CN115939509A - 一种电解液和锂离子电池 - Google Patents
一种电解液和锂离子电池 Download PDFInfo
- Publication number
- CN115939509A CN115939509A CN202211544605.8A CN202211544605A CN115939509A CN 115939509 A CN115939509 A CN 115939509A CN 202211544605 A CN202211544605 A CN 202211544605A CN 115939509 A CN115939509 A CN 115939509A
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- China
- Prior art keywords
- additive
- lithium
- electrolyte
- phosphate
- triazole
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 claims abstract description 78
- 230000000996 additive effect Effects 0.000 claims abstract description 66
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- 150000003852 triazoles Chemical class 0.000 claims abstract description 11
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
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- 239000010439 graphite Substances 0.000 claims description 3
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- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
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- 229910011570 LiFe 1-x Inorganic materials 0.000 claims description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本发明属于锂离子电池技术领域,具体涉及一种电解液,所述电解液中含有第一添加剂、第二添加剂、硫酸乙烯酯;所述第一添加剂为三氮唑类添加剂;所述第二添加剂为含不饱和基团的磷酸酯类添加剂。该电解液采用三氮唑类添加剂、含不饱和基团的磷酸酯类添加剂、硫酸乙烯酯,几者协同,可以提高锂离子电池的高温和低温循环以及存储性能、改善电极成膜效果。同时,本发明还公开了一种锂离子电池。
Description
技术领域
本发明属于锂离子电池技术领域,具体涉及一种电解液和锂离子电池。
背景技术
CN 114094166 A公开了一种锂离子电池非水电解液和锂离子电池;其中1,2,4-三氮唑的磺酸盐的作用是能够优先于电解液被还原,进而成膜抑制电解液的进一步分解。所使用的磺酸盐包括了1-[2-(2,4-二氟苯基)-2,3环氧丙烷]-1H-1,2,4-三氮唑甲磺酸盐及其与其它磺酸盐的组合。
TW201309657A申请保护一种电极用添加剂,其含有胺化合物(A),该胺化合物(A)是具有1个~5个胺基的1,2,4-三唑,是3-胺基-1,2,4-三唑、3,5-二胺基-1,2,4-三唑、3-胺基-5-甲基-1,2,4-三唑、3-胺基-5-乙基-1,2,4-三唑、3-胺基-5-丙基-1,2,4-三唑及3-胺基-5-丁基-1,2,4-三唑中的至少一种。该胺化合物(A)具有胺基,且对于金属锂之氧化电位为3.8V~4.2V)借由中和反应而捕捉电池內微量含有之水分与LiPF6等含锂电解质反应而产生的氢氟酸等酸,由此可抑制自锂过渡金属多氧化物溶出过渡金属离子,使充放电循环性能及高温储藏特性提高。借由使用含有本发明之电极用添加剂的电极,可使锂离子电池或锂离子电容器的高温充放电循环性能及高温储藏特性提高。
