CN108808085B - 一种提高锂离子电池耐热失控性能的电解液 - Google Patents
一种提高锂离子电池耐热失控性能的电解液 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000003223 protective agent Substances 0.000 claims abstract description 7
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- -1 haloalkylphenoxy Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- KFJPWGWEQDFGDD-UHFFFAOYSA-N 4-fluoro-1,3,2-dioxathiolane 2-oxide Chemical compound FC1COS(=O)O1 KFJPWGWEQDFGDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [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
- YFYTYOSYQUYIJL-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Si+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Si+4].[Li+] YFYTYOSYQUYIJL-UHFFFAOYSA-K 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
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- 229910018688 LixC6 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 150000001768 cations Chemical class 0.000 description 2
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- 238000004880 explosion Methods 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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Abstract
本发明公开了一种提高锂离子电池耐热失控性能的电解液,涉及锂离子电池技术领域,包括磷酸三甲酯、环磷腈衍生物阻燃剂和锂盐、保护剂按一定比例的组合。本发明电解液的配方可以提高离子传输速率,改善了锂离子电池基础电性能。电解液难燃或不燃,能够提高电解液的闪电及安全性,在发生热失控时电池内部能够自我保护。
Description
技术领域
本发明涉及锂离子电池技术领域,尤其涉及一种提高锂离子电池耐热失控性能的电解液。
背景技术
近年来,由于对环境保护的要求越来越高以及政府加快了新能源汽车发展的相关政策引导,世界多个国家先后公布了燃油车禁售令。在新能源汽车鼓励政策持续刺激下,市场需求倍增。但由于在各种复杂的应用条件,锂离子电池体系存在发生爆炸和燃烧的安全隐患,这在很大程度上制约了动力锂离子电池的发展。在开发高能量密度以满足市场乘用车需求的同时,安全性是其能否大规模使用的决定因素。
在锂离子电池组工作的过程中,热失控是锂离子电池在使用过程中最有可能碰到的安全问题。模组由上千个电池单体放置在狭小的密闭空间中,并且单体间距小、散热效果差,热量更加容易聚积从而引发安全事故。由于电池滥用锂离子电池内部的化学反应为SEI膜的分解,导致负极材料失去保护而直接与电解液接触,并伴随着嵌入碳负极的锂与电解液发生反应及电解液自身的氧化分解,产生大量的热量诱发负极LixC6分解、LixC6与PVDF粘结剂反应及正极材料的分解。上述相关放热反应释放出的大量热量和气体造成内部温度及压力进一步升高,引燃电解液从而给电池带来燃烧、爆炸的危险。
现阶段,电解液通常采用非水性的体系,包括有机溶剂电解液,即由高纯度的有机溶剂、锂盐、必要的添加剂等原料按照一定的比例配制而成。该电解液溶剂体系均为低闪点的有机碳酸酯类,易分解、易燃烧,在电池发生爆炸时,往往会引发剧烈的燃烧,加重了安全性事故的危害程度。为解决这一难题,增加锂电池的安全性能,迫切需要改善锂电池的耐热失控性能。因此,开发一种热稳定性好、自阻燃的电解液体系,同时兼顾电性能的电解液体系对于锂电池的适用范围、未来前景都是具有十分重要的意义。
发明内容
