CN116417664A - 用于锂二次电池的电解质溶液和包含其的锂二次电池 - Google Patents
用于锂二次电池的电解质溶液和包含其的锂二次电池 Download PDFInfo
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- CN116417664A CN116417664A CN202210921921.6A CN202210921921A CN116417664A CN 116417664 A CN116417664 A CN 116417664A CN 202210921921 A CN202210921921 A CN 202210921921A CN 116417664 A CN116417664 A CN 116417664A
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- Prior art keywords
- electrolyte solution
- lithium secondary
- secondary battery
- cathode
- electrolyte
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
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- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
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- 229910013372 LiC 4 Inorganic materials 0.000 claims description 2
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- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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Abstract
本发明提供了用于锂二次电池的电解质溶液和包含其的锂二次电池。具体地,用于电解质溶液的添加剂改善了锂二次电池的电化学性能。
Description
技术领域
本公开涉及构成锂二次电池的电解质溶液和包含其的锂二次电池。具体地,本公开涉及用于电解质溶液的添加剂,以改善锂二次电池的电化学性能。
背景技术
电池是能够将化学能转化为电能或将电能转化为化学能的能量储存源。电池可以分为不可重复使用的原电池(primary battery,一次电池)和可重复使用的二次电池。与一次使用并丢弃的原电池相比,二次电池是比较环保的,因为它们可以重复使用。
近年来,随着环境问题出现,对具有很少或没有空气污染的混合电动车辆(HEV)和电动车辆(EV)的需求正在增加。具体地,EV是内燃发动机已被完全移除的车辆,这表明了世界未来的发展方向。
锂二次电池被用作EV的能量源。锂二次电池主要由阴极(cathode,正极)、阳极(anode,负极)、电解质和隔膜组成。在阴极和阳极中,重复锂离子的嵌入和脱嵌以产生能量,电解质变成锂离子移动的路径,并且在隔膜中,阴极和阳极相遇以防止电池中的短路。
具体地,阴极与电池的容量密切相关,并且阳极与电池的性能如高速充放电密切相关。
电解质由溶剂、添加剂和锂盐组成。该溶剂变成有助于锂离子在阴极与阴极之间来回移动的传输通道。为了使电池具有良好的性能,锂离子必须在阴极与阳极之间迅速传递。因此,为了获得优异的电池性能,选择最佳的电解质是非常重要的。
具体地,在电池生产过程中进行的化学转化过程中,在阳极上形成称为固体电解质相界面(solid electrolyte interphase)(SEI)的薄膜。SEI是可以通过锂离子但不能通过电子的膜,并且防止电池性能劣化,因为电子穿过SEI并且诱导额外的反应。此外,SEI抑制电解质与阳极的直接反应并且抑制阴极的分离。