可见1,2,4-三氮唑的衍生物根据其连接基团的不同,其功能有一定的区别,其和磺酸基协同可以起到成膜作用,和胺基复配,可以起到高温性能改善的作用。
本案的主要目的是:如何提高锂离子电池的电解液的高温和低温循环以及存储性能、改善成膜效果。
发明内容
本发明的目的是提供一种电解液,该电解液采用三氮唑类添加剂、含不饱和基团的磷酸酯类添加剂、硫酸乙烯酯,硫酸乙烯酯能够降低低温下电极与电解液之间界面膜电荷迁移阻抗,提高电池的低温性能;含不饱和基团的磷酸酯类添加剂能够有效抑制电池初始阻抗,高温储存后阻抗以及低温下阻抗增加,从而提高电池高低温性能;三氮唑类添加剂具有弱碱性,能够降低高电压下HF含量,从而提高电池的高温存储和高电压性能,几者协同,可以提高锂离子电池的高温和低温循环以及存储性能、改善电极成膜效果。
同时,本发明还公开了一种锂离子电池。
本发明的技术方案为:
一种电解液,所述电解液中含有第一添加剂、第二添加剂、硫酸乙烯酯;
所述第一添加剂为三氮唑类添加剂;所述第二添加剂为含不饱和基团的磷酸酯类添加剂。
在上述的电解液中,所述三氮唑类添加剂具体如下通式1:
R为烷基、氟代烷基、H、环烷基、杂环烷基、乙烯基或乙炔基。
所述烷基优选为碳数为1~6的烷基;如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基等;优选为甲基、乙基、正丙基、异丙基;
所述氟代烷基优选为氟代甲基,1-氟代乙基,2-氟代乙基,1-氟代丙基,2-氟代丙基;
环烷基优选为饱和或不饱和的五元环或六元环;所述不饱和的六元环可选择为苯环;
所述杂环烷基可选饱和的五元或六元杂环,所述杂环为氮杂环、硫杂环、氧杂环等;
在上述的电解液中,所述第二添加剂为磷酸三丙烯酯或三丙炔基磷酸酯。
在上述的电解液中,所述第一添加剂、第二添加剂、硫酸乙烯酯的比例为1-10:1-10:10。
优选地,所述第一添加剂、第二添加剂、硫酸乙烯酯的比例为1-8:1-8:10;
优选地,所述第一添加剂、第二添加剂、硫酸乙烯酯的比例为2-8:2-8:10;
优选地,所述第一添加剂、第二添加剂、硫酸乙烯酯的比例为3-7:3-7:10;
优选地,所述第一添加剂、第二添加剂、硫酸乙烯酯的比例为4-6:4-6:10;
在上述的电解液中,所述第一添加剂、第二添加剂、硫酸乙烯酯的总量相当于电解液总量的0.1-10wt%,更优选为,0.5-5wt%;更优选为1-4wt%,wt%后续简称为%;
所述第一添加剂、第二添加剂、硫酸乙烯酯的总量相当于电解液总量的0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%或9%;
在上述的电解液中,所述电解液中的锂盐为六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂、四氟草酸磷酸锂、二氟双草酸磷酸锂和双氟磺酰亚胺锂中的至少一种,锂盐的浓度为0.5-2M。一般来说,较为常用的锂盐的浓度为1-1.5M;但是或高、或低的锂盐浓度也是可以接受的。
在本实施例中,锂盐优选为六氟磷酸锂、双氟磺酰亚胺锂;
更优选为两种锂盐的复配以实现不同锂盐的优势的组合,比如选择六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂、四氟草酸磷酸锂、二氟双草酸磷酸锂中至少一种为主锂盐,选择双氟磺酰亚胺锂为副锂盐;主锂盐的用量大于副锂盐。
锂盐的浓度可选择为:0.5M、1M、1.5M或2M;
作为本发明的非水电解液中使用的非水溶剂,可以优选地列举出选自环状碳酸酯、链状酯、内酯、醚和酰胺中的一种或二种以上。从在宽温度范围内协同地提高电化学特性的观点出发,优选含有链状酯,更优选含有链状碳酸酯,进一步优选含有环状碳酸酯和链状碳酸酯这两者。
更为优选地,所述电解液中的非水有机溶剂为环状有机溶剂和/或链状有机溶剂;
