CN116779965A - 一种锂电池用电解液的混合添加剂及有机电解液和锂电池 - Google Patents
一种锂电池用电解液的混合添加剂及有机电解液和锂电池 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- 239000000654 additive Substances 0.000 title claims abstract description 41
- 230000000996 additive effect Effects 0.000 title claims abstract description 34
- -1 difluoro lithium Chemical compound 0.000 claims abstract description 21
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 21
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical group FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- LKSCJMIATJONBS-UHFFFAOYSA-K trilithium oxalic acid phosphate Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] LKSCJMIATJONBS-UHFFFAOYSA-K 0.000 claims abstract description 3
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- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
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- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- XJYDIOOQMIRSSY-UHFFFAOYSA-N 1,3,2-dioxathiepane 2-oxide Chemical compound O=S1OCCCCO1 XJYDIOOQMIRSSY-UHFFFAOYSA-N 0.000 claims 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
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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
- H01M10/0566—Liquid materials
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Abstract
本发明属于锂电池领域,更具体的说,涉及一种锂电池用电解液的混合添加剂及有机电解液和锂电池,该有机电解液主要用于锂离子电池和锂金属电池。该混合添加剂为氟吡啶和二氟双草酸磷酸锂。该有机电解液包括有机溶剂、锂盐和混合添加剂,锂盐浓度为1.0mol·L‑1,氟吡啶的添加量为有机电解液总质量的0.01%~3.0%,二氟双草酸磷酸锂的添加量为有机电解液总质量的0.01%~3.0%。该混合添加剂能够在电极表面形成稳定的界面膜,有效提高锂电池的循环稳定性和动力学性能。
Description
技术领域
本发明属于锂电池领域,更具体的说,涉及一种锂电池用电解液的混合添加剂及有机电解液和锂电池,该有机电解液主要用于锂离子电池和锂金属电池。
背景技术
不可再生能源的过度使用加剧了全球变暖问题,锂电池在储能、电动汽车(EV)、消费电子等领域得到了广泛应用。然而,在要求实现更宽范围应用的背景下,现有的商用锂电仍然面临着关键的技术挑战-长循环并兼顾良好的动力学性能。
电解液调控电极界面膜,提高界面膜的电化学性能是解决上述问题的可行方法之一。电解液被誉为锂电池的“血液”,对锂电池的性能有着重要的影响。以常规电解液,碳酸乙烯酯类电解液为例,由于其在综合方面的可接受性,被广泛用于锂电池的研究。然而,由于碳酸乙烯酯的还原稳定性差,以及与锂金属存在兼容性问题,困扰了此类电解液的应用前景。因此,研究如何构建稳定的电极界面膜,提高电解液与电极的匹配性进而提升锂电池的电化学性能具有重要意义。通过在常规电解液中引入少量的添加剂被认为是一种简单、有效且经济的方法之一。
在充放电过程中,添加剂能够优先于溶剂在电极表面被氧化或者还原,形成固体电解质界面膜(SEI膜)或者阴极电解质界面膜(CEI膜),减少电解液与电极材料之间的副反应,从而保护电极材料。一个好的SEI膜或CEI膜,需要同时具备良好的化学稳定性和高的锂离子传输速率。然而,单一的添加剂往往在功能上也是单一的,甚至可能对界面膜的另一性能产生负面影响。因此,在电解液中引入多种添加剂是可行且常见的方法。