基于背景技术存在的技术问题,本发明提出了一种提高锂离子电池耐热失控性能的电解液,该电解液能够显著改善锂离子电池在滥用状态下的安全性能,且能够兼顾电芯的电性能。
本发明是通过以下技术方案实现的:
一种提高锂离子电池耐热失控性能的电解液,包括磷酸三甲酯(TMC)、环磷腈衍生物(CPP)、锂盐和保护剂。不含有常规的碳酸酯类易燃有机溶剂,电解液难燃或不燃,在发生热失控时,电池内部有自我保护的机制。
优选地,所述环磷腈衍生物为选自下述式I所示的化合物中的一种或两种以上:
其中,R1、R2、R3、R4、R5、R6各自独立地为选自苯氧基、卤代烷基苯氧基、卤代烷氧基、烷氧基、烷基中的一种。
优选地,所述卤代烷基苯氧基中烷基的碳原子数为1~5,卤代烷氧基、烷氧基、烷基中的碳原子数为1~5。
优选地,所述卤原子为F、Cl或Br。
优选地,所述磷酸三甲酯、环磷腈衍生物的摩尔比为2:1。
优选地,所述锂盐在电解液中的浓度为1~4mol/L。使用高浓度的锂盐,提高电解液的离子导电率,弥补溶剂在电性能上的不足。当锂盐的含量小于1mol/L时,虽然耐热失控的效果明显,但电性能会受影响。当含量大于4mol/L时,电解液碱性过大,影响长期循环下正负电极材料结构稳定性。
优选地,所述锂盐为LiFSI、LiPF6、LiBF4、LiAsF6、LiClO4、LiN(SO2CF3)2、LiN(SO2C2F5)2中的至少一种。
优选地,所述保护剂为SEI成膜保护剂氟代碳酸亚乙烯酯、氟代亚硫酸丙烯酯、氟代碳酸亚乙烯酯、氟代碳酸乙烯酯(FEC)中的至少一种。
本发明的有益效果在于:
环磷腈结构的溶剂具有切断燃烧的自由基链式反应的能力,不仅能够起到传导锂离子的作用,自身还具备不易燃烧的特性,能够在电芯温度过高的情况下构建自我保护的机制。
而且环磷腈的氮原子具有较大极性容易与金属原子产生配位作用,提高对极片的润湿能力,因此,界面间阻抗降低,锂离子的浓差极化减小,从而减小析锂机率;另外,疏水性的取代基易与SEI膜中某些官能团形成氢键等分子间静电作用力,覆盖在SEI膜表面,相当于多了一层形成物理性的保护膜,能够有效的减小溶剂在负极表面还原。选用阳离子-阴离子相互作用弱的锂盐,即使在高浓度下也能提供高离子传输能力。通过提高锂盐的浓度提高电池电解液的离子导电率,能够提高电解液在常温及低温条件下的离子传输速率和降低电解液的凝固点,改善了锂离子电池低温性能。在大量锂盐阴阳离子的存在下,锂离子、溶剂阳离子、锂盐阴离子结合形成新的三维网状结构,可提升电芯的安全性。
本发明所述的电解液以环磷腈为主要溶剂(因衍生物差异,质量浓度在50-60%),协同磷酸三甲酯及高浓度锂盐可以起到传输锂离子及防止热失控电池燃烧的作用。
具体实施方式
为更好理解本发明,下面结合实施例对本发明作进一步描述,以下实施例仅是对本发明进行说明而非对其加以限定。
对比例
按表1中对比例1配制含有添加剂的锂离子电池电解液,并将电解液注入到铝壳15Ah磷酸铁锂体系锂离子电池中。将该电芯在150℃、200℃、300℃下保持30min,观察是否热失控。试验结果见表1。
实施例1~6
按表1中实施例1~6配制含有添加剂的锂离子电池电解液,并将电解液注入到铝壳15Ah磷酸铁锂体系锂离子电池中。将该电芯在150℃、200℃、300℃下保持30min,观察是否热失控。试验结果见表1。
表1对比例和实施例1-6的电解液成分和容量保持率数据
从上表1可看出,本发明制备的电解液注入到铝壳15Ah磷酸铁锂体系锂离子电池中,在300℃条件下加热30min,安全性能依然不受影响。继续升温至400度、500度,电芯保持完整,没有发生热失控。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (7)
2.根据权利要求1所述的一种提高锂离子电池耐热失控性能的电解液,其特征在于:所述卤代烷基苯氧基中烷基的碳原子数为1~5,卤代烷氧基、烷氧基、烷基中的碳原子数为1~5。
3.根据权利要求1所述的一种提高锂离子电池耐热失控性能的电解液,其特征在于:所述卤原子为F、Cl或Br。
4.根据权利要求1所述的一种提高锂离子电池耐热失控性能的电解液,其特征在于:所述磷酸三甲酯、环磷腈衍生物的摩尔比为2:1。
5.根据权利要求1所述的一种提高锂离子电池耐热失控性能的电解液,其特征在于:所述锂盐在电解液中的浓度为1~4mol/L。
6.根据权利要求1或5所述的一种提高锂离子电池耐热失控性能的电解液,其特征在于:所述锂盐为LiFSI、LiPF6、LiBF4、LiAsF6、LiClO4、LiN(SO2CF3)2、LiN(SO2C2F5)2中的至少一种。
7.根据权利要求1所述的一种提高锂离子电池耐热失控性能的电解液,其特征在于:所述保护剂为SEI成膜保护剂氟代碳酸亚乙烯酯、氟代亚硫酸丙烯酯、氟代碳酸亚乙烯酯、氟代碳酸乙烯酯中的至少一种。
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