此外,本发明的电解液中还可以含有如下任一或多种组合的辅助添加剂,辅助添加剂的用量不建议超过5%;优选为0.1-2%;
辅助添加剂为:腈类添加剂、芳香族添加剂、异氰酸酯类添加剂、其他含三键类添加剂、含S=O基类添加剂、环状缩醛类添加剂、其他含P的添加剂、环状酸酐类添加剂、环状磷腈类添加剂、含氟类添加剂;如:
乙腈、丙腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈和癸二腈中的一种或二种以上的腈;环己基苯、氟代环己基苯化合物(1-氟-2-环己基苯、1-氟-3-环己基苯、1-氟-4-环己基苯)、叔丁基苯、叔戊基苯、1-氟-4-叔丁基苯等具有支链烷基的芳香族化合物、联苯、三联苯(邻位体、间位体、对位体)、二苯基醚、氟苯、二氟苯(邻位体、间位体、对位体)、茴香醚、2,4-二氟茴香醚、三联苯的部分氢化物(1,2-二环己基苯、2-苯基双环己基、1,2-二苯基环己烷、邻环己基联苯)等芳香族化合物;选自甲基异氰酸酯、乙基异氰酸酯、丁基异氰酸酯、苯基异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、八亚甲基二异氰酸酯、1,4-亚苯基二异氰酸酯、丙烯酸2-异氰酸根合乙酯、和甲基丙烯酸2-异氰酸根合乙酯中的一种或二种以上的异氰酸酯化合物;选自2-丙炔基甲基碳酸酯、乙酸2-丙炔酯、甲酸2-丙炔酯、甲基丙烯酸2-丙炔酯、甲磺酸2-丙炔酯、乙烯基磺酸2-丙炔酯、2-(甲烷磺酰氧基)丙酸2-丙炔酯、二(2-丙炔基)草酸酯、2-丙炔基草酸甲基酯、2-丙炔基草酸乙基酯、戊二酸二(2-丙炔酯)、2-丁炔-1,4-二基二甲磺酸酯、2-丁炔-1,4-二基二甲酸酯、和2,4-己二炔-1,6-二基二甲磺酸酯中的一种或二种以上的含三键化合物;选自1,3-丙烷磺内酯、1,3-丁烷磺内酯、2,4-丁烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺内酯、2,2-二氧化-1,2-氧硫杂环戊烷-4-基乙酸酯、5,5-二甲基-1,2-氧硫杂环戊烷-4-酮2,2-二氧化物等磺内酯、亚硫酸亚乙酯、六氢苯并[1,3,2]二氧硫杂环戊烷-2-氧化物(也称作1,2-环己烷二醇环状亚硫酸酯)、5-乙烯基-六氢-1,3,2-苯并二氧硫醇-2-氧化物等环状亚硫酸酯、丁烷-2,3-二基二甲磺酸酯、丁烷-1,4-二基二甲磺酸酯、亚甲基甲烷二磺酸酯等磺酸酯、二乙烯基砜、1,2-双(乙烯基磺酰基)乙烷、双(2-乙烯基磺酰基乙基)醚等乙烯基砜化合物中的一种或二种以上的含S=O基化合物;选自1,3-二氧杂环戊烷、1,3-二噁烷、1,3,5-三噁烷等环状缩醛化合物;选自磷酸三甲酯、磷酸三丁酯、磷酸三辛基、磷酸三(2,2,2-三氟乙基)酯、磷酸双(2,2,2-三氟乙基)甲酯、磷酸双(2,2,2-三氟乙基)乙酯、磷酸双(2,2,2-三氟乙基)2,2-二氟乙酯、磷酸双(2,2,2-三氟乙基)2,2,3,3-四氟丙酯、磷酸双(2,2-二氟乙基)2,2,2-三氟乙酯、磷酸双(2,2,3,3-四氟丙基)2,2,2-三氟乙酯、磷酸(2,2,2-三氟乙基)(2,2,3,3-四氟丙酯)甲酯、磷酸三(1,1,1,3,3,3-六氟丙烷-2-基)酯、亚甲基双膦酸甲酯、亚甲基双膦酸乙酯、亚乙基双膦酸甲酯、亚乙基双膦酸乙酯、亚丁基双膦酸甲酯、亚丁基双膦酸乙酯、2-(二甲基磷酰基)乙酸甲酯、2-(二甲基磷酰基)乙酸乙酯、2-(二乙基磷酰基)乙酸甲酯、2-(二乙基磷酰基)乙酸乙酯、2-(二甲基磷酰基)乙酸2-丙炔酯、2-(二乙基磷酰基)乙酸2-丙炔酯、2-(二甲氧基磷酰基)乙酸甲酯、2-(二甲氧基磷酰基)乙酸乙酯、2-(二乙氧基磷酰基)乙酸甲酯、2-(二乙氧基磷酰基)乙酸乙酯、2-(二甲氧基磷酰基)乙酸2-丙炔酯、2-(二乙氧基磷酰基)乙酸2-丙炔酯、焦磷酸甲酯、和焦磷酸乙酯中的一种或二种以上的含磷化合物;乙酸酐、丙酸酐等链状的羧酸酐、或琥珀酸酐、马来酸酐、2-烯丙基琥珀酸酐、戊二酸酐、衣康酸酐、3-磺基-丙酸酐等环状酸酐;甲氧基五氟环三磷腈、乙氧基五氟环三磷腈、苯氧基五氟环三磷腈或乙氧基七氟环四磷腈等环状磷腈化合物;氟代碳酸甲乙酯、氟代碳酸二甲酯、氟代碳酸二乙酯、氟代丙酸乙酯、氟代丙酸丙酯、氟代丙酸甲酯、氟代乙酸乙酯、氟代乙酸甲酯或氟代乙酸丙酯等氟代化合物;