电解质的添加剂是相对于电解质的重量以0.1%至10%的痕量添加的物质。尽管添加痕量,但添加剂对电池的性能和稳定性有很大影响。具体地,添加剂在阳极的表面上诱导SEI的形成并且在控制SEI的厚度中起作用。此外,添加剂可以防止电池过度充电并且可以增加电解质中锂离子的电导率。
另一方面,锂二次电池的能量密度主要取决于阴极和阳极材料的特性,因此有必要开发合适的电解质,以使所开发的阴极和阳极材料表现出优异的电化学性能。
最近,在作为高容量阴极活性材料的NCM基氧化物中,可以通过增加Ni含量或充电电压的高电压来增加阴极容量,但是阴极表面上的残留锂(Li2CO3和LiOH)组分加速电解质分解并且还由于与电解质的界面反应性的增加而增加降解速率,从而使锂二次电池劣化并迅速劣化电化学性能。
因此,需要引入能够形成电化学和化学稳定的SEI的添加剂。
上述作为背景技术描述的内容仅用于提高对本公开的背景的理解,而不应被视为承认它们对应于本领域普通技术人员已知的现有技术。
发明内容
提出本公开旨在解决这些问题,并且本公开的目的是提供一种能够通过添加到锂二次电池的电解质溶液中来改善锂二次电池的电化学性能的电解质溶液添加剂。
本公开涉及一种用于锂二次电池的电解质,包含电解质盐和有机溶剂,该电解质包含由以下式1表示的碳酸亚乙烯酯(vinylene carbonate)(VC),并且该电解质还包含由以下式2表示的添加剂4-(烯丙氧基)苯基氟硫酸酯(4-(allyloxy)phenylfluorosulfate)。
式1:
式2:
可以以相对于电解质的总重量按重量计0.1%至1.0%的量包含4-(烯丙氧基)苯基氟硫酸酯。
可以以相对于电解质的总重量按重量计0.1%至10%的量包含VC。
电解质盐可以与选自由以下组成的组的任何一种或者两种或更多种化合物混合:LiPF6、LiBF4、LiClO4、LiCl、LiBr、LiI、LiB10Cl10、LiCF3SO3、LiCF3.0CO2、Li(CF3SO2)3.0C、LiAsF6、LiSbF6、LiAlCl4、LiCH3SO3、LiCF3SO3、LiN(SO2.0C2F5)2、Li(CF3SO2)2N、LiC4F9SO3、LiB(C6H5)4、以及Li(SO2F)2N(LiFSi)。
可以以0.5M至1.0M的浓度包含电解质盐。
有机溶剂可以是选自由以下组成的组中的任何一种或者两种或更多种溶剂:碳酸酯类溶剂、酯类溶剂、醚类溶剂以及酮类溶剂。
包括电解质溶液的锂二次电池包括阴极、阳极以及插在阴极与阳极之间的隔膜,并且锂二次电池的阴极可以包括镍钴锰(NCM)基阴极活性材料,此时,镍、钴以及锰可以具有6:2:2至8:1:1的重量比率。
根据本公开,当使用用添加剂1和添加剂2的电解质制造锂二次电池时,添加剂2在阴极和阳极中牢固地形成CEI和SEI,从而获得具有增加的电化学特性的锂二次电池。
附图说明
图1是示出4-(烯丙氧基)苯基氟硫酸酯的HOMO和LUMO的能级的图;
图2是示出比较例和实施例的初始电池效率的图;
图3是示出比较例和实施例的高温寿命的图;并且
图4是示出比较例和实施例的高速率特性的图。
具体实施方式
在下文中,将参考附图详细描述解决上述目的和问题的具体内容。另一方面,在理解本公开中,当相同领域中的已知技术的详细描述对理解本公开的核心内容不利时,将忽略该描述,并且本公开的技术精神不限于此,并且可以通过由本领域技术人员改变来不同地实现。
本公开的一个特点是锂二次电池的电化学性能可以通过同时使用作为添加剂的由式1表示的碳酸亚乙烯酯(VC)和作为添加剂的由式2表示的4-(烯丙氧基)苯基氟硫酸酯而增加。
式1和式2如下。
式1:
式2:
在下文中,VC将被表示为添加剂1,并且4-(烯丙氧基)苯基氟硫酸酯将被表示为添加剂2。
通过同时使用添加剂1和添加剂2,阴极电解质相界面(CEI)形成在阴极上,并且SEI形成在阳极上,从而改善电池的寿命和输出特性。
具体地,由于添加剂2与电解质中包含的其他材料相比具有低LUMO能级和高HOMO能级,因此预期首先在阴极与阳极表面上反应以形成CEI和SEI。
图1示出对应于添加剂2的LUMO和HOMO的能级,并且MH-161对应于本公开的添加剂2。参见图1,添加剂2的HOMO能级为-5.96eV,以及LUMO的能级为-1.73eV,并且可以预期反应会发生,因为与EC和FEC用作溶剂、VC用作添加剂和LiPO2F2相比,它在阴极和阳极容易分解。
