CN103715460A - 一种含双硼亚胺锂锂盐的电解质溶液 - Google Patents
一种含双硼亚胺锂锂盐的电解质溶液 Download PDFInfo
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- -1 imine lithium salt Chemical class 0.000 title claims abstract description 29
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- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 18
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
本发明提供一种含双硼亚胺锂锂盐的电解质溶液，该电解质溶液由四类成份组成：含双硼亚胺锂、其他锂盐、碳酸酯类和/或醚类有机溶剂和其他功能添加剂，其中含双硼亚胺锂锂盐在此电解质溶液中的摩尔浓度为0.001～2mol/L，其他锂盐在此电解质溶液中所占的摩尔浓度为0～2mol/L，其他功能添加剂在此电解质溶液中的摩尔浓度为0～0.5mol/L；含双硼亚胺锂为离子型化合物，其阳离子为锂离子。本发明提供的电解质溶液中含有含双硼亚胺锂，能大大提高电解质溶液的低温性能，将其应用于50℃以上高温或-20℃以下低温的锂电池后，其电池容量百分率均有所提高，延长了锂电池的循环寿命和储存寿命。
Description
技术领域
本发明属于化学材料技术领域，具体涉及一种含双硼亚胺锂锂盐的电解质溶液。
背景技术
目前，商业化锂电池电解质主要由有机碳酸酯—如碳酸二甲酯（简称DMC），碳酸二乙酯（简称DEC），碳酸乙烯酯（简称EC）等和锂盐（主要是LiPF6）组成。有机碳酸酯非水电解质溶液的优化和选择是提高锂离子电池综合性能的重要研究方向之一。而应用于锂离子电池的非水电解质溶液，一般应满足以下要求：（1）离子电导率高，一般应达到10-3 S/cm；（2）锂离子迁移数高，以获得高的锂离子电导率；（3）电化学窗口宽，即满足锂离子在正、负极的可逆嵌入和脱出，而电解质不发生化学或电化学分解；（4）热稳定性高，在较宽的工作温度范围内不发生化学或电化学分解；（5）化学稳定性高，即与电池体系的电极材料如正极、负极、集流体、粘结剂、导电剂和隔膜等不发生化学反应；（6）具有较低的界面转移电阻；（7）与目前主要使用的正负极材料兼容性好；（8）无毒、无污染、使用安全，最好能生物降解；（9）容易制备，成本低。
经过几十年的研究和实践，目前应用于商业化二次锂电池的非水电解质溶液一般选择六氟磷酸锂(LiPF6)作为锂盐，溶剂多为高粘度、高介电常数的碳酸乙烯酯（简称EC）、碳酸丙烯酯（简称PC）与低粘度、低介电常数的碳酸二甲酯（简称DMC）、碳酸二乙酯（简称DEC）、或甲基乙基碳酸酯（简称EMC）构成的混合溶剂。此类体系最终能够大规模使用，并非其各项指标具有突出的特性，而且其综合指标基本能满足现有二次锂电池的产业应用要求。
尽管以LiPF6作为锂盐的非水电解质溶液在锂离子电池产业上获得了巨大成功，但是LiPF6自身固有的缺陷限制了其电解质溶液在极限条件下的应用。PF6 –阴离子对称性高，其锂盐LiPF6晶格能大，熔点高，在有机溶剂中溶解度小，因而，LiPF6锂盐在低温下易从有机电解质溶液中结晶析出。LiPF6不稳定，在溶液中，阴离子PF6??存在一个平衡： LiPF6→LiF + PF5，倾向于形成LiF而导致LiPF6分解，从而导致平衡向右进行，进而导致电解液锂盐浓度下降，电导率降低，电池性能劣化。同时，LiPF6对水敏感。在由有机碳酸酯等极性非质子溶剂（dipolar aprotic solvent）组成的电解液体系中，LiPF6锂盐处于高度溶剂化状态，而PF6-溶剂化程度极低，反应活性高；电解液中微量水作为亲核试剂，与作为底物PF6-发生亲核取代反应： LiPF6 + H2O→POF3 + LiF + 2HF，PF5 + H2O→POF3 + 2HF。此反应也就是人们常说的P-F 键对水非常敏感根本原因所在。更为严重的是上述反应所产生的HF对正极材料危害极大，将促进正极材料的溶解，使其储锂容量逐渐衰减。
