CN114300748A - 一种草酸磷酸酯锂添加剂及制备的电解液、应用 - Google Patents
一种草酸磷酸酯锂添加剂及制备的电解液、应用 Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 30
- 239000003792 electrolyte Substances 0.000 title claims abstract description 28
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- -1 fluorosulfonyl group Chemical group 0.000 claims description 15
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
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- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
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- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
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- 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 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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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
本发明提供了一种草酸磷酸酯锂添加剂及制备的电解液、应用;添加本发明所涉及的草酸磷酸酯锂添加剂的电解液用于电池制造,可以有效提升电池的高温性能,提升电池的循环性能,而且能有效降低电池循环后的阻抗,以及高温下的内阻变化率。
Description
技术领域
本发明涉及电解液技术领域;尤其涉及一种草酸磷酸酯锂添加剂及制备的电解液、应用。
背景技术
碳循环及全球变暖已成为影响气候变化、人类生存环境的重大问题,该问题已引起全球性的关注。化石燃料的大量使用导致的温室效应,是全球变暖的最主要因素。为此,我国大力发展清洁能源。近年来,新能源汽车行业迎来飞速发展,这得益于锂离子电池技术的日益成熟。锂离子电池具有能量密度大、工作电压高、循环寿命长、自放电率低、无记忆效应等诸多优点,而被广泛应用于动力电池及消费电子等方面。锂离子电池包括正极、负极、隔膜、电解液等部分,目前电解液主要采用六氟磷酸锂作锂盐,碳酸酯类作溶剂,再添加各种功能添加剂以保证满足不同应用场景的需求。
功能添加剂包括阻燃、成膜、防过充等类型,其中成膜添加剂主要是在电极表面形成保护膜,阻止电极和电解液的直接接触,提升电池高温性能和循环稳定性能。成膜添加剂主要有碳酸亚乙烯酯、氟代碳酸乙烯酯、碳酸乙烯亚乙酯、磺酸酯、硼酸盐、氟硼酸盐等,但这些添加剂的使用,在电池的循环过程中使内阻升高,降低电池的倍率性能和循环寿命。
发明内容
本发明的目的是提供了一种草酸磷酸酯锂添加剂及制备的电解液、应用。
本发明是通过以下技术方案实现的:
本发明涉及一种草酸磷酸酯锂添加剂,添加剂的结构通式为:
其中R1、R2分别为锂基、氰基、苯基、氟磺酰基、三氟甲基磺酰基、氟磺酰亚胺锂磺酰基、三氟甲基磺酰亚胺锂磺酰基、碳原子数为1-6的烷基中的一种。
优选地,所述苯基中的氢至少一个被氟或三氟甲基取代。
优选地,所述烷基中的氢至少一个被氟或三氟甲基取代。
本发明还涉及前述草酸磷酸酯锂添加剂制备的电解液,电解液包括以下重量百分比的各组分:
优选地,所述锂盐为六氟磷酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、双(氟磺酰)亚胺锂、双(三氟甲基磺酰)亚胺锂、三氟甲磺酸锂、四氟硼酸锂、高氯酸锂、(氟磺酰)三氟甲基磺酰亚胺锂、四氯铝酸锂、六氟砷酸锂中的至少一种。
优选地,所述非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、γ-丁内酯、二氧五环、四氢呋喃、二甲基三氟乙酰胺、二甲基亚砜中的至少一种。
优选地,所述其他添加剂为碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、1,3-丙烷磺酸内脂、1,4-丁烷磺酸内酯、硫酸乙烯酯、亚硫酸乙烯酯、硫酸丙烯酯、亚硫酸丙烯酯、硫酸丁烯酯中的至少一种。
本发明还涉及前述草酸磷酸酯锂添加剂制备的电解液的应用,用于锂离子电池的制备,锂电池包括正极、负极、隔膜和所述电解液。
本发明具有以下优点:
本发明由草酸磷酸酯锂添加剂制备得到的电解液,具有较高的离子电导率,且能在电池电极表面形成稳定的保护膜,有助于提升电池的循环和高温性能;同时能有效降低电池循环后的内阻,能提升电池寿命和倍率性能。