具体地,膜的形成可以通过添加剂2末端的乙烯基诱导自由基聚合而预期。如上所描述形成的聚合物是聚合物组分并且可以具有物理柔性,从而抑制由于由阳极问题引起的体积膨胀和收缩引起的膜结构的破裂,以及由于膜结构的破裂和由此导致的阴极活性材料的暴露引起的膜连续变厚的现象。
此外,该分子在电解质中离解以具有OSO2-官能团并且预期形成Li2SO3和ROSO2Li组分的SEI。预期砜基组分(如Li2SO3和ROSO2Li)通过形成具有低电阻和优异的热稳定性的膜而在改善电化学性能方面起作用。
此外,预期键合至分子端的氟(F)在阳极表面上形成LiF,并且预期添加剂2在形成LiF方面更有效,因为氟具有比其他添加剂氟代碳酸乙烯酯(FEC)更高的脱嵌倾向(FEC内部的C-F键的结合能是-1.61eV,并且添加剂2内部的S-F键的结合能是-4.35eV)。
另一方面,可以通过以下机制制备本公开的添加剂2:
(a)1,1′-磺酰基二咪唑(1.5当量),Cs2CO3(0.5当量),THF,rt,12h,(b2AgF(1.8当量),MeCN,80℃,12h
①将4.50ml,29.96mmol的4-(烯丙氧基)苯酚和4.88g,14.98mmol的碳酸铯溶解在45ml的四氢呋喃中,并加入8.91g,44.95mmol的1,1'-磺酰基二咪唑。
②将混合物在室温下搅拌12小时后,通过柱色谱法(column chromatography,柱层析法)(乙酸乙酯/己烷:3/7)获得呈透明油形式的4-(烯丙氧基)苯基1H-咪唑-1-磺酸酯(MH-159)(93%的产率,7.78g)。
作为H-NMR的结果,确认MH-159可以通过获得以下结果值而获得:
1H NMR(300MHz,CDCl3)δ7.71(t,J=1.0Hz,1H),7.28(t,J=1.5Hz,1H),7.16(dd,J=1.6,0.8Hz,1H),6.86–6.79(m,4H),6.01(ddt,J=17.3,10.5,5.3Hz,1H),5.39(dq,J=17.3,1.6Hz,1H),5.30(dq,J=10.5,1.4Hz,1H),4.50(dt,J=5.3,1.5Hz,2H).13C{1H}NMR(101MHz,CDCl3)δ158.4,142.5,137.7,132.6,131.4,122.4,118.5,118.3,116.0,69.3。
③将7.78g,27.76mmol的MH-159溶解在100ml的乙腈中,加入6.34g,49.97mmol的氟化银(I),并将混合物在80℃下搅拌12小时,然后可以通过柱色谱法(乙酸乙酯/己烷:3/7)获得呈黄色油形式的4-(烯丙氧基)苯基氟硫酸酯(MH-161)(90%的产率,5.80g)。
作为H-NMR的结果,确认MH-161可以通过获得以下结果值而获得。
1H NMR(400MHz,CDCl3)δ7.29–7.21(m,3H),7.01–6.91(m,2H),6.04(ddt,J=17.3,10.5,5.3Hz,1H),5.42(dq,J=17.3,1.6Hz,1H),5.32(dq,J=10.5,1.4Hz,1H),4.55(dt,J=5.3,1.5Hz,2H).19F{1H}NMR(377MHz,CDCl3)δ36.4。
在下文中,将描述通过使用添加剂制造锂二次关于电池的电化学性能的实验结果。
阴极包括由Ni、Co和Mn制成的NCM基阴极活性材料,并且具体地,在该实施方式中使用NCM811。可以使用LiCoO2、LiMnO2、LiNiO2、LiNi1-xCoxO2、LiNi0.5Mn0.5O2、LiMn2-xMxO4(M是Al、Li或过渡金属)、LiFePO等作为阴极活性材料,并且可以使用可以用于锂二次电池的所有其他阴极活性材料。
阴极还可以包含导电材料和粘合剂。
导电材料用于向电极赋予电导率。在所配置的电池中不引起化学变化的任何导电材料都可以用作导电材料。例如,天然石墨、人造石墨、炭黑、乙炔黑、科琴黑(Ketjenblack)、碳纤维、金属粉末如铜、镍、铝、银、金属纤维等可以用作导电材料,并且可以使用包括聚苯撑衍生物(polyphenylene derivative,聚亚苯基衍生物)的一种类型的导电材料或者一种或多种类型的导电材料的混合物。