发明内容
本发明的目的是提供一种锂电池用电解液的混合添加剂及有机电解液和锂电池,这种混合添加剂能够构建良好化学稳定性和高锂离子传输速率的电极界面膜,提高锂电池的长循环和动力学性能。
为了达到上述目的,本发明的技术方案是:
一种锂电池用电解液的混合添加剂,该混合添加剂为氟吡啶和二氟双草酸磷酸锂。
所述的锂电池用电解液的混合添加剂,氟吡啶的结构为:
所述的锂电池用电解液的混合添加剂,氟吡啶为2-氟吡啶。
所述的锂电池用电解液的混合添加剂,二氟双草酸磷酸锂的结构为:
所述的锂电池用电解液的混合添加剂,混合添加剂中,氟吡啶与二氟双草酸磷酸锂的质量比例为3:7~7:3。
一种有机电解液,该有机电解液包括有机溶剂、锂盐和混合添加剂,锂盐浓度为1.0mol·L-1,氟吡啶的添加量为有机电解液总质量的0.01%~3.0%,二氟双草酸磷酸锂的添加量为有机电解液总质量的0.01%~3.0%。
所述的有机电解液,有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、氟代碳酸乙酯、y–丁内酯、碳酸二丙酯、N-甲基吡咯烷酮、N-甲基乙酰胺、N-甲基甲酰胺、二甲基甲酰胺、二乙基甲酰胺、乙腈、丁二腈、己二腈、戊二腈、二甲亚矾、亚硫酸二甲酯、碳酸亚乙烯酯、碳酸甲丙酯、1,3-二氧戊环、1,2-二乙氧基乙烷、1,2-二甲氧基乙烷、1,2-二丁氧基、四氢呋喃、1,3-二氧戊环、2-甲基四氢呋喃、环氧丙烷、乙酸乙酯、乙酸甲酯、丁酸甲酯、丁酸乙酯、丙酸甲酯、丙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、乙酸丙酯、乙二醇二甲醚、二甘醇二甲醚、二甲氧基甲烷及其它有机溶剂之一种或者两种以上组成的混合物。
所述的有机电解液,锂盐为六氟磷酸锂、双氟磺酰亚胺锂、双二氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂1,2,2,3,3-六氟丙烷-1,3-二磺酸亚胺锂、高氯酸锂、六氟砷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂及其它锂电池用锂盐之一种或两种以上的混合物。
所述的有机电解液的制备方法,包括如下步骤:
(1)在溶解有锂盐的有机溶剂中加入混合添加剂,混合添加剂无顺序地依次加入;或者,先将混合添加剂加入有机溶剂中,再将锂盐溶解于有机溶剂和混合添加剂的混合溶液中;
(2)密封后,常温搅拌24小时或者50℃~70℃下加热搅拌10~30min;
(3)常温搅拌直至混浊物或沉淀消失,制得有机电解液。
一种锂电池,在锂离子电池或锂金属电池中,采用含混合添加剂的有机电解液。
本发明的设计思想是:
氟吡啶能够在电极-电解液界面膜上形成丰富的LiF,有助于提高SEI/CEI膜的稳定性。然而LiF低的离子电导率(≈10-12S cm-1),限制了Li+在界面膜的传输,造成电池动力学性能下降。因此,为了同时提高SEI/CEI膜的锂离子传输能力,引入锂盐类添加剂二氟双草酸磷酸锂,其能够在电极-电解液界面膜上形成丰富的LixPOyFz,该成分能够显著改善锂离子在SEI/CEI膜的传输性能。氟吡啶和二氟双草酸磷酸锂的综合作用,构建了稳定且高锂离子传输能力的SEI/CEI膜,从而实现对锂电池性能的有效提升。
本发明的优点及有益效果如下:
本发明的锂电池用电解液中,采用了氟吡啶和二氟双草酸磷酸锂作为电解液混合添加剂,可优先溶剂在电极表面分解形成一层致密的保护膜,提高了正负极表面膜的稳定性,减少电解液有机溶剂在电极表面的分解。含有这种混合添加剂的电解液改善了锂电池的动力学性能,提高了使用寿命。
附图说明
图1.实施例1与对比例循环曲线图。
图2.实施例2与对比例循环曲线图。
图3.实施例3与对比例循环曲线图。
图4.实施例2与对比例倍率性能曲线图。
具体实施方式
为了使本发明的技术方案能够被更好的理解,下面结合具体实施例对本发明的内容进行进一步的阐述。
本发明所有的实施例和对比例所采用的电池体系一致,且所有电池的实际容量都在1.5~1.6mAh范围内。阴极为硫化聚丙烯腈,负极为金属锂,还包括隔离膜和电解液,通过电池组装、活化等工艺得到扣式电池。其中,在阴极的制备过程中,首先将硫化聚丙烯腈、聚偏二氟乙烯(PVDF)、导电碳黑按质量比例为7:2:1混合均匀,以N-甲基吡咯烷酮为溶剂制备获得。隔离膜为微孔性PP类薄膜。本发明所有的循环测试都是在常温25℃的环境中进行,电压测试范围均为1.0~3.0V,且循环充电电流和放电电流均为1.0C。
对比例
本对比例中,电解液溶剂为碳酸乙烯酯/碳酸二乙酯(EC/DEC,体积比=1:1),锂盐为六氟磷酸锂,浓度为1mol·L-1。
实施例1
