CN109962286B - 用于锂金属二次电池的液体电解质制剂和包含所述液体电解质制剂的锂金属二次电池 - Google Patents
用于锂金属二次电池的液体电解质制剂和包含所述液体电解质制剂的锂金属二次电池 Download PDFInfo
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- 238000009472 formulation Methods 0.000 title claims abstract description 49
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Abstract
Description
技术领域
本发明涉及一种用于锂金属二次电池的液体电解质制剂。本发明还涉及制备这种液体电解质制剂的方法和包含所述液体电解质制剂的锂金属二次电池。
背景技术
常规的溶剂基电解质制剂不适合进行可逆的锂电沉积。虽然锂溶解顺利进行,但锂金属在锂上的沉积伴随着显著的电解质分解。分解产物在锂上形成所谓的固体电解质界面(SEI)。每个循环都发生分解,并显示出这种系统的低库仑效率。这种现象导致电解质消耗和电池“干燥”。
此外,这种电解质的分解伴随着气体逸出,这将导致袋状电池和其他压敏设计中的电池故障。
此外,锂沉积不均匀地发生并导致树枝状晶体的形成。这种现象对于金属电极是常见的,并且经常阻止它们在二次电池中使用。树枝状锂沉积物可能破裂,导致死锂,或者通过隔膜或在隔膜周围生长,导致电池短路。
高表面树枝状沉积物与有机溶剂的可燃性(低火焰点和高挥发性)之间的组合代表严重危害。任何电池故障都可能导致火灾和爆炸,就像20世纪80年代后期的早期商业产品一样。
离子液体已被用作有机溶剂的替代物,因为它们具有非挥发性和不可燃性,这使得离子液体电解质本身更安全。然而,锂金属沉积受到与有机溶剂相同的问题的困扰。
基于离子液体的大量制剂仍然对锂金属具有反应性以确保足够的库仑效率。导致高阻抗的SEI在操作中持续增长并导致电池故障。
另一个缺点是混合物的高粘度,特别是当加入锂盐时。这导致具有低电导率或低锂活性的混合物,其限定了低于大多数应用所需的速率能力。
尽管某些类型的离子液体显示出高达5.5V对Li+/Li或更高的电化学窗口,但允许锂金属沉积且库仑效率超过90%的离子液体在较高电压下不稳定。特别地,对锂还原稳定的阴离子在正电流收集器上分解和/或腐蚀正电流收集器低至2.5V vs.Li+/Li。
发明内容
鉴于上述情况,本发明的一个目的是提供一种基于离子液体的电解质制剂,其允许可逆的锂溶解-沉积。
本发明的另一个目的是提供一种具有宽电化学稳定性窗口的电解质。
本发明的另一个目的是提供一种电解质,其允许锂金属循环效率超过98%。
本发明的另一个目的是提供一种与商业锂离子电池电解质相比具有高离子电导率(至少1mS/cm 25℃)的电解质。
本发明的另一个目的是提供具有良好润湿性的电解质。
本发明的另一个目的是提供一种分解而不产生气体的电解质。
通过用于锂金属二次电池的液体电解质制剂实现这些目的和进一步的优点,所述液体电解质制剂包含:
-导电锂盐,其选自包括LiCl,LiF,LiTFSI,LiFSI,LiCN,LiC2N3,LiN3,LiNO2,LiNO3,LiBF4,LiPF6,LiAsF6,LiSbF6,LiAlCl4的组,
-作为抗腐蚀剂的第二离子液体,所述第二离子液体具有式(CATION)(ANION),其中(CATION)如上所定义,并且(ANION)是包含至少一个腈官能团的阴离子。
本发明的液体电解质制剂允许获得具有至少5V vs.Li+/Li的电化学窗口的电池。
本发明还涉及制备如上定义的液体电解质制剂的方法,包括以下步骤:
a)将导电锂盐溶解在第一离子液体中以获得混合物,
b)在50℃-130℃的温度下加热步骤a)的混合物,
c)任选加入稳定剂,
d)向步骤b)或步骤c)的混合物中加入第二离子液体,同时保持温度在50℃至130℃之间,
e)搅拌步骤d)的混合物,同时保持温度在50℃和130℃之间,直到混合物完全不含悬浮物,
f)将步骤e)的混合物冷却至室温(25℃)。
本发明还涉及包含如上定义的液体电解质制剂的锂金属二次电池。
本发明的有利实施方案在从属权利要求中限定并在说明书中进行解释。
附图说明
当考虑下面的详细描述时,将更好地理解本发明,并且除了上述目的之外的目的将变得显而易见。该描述参考附图,其中:
图1:在实施例1的不锈钢2025纽扣电池中进行的不锈钢vs.金属锂的10mV/s循环伏安法,
图2:在实施例2的不锈钢2025纽扣电池中在不锈钢上以0.5mA/cm2和0.1mAh/cm2进行的恒电流锂沉积-溶解,
图3:在使用(连续)和不使用(虚线)抗腐蚀剂的不锈钢vs.金属锂上的10mV/s循环伏安法。该图显示了循环2,20,50和100。该测量在不锈钢2025纽扣电池中进行。
图4:在2025纽扣电池中测量100次循环的阴极和阳极容量。
图5:在实施例4的不锈钢2025纽扣电池中以1.25mA/cm2的电流脉冲进行2小时沉积2.5mAh/cm2的电位vs.Li/Li+随时间的变化。
图6:在实施例5的不锈钢2025纽扣电池中以0.5mA/cm2进行的LiCoO2的恒电流循环。
图7:在实施例6的不锈钢2025纽扣电池中以0.2mA/cm2进行的LiFePO4的恒电流循环。
图8:在实施例7的不锈钢2025纽扣电池中以0.5mA/cm2进行的LixHyV3O8的恒电流循环。
图9:实施例8的以0.4mA/cm2的袋形式LFP-锂二次电池的充放电曲线。
具体实施方式
如上所述,本发明涉及一种用于锂金属二次电池的液体电解质制剂,其包含:
-导电锂盐,其选自包括双(氟磺酰基)亚胺锂(LiFSI),LiTFSI,LiCl,LiF,LiCN,LiC2N3,LiN3,LiNO2,LiNO3,LiBF4,LiPF6,LiAsF6,LiSbF6,LiAlCl4的组,
-具有式(CATION)(ANION)的第二离子液体,其中(CATION)如上所定义且(ANION)是包含至少一个腈(即至少一个腈官能团(N≡))的阴离子,并且优选至少两个腈。
如本领域技术人员所知,离子液体是熔点低于100℃的液体盐。
第一离子液体用作导电锂盐的溶剂,第二离子液体用作抗腐蚀剂。
因此,第一离子液体(CATION)FSI可以是PYR14FSI,PYR13FSI,PIP13FSI,PIP14FSI。
优选地,第二离子液体的(ANION)选自包括二氰胺(DCA),三氰甲基化合物(TCM),四氰基硼酸盐(TCB),4,5-二氰基-1,2,3-三唑内酯(triazolide)(DCTA)和3,5-二氰基-1,2,4-三唑内酯(DCTR)的组。
因此,第二离子液体(CATION)(ANION)可以是PYR14DCA,PYR14TCM,PYR14TCB,PYR14DCTA,PYR14DCTR,PYR13DCA,PYR13TCB,PYR13DCTA,PYR13DCTR,PIP13DCA,PIP13TCB,PIP13DCTA,PIP13DCTR,PIP14DCA,PIP14TCB,PIP14DCTA,PIP14DCTR。
优选地,(CATION)FSI/(CATION)(ANION)对是:
-Pyr14FSI/Pyr14DCA
-Pyr13FSI/Pyr14DCA
-Pyr13FSI/Pyr13DCA
-Pyr14FSI/Pyr14DCA
有利地,液体电解质制剂还可包含防止沉淀物形成的稳定剂。优选地,这种稳定剂选自包括氯化锂和水的组。如果用作抗腐蚀剂的第二离子液体(CION)(ANION)在LiFSI-(CATION)FSI混合物中是稳定的(例如),则不需要稳定剂,这可能是在非常低的浓度下(100ppm级)的情况。使用的稳定剂的量将与第二离子液体(CATION)(ANION)的量成比例。
有利地,导电锂盐的量基于液体电解质制剂为5重量%至40重量%,和第二离子液体的量基于液体电解质制剂为0.01重量%至5重量%。稳定剂的含量小于1%,并且当使用时,基于液体电解质制剂,其含量为0.001%-1%。
有利地,本发明的液体电解质制剂还可包含非质子芳族溶剂。优选地,非质子芳族溶剂选自包括苯,甲苯,二甲苯,杜烯的组。
本发明的液体电解质制剂的离子电导率为0.1-50mS/cm 25℃(优选至少1mS/cm25℃)。
本发明的电解质制剂很好地润湿聚丙烯和聚乙烯。隔膜中的吸收通常在几秒钟内发生。
本发明还涉及制备如上所述的液体电解质制剂的方法,包括以下步骤:
a)将导电锂盐溶解在第一离子液体中以获得混合物,
b)在50℃-130℃的温度下加热步骤a)的混合物,
c)任选加入稳定剂,
d)向步骤b)或步骤c)的混合物中加入第二离子液体,同时保持温度在50℃至130℃之间,
e)搅拌步骤d)的混合物,同时保持温度在50℃和130℃之间,直到混合物完全不含悬浮物,