粘合剂用于将活性材料的颗粒很好地彼此粘附或粘附至集电器,该集电器用于机械地稳定电极。也就是说,在锂离子重复嵌入和脱嵌的过程中稳定地固定活性材料以防止活性材料与导电材料之间的结合松散。粘合剂可以包括聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰纤维素、聚氯乙烯、羧化聚氯乙烯(carboxylated polyvinyl chloride)、聚氟乙烯、包括环氧乙烷的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏二氟乙烯、聚乙烯、聚丙烯、苯乙烯-丁二烯橡胶、丙烯酸酯化苯乙烯-丁二烯橡胶(acrylated styrene-butadiene rubber)、环氧树脂、尼龙等,但不限于此。
阳极包括碳(C)基阳极活性材料或硅(Si)基阳极活性材料中的任何一种或多种,并且碳基阳极材料可以包括选自由人造石墨、天然石墨、石墨化碳纤维、石墨化中间相碳微珠、富勒烯和无定形碳组成的组中的一种或多种材料,并且硅基阳极活性材料可以包括SiOx和硅碳复合材料中的任何一种。具体地,在此实施方式中使用石墨阳极活性材料。
如同阴极,阳极还可以包含粘合剂和导电材料。
电解质溶液由有机溶剂和添加剂组成。
有机溶剂可以包括选自由以下组成的组中的任何一种或者两种或更多种溶剂:碳酸酯类溶剂、酯类溶剂、醚类溶剂以及酮类溶剂。
此时,碳酸酯类溶剂可以包括碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(EMC)、碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、氟代碳酸乙烯酯(FEC)、碳酸亚乙烯酯(VC)等。此外,γ-丁内酯(GBL)、乙酸正甲酯、乙酸正乙酯、乙酸正丙酯等可以用作酯类溶剂,并且二丁基醚可以用作醚类溶剂,但不限于此。
溶剂还可以包括芳烃类有机溶剂。芳烃类有机溶剂的具体实例可以单独地或组合地包括苯、氟苯、溴苯、氯苯、环己基苯、异丙基苯、正丁基苯、辛基苯、甲苯、二甲苯、均三甲苯等。
隔膜防止阴极与阳极之间的短路并且提供锂离子移动的通道。这种隔膜可以包括已知的材料如聚烯烃类聚合物膜如聚丙烯、聚乙烯、聚乙烯/聚丙烯、聚乙烯/聚丙烯/聚乙烯以及聚丙烯/聚乙烯/聚丙烯,或它们的多层、微孔膜、织造织物和非织造织物。此外,可以使用在多孔聚烯烃膜上涂覆有具有优异的稳定性的树脂的膜。
实施例
对应于比较例和实施例的电池的制备和实验
<阴极的制备>
为了制备阴极,将PVdF溶解在NMP中以制备粘合剂溶液。
通过在粘合剂溶液中混合阴极活性材料和用作导电材料的科琴黑来制备浆料。将浆料涂覆在铝箔的两侧上并干燥。
在此之后,进行轧制过程(rolling process)和干燥过程,并且将铝电极超声焊接以制备阴极。在轧制过程中,将厚度调整为120μm至150μm。
在这种情况下,将Li[Ni1-x-yCoxMny]O2(1-x-y≥0.6)(其中Ni、Co和Mn以8:1:1的重量比率混合的材料)用作阴极活性材料。
阳极的制备
通过在粘合剂溶液中混合阳极活性材料和用作导电材料的科琴黑来制备浆料。将浆料涂覆在铝箔的两侧上并且干燥。
在此之后,进行轧制过程和干燥过程,并且将铝电极超声焊接以制备阴极。在轧制过程中,将厚度调整为120μm至150μm。
此时,使用石墨作为阳极活性材料。
电解质溶液的制备
将体积比为25:45:30的碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)以及碳酸二乙酯(DEC)的混合物用作有机溶剂,并且将0.5M LiPF6和0.5M LiFSi作为锂盐溶解在溶剂中,并且注入电解质。另外,根据各个实施例,将不同比例的添加剂2加入到有机溶剂中。
纽扣电池的制备
在阴极与阳极之间插入隔膜之后,然后卷绕以制备卷芯(jelly roll)。使用所制备的卷芯和电解质制备纽扣电池。
比较例1
仅添加剂1(按重量计1.0%)用作电解质中的添加剂,并且它是不包括添加剂2的锂二次电池。
比较例2
它是使用还包含作为添加剂的添加剂1(按重量计1.0%)和LiPO2F2(按重量计0.5%)的电解质溶液的锂二次电池。
实施例1
它是使用包含添加剂1(按重量计1.0%)和添加剂2(按重量计0.1%)的电解质溶液的锂二次电池。