综上所述，在追求更高能量密度、更高功率密度、更长使用寿命以及更低使用成本的锂离子动力电池和储能电池的实践中，寻找LiPF6基非水电解液的替代品，开发具有更高电导率、更高锂离子迁移数、更高电化学稳定性以及更宽操作温度的电解质材料成为国内外众多研究者努力的目标。
发明内容
基于以上技术背景，本发明的目的在于提供一种含双硼亚胺锂锂盐的电解质溶液，以提高电解质溶液的稳定性和对水敏感性，使其在高温、低温的环境中使用时电池容量百分率有所提高，延长锂电池的循环寿命和储存寿命。
本发明的方案是通过如下技术措施来实现的：
一种含双硼亚胺锂锂盐的电解质溶液，其特点在于该电解质溶液由四类组份组成：（A）含双硼亚胺锂，（B）其他锂盐，（C）碳酸酯类和/或醚类有机溶剂和（D）其他功能添加剂，其中组分（A）含双硼亚胺锂锂盐在此电解质溶液中所占的摩尔浓度范围是0.001～2mol/L，组分（B）其他锂盐在此电解质溶液中所占的摩尔浓度范围是0～2mol/L，组分（D）其他功能添加剂在此电解质溶液中所占的摩尔浓度范围是：0～0.5 mol/L，其中所述的（A）含双硼亚胺锂为离子型化合物，其阳离子为锂离子，其阴离子结构式如下：
结构式中，R1、R2独立地选自卤素、烷基、烷氧基、卤代烷基、卤代烷氧基、烯烃基、卤代烯烃基、苯基、联苯基、卤代苯基或卤代联苯基。
以上所述的卤素为F、Cl、Br中的一种或两种，卤代包含部分取代和全取代。
以上所述的组分（B）其他锂盐为具有如下分子式的化合物中的至少一种：LiBF4、LiPF6、LiAsF6、LiClO4、LiSO3CF3、LiC2O4BC2O4、LiF2BC2O4、LiBFa[(C6Fx(CnFmH(2n+1-m))yH(5-x-y))](4-a)，a=0，1，2，3；x=0，1，2，3，4，5；y=0，1，2，3，4，5；n、m为大于等于零的整数，以及LiPFb[(C6Fs(CpFqH(2p+1-q))tH(5-s-t))](6-b)，b=0，1，2，3，4，5；s=0，1，2，3，4，5；t=0，1，2，3，4，5；p，q为大于等于零的整数。
以上所述的（C）碳酸酯类有机溶剂为环状的碳酸酯类和/或链状碳酸酯类化合物；所述的醚类有机溶剂选自四氢呋喃、2-甲基四氢呋喃、1，3-二氧环戊烷、二甲氧甲烷、1，2-二甲氧乙烷和二甘醇二甲醚中的至少一种。
以上所述的环状的碳酸酯类化合物选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯和碳酸亚丁酯中的至少一种；所述的链状的碳酸酯类化合物选自碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲基乙基酯、碳数为3～8的直链或支链脂肪单醇与碳酸合成的碳酸酯衍生物中的至少一种。
以上所述的组分（D）其他功能添加剂选自下列化合物中的至少一种：联苯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯、1、3-丙磺酸内酯、1、4-丁磺酸内酯、1、3-（1-丙烯）磺内酯、亚硫酸乙烯酯、硫酸乙烯酯、环己基苯、叔丁基苯、叔戊基苯和丁二氰。
本发明的电解质溶液用于50℃以上高温或-20℃以下低温环境下使用的锂电池中。
本发明提供了一种含双硼亚胺锂锂盐的电解质溶液，该电解质溶液中含有含双硼亚胺锂，能大大提高电解质溶液的稳定性和对水敏感性，在-40℃至80℃环境下使用时电池容量百分率均有所提高，有利于锂电池的循环寿命和储存寿命的提高。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，本发明用以下具体实施例进行说明，但本发明绝非仅限于这些例子。
本发明以表格的形式例举了1～84种基于含双硼亚胺锂的电解质溶液的成份组成、以及各电解质溶液的电池容量百分比的测试数据，详见下表：
