CN110137571A - 一种含硫的电解液及锂离子电池 - Google Patents
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 40
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 33
- 239000011593 sulfur Substances 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 4
- LKSCJMIATJONBS-UHFFFAOYSA-K trilithium oxalic acid phosphate Chemical class P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] LKSCJMIATJONBS-UHFFFAOYSA-K 0.000 claims description 4
- -1 3,3,3- tri- Fluoropropyl Chemical group 0.000 claims description 3
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- 239000002253 acid Substances 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 2
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 229960002645 boric acid Drugs 0.000 claims 1
- 235000010338 boric acid Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
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- SOHBHOFMMCSVMW-UHFFFAOYSA-N boric acid;difluoro oxalate;lithium Chemical compound [Li].OB(O)O.FOC(=O)C(=O)OF SOHBHOFMMCSVMW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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Abstract
一种含硫的电解液及锂离子电池,属于锂离子电池技术领域。所述的含硫的电解液包括添加剂Y,所述的添加剂Y如结构式I所示,其中,R1、R2各自独立地分别为取代或未取代的C1~6烷基和烷氧基中的任一种,还公开了一种锂离子电池,本发明中含硫的电解液中的添加剂Y,能够在低电位下通过单电子氧化改善锂离子电池正极和电解液的界面性质,提高电池的循环稳定性;在超过4.6V时通过双电子氧化在正极形成稳定且高阻抗的界面膜,提高电池的防过充性能,确保电池的安全性。
Description
技术领域
本发明属于锂离子电池技术领域,具体涉及一种含硫的电解液及锂离子电池。
背景技术
由于相对其他二次电池来说锂离子电池具有独特的优点,例如:循环性能好、工作电压高和对环境友好等,使得锂离子电池在近年来被广大的研究人员所关注且在多个领域得到了应用,包括手机等消费类电池和国防工业。随着人们对锂离子电池能量密度的需求越来越高,高镍正极材料是当前的主流研究方向,但是,高镍正极材料循环稳定性和安全性能较差。
当前,电解液中添加剂的使用是解决高镍材料循环稳定性问题的有力手段。目前使用最多的PS、VC等成膜添加剂具有明显的有利效果,但是它们对安全性能是没有贡献的。然后,FB、CHB等物质能明显改善电池的过充特性,但是它们极大劣化了电池的电性能。因此,兼顾锂离子电池的电性能和安全性能是当前面临最大的挑战之一。
发明内容
本发明的目的是为了解决现有锂离子电池电性能与安全性能难以兼顾的问题,提供一种含硫的电解液及锂离子电池,该电解液能够提高锂离子电池的循环性能,且兼顾防过充的作用,提高电池安全性能。
为实现上述目的,本发明采取的技术方案如下:
一种含硫的电解液,包括有机溶剂、添加剂和锂盐,所述添加剂包括添加剂Y,所述添加剂Y的结构式如I所示:
其中,R1、R2各自独立地分别为C1~6烷基、烷氧基、取代C1~6烷基或取代烷氧基中的任一种。
一种含有上述的含硫的电解液的锂离子电池,所述锂离子电池包括含有正极活性材料的正极片、含有负极活性材料的负极片、隔膜和含硫的电解液。
本发明相对于现有技术的有益效果为:本发明中含硫的电解液中的添加剂Y,能够在低电位下通过单电子氧化改善锂离子电池正极和电解液的界面性质,提高电池的循环稳定性;在超过4.6V时通过双电子氧化在正极形成稳定且高阻抗的界面膜,提高电池的防过充性能,确保电池的安全性。
具体实施方式