本发明所涉及的草酸磷酸酯锂盐添加剂能在电极表面形成稳定保护膜,阻止高温下电解液和电极的副反应;同时,能有效防止正极中金属阳离子的高温溶出,进而提升电池的高温性能;本发明所涉及的草酸磷酸酯锂盐添加剂引入强吸电子基团(如:氟、磺酰基等),能提升电解液的电导率,从而提升电池的循环性能。上述两种机理都能显著降低电池的内阻,提升电池的寿命和倍率性能。
具体实施方式
下面结合具体实施例对本发明进行详细说明。应当指出的是,以下的实施实例只是对本发明的进一步说明,但本发明的保护范围并不限于以下实施例。
实施例
本实施例涉及一种草酸磷酸酯锂添加剂,添加剂的结构通式为:
其中R1、R2分别为锂基、氰基、苯基、氟磺酰基、三氟甲基磺酰基、氟磺酰亚胺锂磺酰基、三氟甲基磺酰亚胺锂磺酰基、碳原子数为1-6的烷基中的一种。
1、电解液的制备
实施例1-14、对比例1-4所涉及的电解液均按照以下方法进行配制:
将碳酸乙烯酯(EC,溶剂)、碳酸二甲酯(DMC,溶剂)、碳酸甲乙酯(EMC,溶剂)按照质量比EC:DMC:EMC=2:3:5混合均匀,加入六氟磷酸锂(锂盐)至锂盐浓度为1mol/L,加入草酸磷酸酯锂和其他添加剂,溶解搅拌均匀即制得所需电解液。
实施例1-10及对比例1-7中添加剂种类及用量如表1所示。
表1
表1中,结构1对应的草酸磷酸酯锂添加剂为:三氟甲基磺酰亚胺锂磺酸草酸磷酸酯锂锂盐,其结构式为:
表1中,结构2对应的草酸磷酸酯锂添加剂为:三氟甲醇全氟丙醇草酸磷酸四酯锂盐,其结构式为:
2、正极片的制备
将正极材料镍钴锰酸锂(LiNi0.5Co0.2Mn0.3)、导电剂Super P、碳纳米管、聚偏氟乙烯按照质量比95.5:1.5:1.5:1.5均匀分散在N,N-二甲基吡咯烷酮溶剂中,制成正极浆料;将分散好的浆料均匀涂覆在厚度为14μm的铝箔上,置于80℃鼓风烘箱中烘干,辊压、模切后制成正极片。
3、负极片的制备
将石墨、导电剂Super P、羧甲基纤维素、丁苯橡胶按照质量比94:3:2:1均匀分散在去离子水中,制成负极浆料;将分散好的负极浆料涂敷在厚度为10μm的铜箔上,置于80℃鼓风烘箱中烘干,辊压、模切后制成负极片。
4、锂离子电池的制备
将正极片、负极片、隔膜(正极片、负极片、隔膜和电解液)按照叠片工艺制成极芯,将极芯装入铝塑膜中,经历顶侧封、烘烤、注液、化成等工序制成软包电池。
5、性能测试
1)循环性能测试
充放电标准方式:常温下,以1C恒流充电至电压为4.3V,再恒压充电至电流为0.05C;以1C恒流放电至电压为3V,循环500周。
首周效率计算公式:首周放电比容量/首周充电比容量*100%
第N周循环容量保持率=第N周放电比容量/首周放电比容量*100
2)高温荷电保持率及恢复能力测试
a)电池按充电标准方式进行充电(测试内阻);
b)在55℃下储存7天;
c)室温下,搁置5h(测试内阻),电池以1C电流放电至终止电压3V;
d)电池按充电标准方式进行充电;
f)室温下,电池以1C电流放电至终止电压3V时停止试验;
荷电保持容量百分比=实际放电比容量/储存前常温1C充电比容量*100%;
容量恢复率=实际放比电容量/储存前常温1C充电比容量*100%。
上述性能测试结果,见表2所示。
表2
从实施例1-10和对比例1-7的测试结果可以看出:添加本发明所涉及的草酸磷酸酯锂添加剂的电解液用于电池制造,可以有效提升电池的高温性能,提升电池的循环性能,而且能有效降低电池循环后的阻抗,以及高温下的内阻变化率。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (8)
2.如权利要求1所述的草酸磷酸酯锂添加剂,其特征在于,所述苯基中的氢至少一个被氟或三氟甲基取代。
3.如权利要求1所述的草酸磷酸酯锂添加剂,其特征在于,所述烷基中的氢至少一个被氟或三氟甲基取代。
5.如权利要求4所述的草酸磷酸酯锂添加剂制备的电解液,其特征在于,所述锂盐为六氟磷酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、双(氟磺酰)亚胺锂、双(三氟甲基磺酰)亚胺锂、三氟甲磺酸锂、四氟硼酸锂、高氯酸锂、(氟磺酰)三氟甲基磺酰亚胺锂、四氯铝酸锂、六氟砷酸锂中的至少一种。
6.如权利要求4所述的草酸磷酸酯锂添加剂制备的电解液,其特征在于,所述非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、γ-丁内酯、二氧五环、四氢呋喃、二甲基三氟乙酰胺、二甲基亚砜中的至少一种。
7.如权利要求4所述的草酸磷酸酯锂添加剂制备的电解液,其特征在于,所述其他添加剂为碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、1,3-丙烷磺酸内脂、1,4-丁烷磺酸内酯、硫酸乙烯酯、亚硫酸乙烯酯、硫酸丙烯酯、亚硫酸丙烯酯、硫酸丁烯酯中的至少一种。
8.一种如权利要求4所述的草酸磷酸酯锂添加剂制备的电解液的应用,其特征在于,用于锂离子电池的制备,锂电池包括正极、负极、隔膜和所述电解液。
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