f)在室温(25℃)下冷却步骤e)的混合物。
所有制备步骤均在充满氩气的手套箱中进行。
本发明还涉及包含如上公开的液体电解质制剂的锂金属二次电池。
在这种二次电池中,负极的材料是诸如锂,钠,镁,铝,锌的金属。
正电极的材料可选自包括锂过渡金属氧化物(如LiMO2,其中M=Co,Ni,Mn,Al或混合物),锂过渡金属磷酸盐(如LiMPO4,其中M=Fe,Ni,Co,V)和LixHyV3O8的组,如EP 2698854中所公开的。
这种二次电池是本领域技术人员公知的,并且在此不需要进一步的细节。
本发明的液体电解质制剂允许提供锂金属二次电池,其中电解质分解时不产生气体。已显示低电位的FSI分解不产生任何气体。其他钝化或副反应不会导致袋状式电池的可观察到的充气。
本发明的液体电解质制剂允许提供具有宽电化学稳定性窗口的锂金属二次电池。本发明的电解质制剂允许在使用铜和钢集电器的-0.5V vs.Li+/Li和使用钢或铝集电器的至多5V之间操作。
本发明的液体电解质制剂允许提供锂金属二次电池,其允许锂金属循环效率超过98%。在循环时,为了保存电池成分,库仑效率(CE)作为一种趋势应该变得越来越高。
以下实施例说明了本发明,但并未因此限制其范围。
电解质制剂
以下制剂用于以下实施例中:
-Pyr14FSI作为第一离子液体
-比率LiFSI:Pyr14FSI 1:3(重量)
-1重量%Pyr14DCA作为第二离子液体(防腐剂)
-0.01重量%LiCl作为稳定剂。
LiFSI购自CoorsTek Specialty Chemicals,Pyr14FSI和Pyr14DCA购自Solvionic,无水LiCl购自Sigma-Aldrich Inc.。
LiFSI溶解于Pyr14FSI中。将溶液加热至约80℃并加入LiCl。将混合物保持在80℃的温度并加入Pyr14DCA。搅拌溶液并保持温热直至完全不含悬浮物,然后冷却至室温。所有制备步骤均在充满氩气的手套箱中进行。
实施例1
组装2025纽扣电池以确定是否发生锂沉积-溶解并且验证没有看到明显的腐蚀。为此,将由1cm2锂箔(0.1mm厚)制成的负极,Celgard 2400隔膜和作为正极的不锈钢盘堆叠在2025壳体中。如果需要,可以使用附加的不锈钢盘作为间隔物。然后在-3mA至5V之间以10mV/s进行循环测量,进行100个循环,如图1所示(图1显示循环2,20,50和100)。锂沉积和溶解的模式清晰且稳定,而没有其他电化学过程可见。因此,这种系统的电化学窗口为至少5V vs.Li+/Li。
实施例2
除了电解质之外,使用与实施例1相同的组分的相同步骤。电解质不含任何第二离子液体(CATION)(ANION)作为抗腐蚀剂或稳定剂。从第一个循环开始,不锈钢的腐蚀很明显,并随着时间的推移而增加(图2)。图2显示了循环1,5,10,30,50,80和99。库仑效率在第一个循环中达到75%并且在循环时增加到第99个循环达到99%以上。
实施例3
使用与实施例1相同的结构和组分。以0.5mA至0.1mAh进行锂沉积,并且以0.5mA至500mV进行锂溶解。该设置旨在确定给定电流速率下的库仑效率(CE)。虽然CE在第一个循环中仅达到约75%,但其值在后续循环中迅速改善,并且在20个循环后达到99%以上(图4)。
实施例4
使用具有两个锂电极的实施例1的2025底部电池构造构建对称锂-锂电池。在第一半循环中施加1.25mA/cm2的电流2小时。在第二半循环中,施加-1.25mA/cm2的电流两小时。以这种方式,2.5mAh/cm2的锂沉积并溶解在每个电极上。每十个循环,测量停止并在两小时后恢复循环(图5)。该程序旨在鉴定SEI和沉积锂的性质。当电解质制剂不合适时,通常观察到上升的阻抗。在大多数情况下,这最终会导致电池短路。在本实施例中,沉积过电压在循环时降低,这对应于沉积-溶解过程的稳定化。重要的是要注意在2小时制动后过电压不会显著增加,这暗示了稳定的SEI,可防止大块锂的持续降解。
实施例5
使用与实施例1相同的结构构建二次锂金属电池,其中LiCoO2涂覆在铝(6至8mg/cm2)上作为正电极,锂箔作为负电极。图6显示了LiCoO2以0.5mA/cm2的恒电流循环(活性材料负载为1mg/cm2,涂覆在裸铝箔上)。图6显示了循环7,8,9和10。在选定的循环范围内,不能检测到容量损失或过电压增加。
实施例6