由上述实施例可见，电解质溶液中含有含双硼亚胺锂，能大大提高电解质溶液的高温和低温性能，将其应用于锂电池后，锂电池在高温（50℃以上）和低温（-20℃以下）的情况下，其电池容量百分率均有所提高，有利于锂电池的循环寿命和储存寿命的提高。
Claims (7)
1.一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：该电解质溶液由四类组份组成：（A）含双硼亚胺锂，（B）其他锂盐，（C）碳酸酯类和/或醚类有机溶剂和（D）其他功能添加剂，其中组分（A）含双硼亚胺锂锂盐在此电解质溶液中所占的摩尔浓度范围是0.001～2mol/L，组分（B）其他锂盐在此电解质溶液中所占的摩尔浓度范围是0～2mol/L，组分（D）其他功能添加剂在此电解质溶液中所占的摩尔浓度范围是：0～0.5 mol/L，其中所述的（A）含双硼亚胺锂为离子型化合物，其阳离子为锂离子，其阴离子结构式如下：
结构式中，R1、R2独立地选自卤素、烷基、烷氧基、卤代烷基、卤代烷氧基、烯烃基、卤代烯烃基、苯基、联苯基、卤代苯基或卤代联苯基。
2.根据权利要求1所述的一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：所述的卤素为F、Cl、Br中的一种或两种，卤代包含部分取代和全取代。
3.根据权利要求1所述的一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：所述的组分（B）其他锂盐为具有如下分子式的化合物中的至少一种：LiBF4、LiPF6、LiAsF6、LiClO4、LiSO3CF3、LiC2O4BC2O4、LiF2BC2O4、LiBFa[(C6Fx(CnFmH(2n+1-m))yH(5-x-y))](4-a)，a=0，1，2，3；x=0，1，2，3，4，5；y=0，1，2，3，4，5；n、m为大于等于零的整数，以及LiPFb[(C6Fs(CpFqH(2p+1-q))tH(5-s-t))](6-b)，b=0，1，2，3，4，5；s=0，1，2，3，4，5；t=0，1，2，3，4，5；p，q为大于等于零的整数。
4.根据权利要求1所述的一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：所述的（C）碳酸酯类有机溶剂为环状的碳酸酯类和/或链状碳酸酯类化合物；所述的醚类有机溶剂选自四氢呋喃、2-甲基四氢呋喃、1，3-二氧环戊烷、二甲氧甲烷、1，2-二甲氧乙烷和二甘醇二甲醚中的至少一种。
5.根据权利要求4所述的一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：所述的环状的碳酸酯类化合物选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯和碳酸亚丁酯中的至少一种；所述的链状的碳酸酯类化合物选自碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲基乙基酯、碳数为3～8的直链或支链脂肪单醇与碳酸合成的碳酸酯衍生物中的至少一种。
6.根据权利要求1所述的一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：所述的组分（D）其他功能添加剂选自下列化合物中的至少一种：联苯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯、1、3-丙磺酸内酯、1、4-丁磺酸内酯、1、3-（1-丙烯）磺内酯、亚硫酸乙烯酯、硫酸乙烯酯、环己基苯、叔丁基苯、叔戊基苯和丁二氰。
7.根据权利要求1所述的一种含双硼亚胺锂锂盐的电解质溶液，其特征在于：该电解质溶液用于50℃以上高温或-20℃以下低温环境下使用的锂电池中。
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