所述环状有机溶剂为PC、EC和BC中的一种或多种组合;
所述链状有机溶剂为DMC、DEC、EMC、MPC、MF、EF、MA、EA中的一种或多种组合。
更优选为环状有机溶剂和链状有机溶剂的组合,两者比例为1-5:1-5;更优选地,两者比例为1-2:1-2;更优选为1:1;
同时,本发明还公开了一种锂离子电池,采用的电解液如上任一所述。
在上述的锂离子电池中,所述锂离子电池的正极选自锂的过渡金属氧化物,其中,所述锂的过渡金属氧化物为LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、Li2Mn1-xO4,其中,M为选自Ni、Co、Mn、Al、Cr、Mg、Zr、Mo、V、Ti、B、F中的一种或多种,0≤a<0.2,0≤x<1;,负极选自石墨、硅碳复合材料、钛酸锂中的至少一种。
在本发明中,所述锂离子电池众所周知的应该包含隔膜和负极;
负极中的负极活性材料包含碳质材料、硅碳材料、合金材料、含锂金属复合氧化物材料中的至少一种,但不限于此,负极活性材料可选用本领域技术公知的各种可被用作电化学装置的负极活性材料的能够电化学性地嵌入、脱嵌活性离子的传统公知的材料;
负极片的制备方法是本领域技术公知的可被用于电化学装置的负极片的制备方法;负极活性物质层还包含粘合剂和溶剂。负极活性材料加入粘合剂和溶剂并根据需要加入增稠剂、导电剂、填充材料等而制成负极浆料,然后将负极浆料涂覆在负极集流体上,干燥后经过压制制备得到负极片,负极浆料在干燥冷压后形成负极活性物质层。同样地,在负极浆料的制备中,通常加入溶剂。溶剂在干燥过程中去除。粘合剂是本领域公知的可被用作负极活性物质层的粘合剂,粘合剂例如但不限于丁苯橡胶。溶剂是本领域公知的可被用作负极活性物质层的溶剂,溶剂例如但不限于水。增稠剂是本领域公知的可被用作负极活性物质层的增稠剂,增稠剂例如但不限于羧甲基纤维素。在一些实施例中,当负极活性材料包含合金材料时,可使用蒸镀法、溅射法、镀敷法等方法形成负极活性物质层;
隔离膜是本领域技术公知的可被用于电化学装置并且对于所使用的电解液稳定的隔离膜,例如但不限于,树脂、玻璃纤维、无机物。
比如,隔离膜包含聚烯烃、芳香族聚酰胺、聚四氟乙烯、聚醚砜中的至少一种。优选地,聚烯烃包含聚乙烯、聚丙烯中的至少一种。优选地,聚烯烃包含聚丙烯。优选地,隔离膜由多层材料层叠而成,例如,隔离膜为由按照聚丙烯、聚乙烯、聚丙烯的顺序层积而成的三层隔离膜。
本发明的有益效果如下:
本发明的电解液采用三氮唑类添加剂、含不饱和基团的磷酸酯类添加剂、硫酸乙烯酯;
其中,硫酸乙烯酯能够降低低温下电极与电解液之间界面膜电荷迁移阻抗,提高电池的低温性能;
含不饱和基团的磷酸酯类添加剂能够有效抑制电池初始阻抗,高温储存后阻抗以及低温下阻抗增加,从而提高电池高低温性能;
三氮唑类添加剂具有弱碱性,能够降低高电压下HF含量,从而提高电池的高温存储和高电压性能;
几者协同,可以提高锂离子电池的高温和低温循环以及存储性能、改善电极成膜效果。
具体实施方式
实施例1
1、电解液的制备:采用EC、DEC作为溶剂,体积比1:1混合后加入的锂盐LiPF6,调节体系锂盐的浓度为1.0M;加入添加剂:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯;其分别相当于电解液总重的0.2%、0.2%、0.6%。
2、正极片的制备:将正极材料(LiNi0.5Mn1.5O4)、导电剂SuperP、粘接剂PVDF和碳纳米管(CNT)按质量比95:2.3:2:0.7混合均匀制成一定粘度的锂离子电池正极浆料,涂布在集流体用铝箔的两面上,其涂布量为35g/m2,在85℃下烘干后进行冷压;然后进行切边、裁片、分条,分条后在真空条件下85℃烘干4小时,焊接极耳,制成满足要求的锂离子电池正极片。
3、负极片的制备:将石墨与导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1.5:1.0:2.5的比例制成浆料,混合均匀,用混制的浆料涂布在铜箔的两面后,烘干、辊压后得到负极片,制成满足要求的锂离子电池负极片。