使用与实施例1相同的结构构建二次锂金属电池,其中LFP涂覆在铝(12至15mg/cm2)上作为正电极,锂箔作为负电极。图7显示了LiFePO4以0.2mA/cm2的恒电流循环(活性材料负载为13mg/cm2,涂覆在裸铝箔上)。图7显示了循环7,8,9和10。在选定的循环范围内,不能检测到容量损失或过电压增加。
实施例7
使用与实施例1相同的结构构建二次锂金属电池,其中LixHyV3O8涂覆在铝(10-12mg/cm2)上作为正电极,锂箔作为负电极。图8显示LixHyV3O8以0.5mA/cm2的恒电流循环(活性材料负载为10mg/cm2,涂覆在碳涂覆的铝箔上)。图8显示了循环55,60,65和75。在所选择的循环范围内,不能检测到容量损失和过电压增加。
实施例8
使用袋箔和不锈钢集电器构建二次棱柱形锂金属电池。负极由50μm的锂箔组成和正极由LFP组成(钢上涂层12-15mg/cm2)。在真空密封之前,在阴极表面上引入8μl/cm2的电解质。使用Teijin MFS FZA1101作为隔膜。电化学测量以0.4V/cm2在2V和3.8V之间进行。没有外部压力施加到电池上。图9显示了前50个循环的充放电曲线。
Claims (12)
2.根据权利要求1的液体电解质制剂,其中它还包含防止沉淀物形成的稳定剂。
3.根据权利要求2的液体电解质制剂,其中稳定剂选自包括氯化锂和水的组。
4.根据权利要求2的液体电解质制剂,其中稳定剂的量基于液体电解质制剂为0.001重量%-1重量%。
5.根据权利要求1的液体电解质制剂,其中导电锂盐的量基于液体电解质制剂为5重量%至40重量%。
6.根据权利要求1的液体电解质制剂,其中所述第二离子液体的量基于所述液体电解质制剂为0.01重量%至5重量%。
7.根据权利要求1的液体电解质制剂,其中第一离子液体(CATION)FSI选自包括PYR14FSI,PYR13FSI,PIP13FSI和PIP14FSI的组。
8.根据权利要求1的液体电解质制剂,其中(ANION)选自包括二氰胺(DCA),三氰甲基化合物(TCM),四氰基硼酸盐(TCB),4,5-二氰基-1,2,3-三唑内酯(DCTA)和3,5-二氰基-1,2,4-三唑内酯(DCTR)的组。
9.根据权利要求1的液体电解质制剂,其中它还包含非质子芳族溶剂。
10.根据权利要求9的液体电解质制剂,其中非质子芳族溶剂选自包括苯,甲苯,二甲苯,杜烯的组。
11.一种制备锂金属二次电池的液体电解质制剂的方法,所述液体电解质制剂包含:
-导电锂盐,其选自包括LiTFSI,LiFSI,LiCl,LiF,LiCN,LiC2N3,LiN3,LiNO2,LiNO3,LiBF4,LiPF6,LiAsF6,LiSbF6,LiAlCl4的组,
-作为抗腐蚀剂的第二离子液体,所述第二离子液体具有式(CATION)(ANION),其中(CATION)如上所定义,并且(ANION)是包含至少一个腈官能团的阴离子,
其中所述方法包括以下步骤:
a)将导电锂盐溶解在第一离子液体中以获得混合物,
b)在50℃-130℃的温度下加热步骤a)的混合物,
c)任选加入稳定剂,
d)向步骤b)或步骤c)的混合物中加入第二离子液体,同时保持温度在50℃至130℃之间,
e)搅拌步骤d)的混合物,同时保持温度在50℃和130℃之间,直到混合物完全不含悬浮物,
f)将步骤e)的混合物冷却至室温。
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JP2019114531A (ja) | 2019-07-11 |
CN109962286A (zh) | 2019-07-02 |
EP3503268B1 (en) | 2020-09-16 |
KR102181846B1 (ko) | 2020-11-24 |
ES2833924T3 (es) | 2021-06-16 |
US11050090B2 (en) | 2021-06-29 |
PL3503268T3 (pl) | 2021-04-06 |
US20190198930A1 (en) | 2019-06-27 |
EP3503268A1 (en) | 2019-06-26 |
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JP6744899B2 (ja) | 2020-08-19 |
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