实施例2
它是使用还包含添加剂1(按重量计1.0%)和添加剂2(按重量计0.5%)的电解质溶液的锂二次电池。
实施例3
它是使用包含添加剂1(按重量计1.0%)和添加剂2(按重量计0.1%)的电解质溶液的锂二次电池。
对于比较例1至2和实施例1至3,测量电池初始充电和放电效率的结果、在高温(45℃)下充电和放电100次循环之后的寿命特性以及高速率(2C速率)下的速率比特性(rate-specific characteristic)示于表1、表2和表3中。
表1
表1示出比较例和实施例的电池初始效率,并且电池初始效率是指在完成锂二次电池的制造、进行充电以及然后进行放电后,通过将放电容量除以充电一次后的充电容量而获得的值。将截止电压设定为2.5V至4.2V,并且在45℃下在1C下测试C速率。
作为实验的结果,在其中加入按重量计0.1%的添加剂2的实施例2的情况下,确认了初始电池效率是最好的。在实施例1和3的情况下,发现实验结果不如比较例的结果。
图2示出了针对此的图。
表2
表2示出比较例和实施例的高温寿命,并且示出在重复100次循环的充电和放电之后与初始充电/放电容量相比可以维持多少充电/放电容量。将截止电压设定为2.5V至4.2V,并且在45℃下在1C下测试C速率。
作为实验的结果,在其中加入按重量计0.1%的添加剂2的实施例2的情况下,确认了初始电池效率是最好的。实施例3示出与比较例2相似的高温寿命,并且实施例1示出高于比较例的高温寿命。
图3示出了针对此的图。
表3
表3示出比较例和实施例的速率比特性,并且示出了与其他实验相比,通过将速率增加2倍,与现有的1C速率相比能够保持多少充电/放电容量。同样,将截止电压设置为2.5V至4.2V,并在45℃下进行实验。
作为实验的结果,在其中加入按重量计0.1%的添加剂2的实施例2的情况下,确认了速率比特性是最好的。
图4示出了针对此的图。
通过上述实验,当使用用添加剂1和添加剂2两者的电解质溶液制造锂二次电池时,可以获得具有改善的电化学性能的锂二次电池。推测这是由于添加剂2在阴极和阳极处强烈地形成CEI和SEI的事实。
从实验结果可以确认,当以2:1的重量比率添加时,添加剂1和添加剂2示出最高的电化学特性。
虽然相对于本公开的特定实施方式进行了示出和描述,但在本领域内的是,在不背离由所附权利要求提供的本公开的精神的情况下,可以对本公开进行各种改进和改变。这对于本领域普通技术人员是显而易见的。
Claims (10)
2.根据权利要求1所述的电解质溶液,其中,相对于所述电解质溶液的总重量以按重量计0.1%至1.0%包括所述4-(烯丙氧基)苯基氟硫酸酯。
3.根据权利要求1所述的电解质溶液,其中,相对于所述电解质溶液的总重量以按重量计0.1%至10%包括所述碳酸亚乙烯酯。
4.根据权利要求1所述的电解质溶液,其中,所述4-(烯丙氧基)苯基氟硫酸酯和所述碳酸亚乙烯酯以1:2的重量比率添加。
5.根据权利要求1所述的电解质溶液,其中,所述电解质盐是选自由以下组成的组中的任何一种化合物或者两种或更多种化合物的混合物:LiPF6、LiBF4、LiClO4、LiCl、LiBr、LiI、LiB10Cl10、LiCF3SO3、LiCF3.0CO2、Li(CF3SO2)3.0C、LiAsF6、LiSbF6、LiAlCl4、LiCH3SO3、LiCF3SO3、LiN(SO2.0C2F5)2、Li(CF3SO2)2N、LiC4F9SO3、LiB(C6H5)4以及Li(SO2F)2N(LiFSi)。
6.根据权利要求1所述的电解质溶液,其中,以0.5M至1.0M的浓度范围包括所述电解质盐。
7.根据权利要求1所述的电解质溶液,其中,所述有机溶剂为选自由以下组成的组中的任何一种或者两种或更多种溶剂的混合物:碳酸酯类溶剂、酯类溶剂、醚类溶剂以及酮类溶剂。
8.一种锂二次电池,包括阴极、阳极、插在所述阴极与所述阳极之间的隔膜以及权利要求1所述的电解质溶液。
9.根据权利要求8所述的锂二次电池,其中,所述阴极包括镍钴锰基阴极活性材料。
10.根据权利要求9所述的锂二次电池,其中,在所述阴极活性材料中,以6:2:2至8:1:1的重量比率包含镍、钴和锰。
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