4、锂离子电池的制备:将根据上述工艺制备的正极片、负极片和隔膜经叠片工艺制作成厚度为4.7mm,宽度为55mm,长度为60mm的锂离子电池,在75℃下真空烘烤10小时,注入上述电解液。静置24小时后,用0.lC(100mA)的恒流恒压充电至4.8V,然后用0.1C(180mA)恒流放电至3.0V;然后以0.5C(500mA)恒压充电至4.8V,再用0.5C(500mA)恒流放电至3.0V重复2次充放电,最后再以1C(1000mA)将电池充电至4.8V,完成电池制作。
实施例2
大体同实施例1,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.4%、0.4%、1.2%。
实施例3
大体同实施例1,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.8%、0.8%、2.4%。
实施例4
大体同实施例1,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.1%、0.1%、0.8%。
实施例5
大体同实施例2,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.2%、0.2%、1.6%。
实施例6
大体同实施例2,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.3%、0.3%、1.4%。
实施例7
大体同实施例2,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.5%、0.5%、1%。
实施例8
大体同实施例2,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.6%、0.6%、0.8%。
实施例9
大体同实施例2,不同的地方在于:1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.8%、0.8%、0.4%。
实施例10
大体同实施例2,不同的地方在于:第一添加剂为:1,2,4-1-甲基-三氮唑。
实施例11
大体同实施例2,不同的地方在于:第一添加剂为:1,2,4-1-氟代-三氮唑。
实施例12
大体同实施例2,不同的地方在于:第二添加剂为三丙炔基磷酸酯。
对比例1
大体同实施例2,不同地方在于,不含任意添加剂。
对比例2
大体同实施例2,不同的地方在于,不含第一添加剂,磷酸三丙烯酯、硫酸乙烯酯分别相当于电解液总重的0.6%、1.4%。
对比例3
大体同实施例2,不同的地方在于,不含第二添加剂,1,2,4-三氮唑、硫酸乙烯酯分别相当于电解液总重的0.6%、1.4%。
对比例4
大体同实施例2,不同的地方在于,不含硫酸乙烯酯,1,2,4-三氮唑、磷酸三丙烯酯分别相当于电解液总重的1%、1%。
对比例5
大体同实施例2,不同的地方在于,添加剂仅包含2%的1,2,4-三氮唑。
对比例6
大体同实施例2,不同的地方在于,添加剂仅包含2%的磷酸三丙烯酯。
对比例7
大体同实施例2,不同的地方在于,添加剂仅包含2%的硫酸乙烯酯。
性能测试
测试项目1:高温性能测试
对实施例1~12和对比例1~7中的锂离子电池进行高温循环性能和高温存储性能测试,测试方法如下;
高温循环性能:在45℃下,将锂离子电池先以1C恒流充电至电压4.8V,以4.8V恒压充电至电流为0.05C,然后1C恒流放电至3V,记录第1次循环的放电容量。进行200次循环充放电测试,记录第200次循环的放电容量。
容量保持率=(第200次放电容量/第1次放电容量)×100%
高温存储性能:在常温下,将锂离子电池以1C恒流充电至电压为4.8V,以4.8V恒压充电至电流为0.05C,然后以1C放电至3V,记录为存储前放电容量;将锂离子电池以1C恒流充电至电压为4.8V,以4.8V恒压充电至电流为0.05C,之后放入60℃烘箱中存储14天后,取出冷却至室温,先以1C放电至3V,记录存储后放电容量;然后将放电后的锂离子电池以1C恒流充电至电压为4.8V,以4.8V恒压充电至电流为0.05C,再以1C放电至3V,以上述工步循环10周,以第10周的放电容量为存储后恢复容量。