本实施例中,电解液溶剂为碳酸乙烯酯/碳酸二乙酯(EC/DEC,体积比=1:1),锂盐为六氟磷酸锂,浓度为1mol·L-1。2-氟吡啶的添加量为电解液总质量的0.3%,二氟双草酸磷酸锂的添加量为电解液总质量的0.7%。
实施例2
本实施例中,电解液溶剂为碳酸乙烯酯/碳酸二乙酯(EC/DEC,体积比=1:1),锂盐为六氟磷酸锂,浓度为1mol·L-1。2-氟吡啶的添加量为电解液总质量的0.5%,二氟双草酸磷酸锂的添加量为电解液总质量的0.5%。
实施例3
本实施例中,电解液溶剂为碳酸乙烯酯/碳酸二乙酯(EC/DEC,体积比=1:1),锂盐为六氟磷酸锂,浓度为1mol·L-1。2-氟吡啶的添加量为电解液总质量的0.7%,二氟双草酸磷酸锂的添加量为电解液总质量的0.3%。
如图1至图3所示,实施例1、实施例2和实施例3同对比例的常温循环性能的曲线图。由图可知,与对比例相比,本发明的所有实施例均有更好的循环性能。
为了能够更加清晰的表述所有实施例的性能优势,表一对实施例1至3和对比例的循环克容量衰减率进行简要的汇总。
表一
实施例4
本实施例进行倍率性能测试,分别采用对比例和实施例2的电解液,在常温25℃的环境中进行,电压测试范围均为1.0~3.0V。
如图4所示,实施例2与对比例的倍率性能对比图。由图可知,与对比例相比,本发明的实施例2有更佳的倍率性能,表明其能够改善电池的动力学性能。
结合以上所描述的实施例,在有机电解液中共同加入氟吡啶和二氟双草酸磷酸锂混合添加剂,该混合添加剂能够在电极表面形成稳定的界面膜,用于锂电池可改善其循环稳定性及动力学性能,其中:首次循环库伦效率99.5~99.9%,循环200次克容量为950~1400mAh·g-1,克容量保持率75~98%,具有较好的应用前景。
最后需要说明的是,以上所描述的实施例仅用于描述本发明的技术方案,而非对其限制。本发明还可以对上述实施方式进行适当的修改,或者对其中部分或者全部技术特征进行等同替换。因此,对本发明的一些修改或者变更也应当落入本发明的权利要求的保护范围内。
Claims (10)
1.一种锂电池用电解液的混合添加剂,其特征在于,该混合添加剂为氟吡啶和二氟双草酸磷酸锂。
2.根据权利要求1所述的锂电池用电解液的混合添加剂,其特征在于,氟吡啶的结构为:
3.根据权利要求2所述的锂电池用电解液的混合添加剂,其特征在于,氟吡啶为2-氟吡啶。
4.根据权利要求1所述的锂电池用电解液的混合添加剂,其特征在于,二氟双草酸磷酸锂的结构为:
5.根据权利要求1所述的锂电池用电解液的混合添加剂,其特征在于,混合添加剂中,氟吡啶与二氟双草酸磷酸锂的质量比例为3:7~7:3。
6.一种使用权利要求1至5之一所述混合添加剂的有机电解液,其特征在于,该有机电解液包括有机溶剂、锂盐和混合添加剂,锂盐浓度为1.0mol·L-1,氟吡啶的添加量为有机电解液总质量的0.01%~3.0%,二氟双草酸磷酸锂的添加量为有机电解液总质量的0.01%~3.0%。
7.根据权利要求6所述的有机电解液,其特征在于,有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、氟代碳酸乙酯、y–丁内酯、碳酸二丙酯、N-甲基吡咯烷酮、N-甲基乙酰胺、N-甲基甲酰胺、二甲基甲酰胺、二乙基甲酰胺、乙腈、丁二腈、己二腈、戊二腈、二甲亚矾、亚硫酸二甲酯、碳酸亚乙烯酯、碳酸甲丙酯、1,3-二氧戊环、1,2-二乙氧基乙烷、1,2-二甲氧基乙烷、1,2-二丁氧基、四氢呋喃、1,3-二氧戊环、2-甲基四氢呋喃、环氧丙烷、乙酸乙酯、乙酸甲酯、丁酸甲酯、丁酸乙酯、丙酸甲酯、丙酸乙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、乙酸丙酯、乙二醇二甲醚、二甘醇二甲醚、二甲氧基甲烷及其它有机溶剂之一种或者两种以上组成的混合物。
8.根据权利要求6所述的有机电解液,其特征在于,锂盐为六氟磷酸锂、双氟磺酰亚胺锂、双二氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂1,2,2,3,3-六氟丙烷-1,3-二磺酸亚胺锂、高氯酸锂、六氟砷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂及其它锂电池用锂盐之一种或两种以上的混合物。
9.根据权利要求6所述的有机电解液,其特征在于,该有机电解液的制备方法,包括如下步骤:
(1)在溶解有锂盐的有机溶剂中加入混合添加剂,混合添加剂无顺序地依次加入;或者,先将混合添加剂加入有机溶剂中,再将锂盐溶解于有机溶剂和混合添加剂的混合溶液中;
(2)密封后,常温搅拌24小时或者50℃~70℃下加热搅拌10~30min;
(3)常温搅拌直至混浊物或沉淀消失,制得有机电解液。
10.一种使用权利要求6所述有机电解液的锂电池,其特征在于,在锂离子电池或锂金属电池中,采用含混合添加剂的有机电解液。
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