，电解质中LiSCN的浓度为1-10重量％。
13.应用在按照权利要求1-11中任一项或多项所述的可再充电的、非水性锂电池中的电解质，其特征在于，含有硫氰化锂作为电解质组分。
14.按照权利要求13所述的电解质，其特征在于，在电解质中含有的LiSCN的浓度为0.01-15重量％。
15.LiSCN作为氧化还原穿梭化合物在可再充电的、非水性锂电池的电解质中的应用。
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