高温存储容量保持率=(存储后放电容量/存储前放电容量)×100%
高温存储容量恢复率=(存储后恢复容量/存储前放电容量)×100%
测试项目2:低温性能测试
对实施例1~12和对比例1~7中的锂离子电池进行低温放电性能测试,测试方法如下;
在常温下,将锂离子电池以1C恒流充电至电压为4.8V,以4.8V恒压充电至电流为0.05C,记录为室温放电容量。然后将电池放入-20℃低温柜中,搁置时间>4h,待电池温度降至-20℃,再以0.5C放电至3V,记录为-20℃0.5C放电容量。
-20℃放电容量保持率=(-20℃0.5C放电容量/室温放电容量)×100%
测试结果如下表1所示:
表1锂离子电池测试结果
结果分析
1.通过对比例1-4可见,任意两者的组合,对于高温性能可协同增加,但是对于低温性能来说,1,2,4-三氮唑的表现会受到其他两者的拖累,并未表现出优异的效果。
2.根据对比例1、5-7的对比可见,单用1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯,三者在电池的电化学性能上表现的趋势是类似的,这三者在高低温性能上具有一定的贡献,其中最为优异的是1,2,4-三氮唑;
3.通过实施例2和对比例1-3的对比可见,高温存储、循环,低温存储循环性能都有明显的改善,这说明初始阻抗的降低、循环过程阻抗升高的抑制、以及对于电解液中持续分解出来的HF的抑制是达到上述目的的根本原因之一。
4.通过实施例2和实施例10-12的对比可以发现,当第一添加剂为1,2,4-1-氟代-三氮唑,第二添加剂为三丙烯基磷酸酯,整个体系的表现最优。
5.通过实施例1-3的对比可以发现,1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯占电解液总重的2%时,整个体系的表现最优。
6.通过实施例1、4和2、5、6、7、8、9的对比发现,1,2,4-三氮唑、磷酸三丙烯酯、硫酸乙烯酯比例为1:1:3时,整个体系的表现最优。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
1.一种电解液,其特征在于,所述电解液中含有第一添加剂、第二添加剂、硫酸乙烯酯;
所述第一添加剂为三氮唑类添加剂;所述第二添加剂为含不饱和基团的磷酸酯类添加剂。
3.根据权利要求1所述的电解液,其特征在于,所述第二添加剂为磷酸三丙烯酯或三丙炔基磷酸酯。
4.根据权利要求1所述的电解液,其特征在于,所述第一添加剂、第二添加剂、硫酸乙烯酯的比例为1-10:1-10:10。
5.根据权利要求1所述的电解液,其特征在于,所述第一添加剂、第二添加剂、硫酸乙烯酯的总量相当于电解液总量的0.1-10wt%。
6.根据权利要求1所述的电解液,其特征在于,所述电解液中的锂盐为六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂、四氟草酸磷酸锂、二氟双草酸磷酸锂和双氟磺酰亚胺锂中的至少一种,锂盐的浓度为0.5-2M。
7.根据权利要求1所述的电解液,其特征在于,所述电解液中的非水有机溶剂为环状有机溶剂和/或链状有机溶剂;
所述环状有机溶剂为碳酸丙烯酯、碳酸乙烯酯和碳酸丁烯酯中的一种或多种组合;
所述链状有机溶剂为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、甲酸甲酯、甲酸乙酯、乙酸甲酯、乙酸乙酯的一种或多种组合。
8.一种锂离子电池,其特征在于,采用的电解液如权利要求1-7任一所述。
9.根据权利要求8所述的锂离子电池,其特征在于,所述锂离子电池的正极选自锂的过渡金属氧化物,其中,所述锂的过渡金属氧化物为LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、Li2Mn1-xO4,其中,M为选自Ni、Co、Mn、Al、Cr、Mg、Zr、Mo、V、Ti、B、F中的一种或多种,0≤a<0.2,0≤x<1;负极选自石墨、硅碳复合材料、钛酸锂中的至少一种。
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