下面结合实施例对本发明的技术方案作进一步的说明,但并不局限于此,凡是对本发明技术方案进行修正或等同替换,而不脱离本发明技术方案的精神范围,均应涵盖在本发明的保护范围之中。
具体实施方式一:本实施方式记载的是一种含硫的电解液,包括有机溶剂、添加剂和锂盐,所述添加剂包括添加剂Y,所述添加剂Y的结构式如I所示:
其中,R1、R2各自独立地分别为C1~6烷基、烷氧基、取代C1~6烷基或取代烷氧基中的任一种,具体地,取代C1~6烷基或取代烷氧基指的是C1~6烷基或烷氧基上的氢被其他元素取代后的基团。
具体实施方式二:具体实施方式一所述的一种含硫的电解液,所述添加剂Y为以下物质中的一种:
具体实施方式三:具体实施方式一所述的一种含硫的电解液,所述添加剂Y的用量占含硫的电解液总重量的0.01%~8%。
具体实施方式四:具体实施方式一所述的一种含硫的电解液,所述添加剂还包括3,3,3-三氟丙基碳酸酯,其用量占含硫的电解液总重量的0.1%~5%。
具体实施方式五:具体实施方式一所述的一种含硫的电解液,所述有机溶剂为碳酸酯、羧酸酯和氟代醚中的一种或多种。
具体实施方式六:具体实施方式一所述的一种含硫的电解液,所述锂盐为六氟磷酸锂、二氟磷酸锂、双氟磺酰亚胺锂、二氟双草酸磷酸锂、四氟草酸磷酸锂、二氟草酸硼酸锂、双(三氟甲基磺酰)亚胺锂和双草酸硼酸锂中的一种或多种,其用量占含硫的电解液总重量的8%~20%。
具体实施方式七:一种含有具体实施方式一至六任一具体实施方式所述的含硫的电解液的锂离子电池,所述锂离子电池包括含有正极活性材料的正极片、含有负极活性材料的负极片、隔膜和含硫的电解液。
本发明中对比例和实施例的电解液和锂离子电池的实验信息如表1和表2,实验对应的测试结果见表3和表4。在没有特殊说明的情况下,有机溶剂的用量为除去下表1和2中所对应第3和4列所记载的含量之外的余量。具体地,对比例和实施例中的电解液及锂离子电池的制备过程均采用现有的制备工艺来制备。
表1对比例实验信息
表2实施例实验信息
对实施例和对比例中的锂离子电池进行高温循环测试,具体的测试条件如下:
高温循环测试:把电池搁置在45℃条件下,在2.8~4.2V的充放电压区间下使用1C电流进行充放电循环,记录初始容量为Q,选循环至500周的容量为Q2,由如下公式计算电池高温循环500周的容量保持率:容量保持率(%)=Q2/Q×100%。
安全性测试:将电池恒流恒压充电至4.2V,随后以1C的电池持续充电至5.46V,电池不起火为通过。
表3对比例实验测试结果
对比例 | 高温循环容量保持率 | 安全性测试 |
1 | 69.06% | 不通过 |
2 | 71.85% | 不通过 |
3 | 64.38% | 不通过 |
4 | 68.21% | 不通过 |
5 | 59.06% | 不通过 |
6 | 71.37% | 不通过 |
表4实施例实验测试结果
对比例 | 高温循环容量保持率 | 安全性测试 |
1 | 87.67% | 通过 |
2 | 90.12% | 通过 |
3 | 85.38% | 通过 |
4 | 88.87% | 通过 |
5 | 87.09% | 通过 |
6 | 84.37% | 通过 |
通过以上数据可以明显看出,添加剂Y对锂离子电池高温循环和安全性能都有明显的有利效果,本发明使用添加剂Y加入到电解液中具有突出的优势,主要表现在改善电池的高温循环性能和过充性能。实施例1~6明显优于对比例,因此本发明的电解液制备的电池具有极高的耐用性能,具有极高的市场价值和社会效益。以上是针对本发明的可行实施例的具体说明,但并不能限制本发明的保护范围。
Claims (7)
1.一种含硫的电解液,包括有机溶剂、添加剂和锂盐,其特征在于:所述添加剂包括添加剂Y,所述添加剂Y的结构式如I所示:
其中,R1、R2各自独立地分别为C1~6烷基、烷氧基、取代C1~6烷基或取代烷氧基中的任一种。
2.根据权利要求1所述的一种含硫的电解液,其特征在于:所述添加剂Y为以下物质中的一种:
3.根据权利要求1所述的一种含硫的电解液,其特征在于:所述添加剂Y的用量占含硫的电解液总重量的0.01%~8%。
4.根据权利要求1所述的一种含硫的电解液,其特征在于:所述添加剂还包括3,3,3-三氟丙基碳酸酯,其用量占含硫的电解液总重量的0.1%~5%。
5.根据权利要求1所述的一种含硫的电解液,其特征在于:所述有机溶剂为碳酸酯、羧酸酯和氟代醚中的一种或多种。
6.根据权利要求1所述的一种含硫的电解液,其特征在于:所述锂盐为六氟磷酸锂、二氟磷酸锂、双氟磺酰亚胺锂、二氟双草酸磷酸锂、四氟草酸磷酸锂、二氟草酸硼酸锂、双(三氟甲基磺酰)亚胺锂和双草酸硼酸锂中的一种或多种,其用量占含硫的电解液总重量的8%~20%。
7.一种含有权利要求1~6任一权利要求所述的含硫的电解液的锂离子电池,其特征在于:所述锂离子电池包括含有正极活性材料的正极片、含有负极活性材料的负极片、隔膜和含硫的电解液。
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