CN114497689A - 锂离子电池电解液及锂离子电池 - Google Patents
锂离子电池电解液及锂离子电池 Download PDFInfo
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- CN114497689A CN114497689A CN202011267857.1A CN202011267857A CN114497689A CN 114497689 A CN114497689 A CN 114497689A CN 202011267857 A CN202011267857 A CN 202011267857A CN 114497689 A CN114497689 A CN 114497689A
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- Prior art keywords
- compounds
- additive
- electrolyte
- lithium ion
- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 claims abstract description 50
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- -1 phosphazene compound Chemical class 0.000 claims description 58
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000001033 ether group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical group 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
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- YFWBUVZWCBFSQN-UHFFFAOYSA-N 1,2-dimethoxy-4-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1OC YFWBUVZWCBFSQN-UHFFFAOYSA-N 0.000 claims description 3
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- 229910019142 PO4 Inorganic materials 0.000 claims description 3
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- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
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- FZMPLKVGINKUJZ-UHFFFAOYSA-N 1,2-difluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C(F)=C1 FZMPLKVGINKUJZ-UHFFFAOYSA-N 0.000 claims description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- NSSFZNLWTXERTH-UHFFFAOYSA-N 1-[dipropyl-(tripropylsilylamino)silyl]propane Chemical compound CCC[Si](CCC)(CCC)N[Si](CCC)(CCC)CCC NSSFZNLWTXERTH-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- BTQZKHUEUDPRST-UHFFFAOYSA-N 1-fluoro-3-methylbenzene Chemical compound CC1=CC=CC(F)=C1 BTQZKHUEUDPRST-UHFFFAOYSA-N 0.000 claims description 2
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 claims description 2
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- HJGJHDZQLWWMRT-UHFFFAOYSA-N 2,2,2-trifluoroethyl hydrogen carbonate Chemical compound OC(=O)OCC(F)(F)F HJGJHDZQLWWMRT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims description 2
- KTFWCQSCWRZZCH-UHFFFAOYSA-N BrC1=CC(=C(C=C1)COCC1=C(C=C(C=C1)Br)F)F Chemical compound BrC1=CC(=C(C=C1)COCC1=C(C=C(C=C1)Br)F)F KTFWCQSCWRZZCH-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- HIYJCTIYKIUGET-UHFFFAOYSA-N C[SiH](C)C.C(C)NCC Chemical compound C[SiH](C)C.C(C)NCC HIYJCTIYKIUGET-UHFFFAOYSA-N 0.000 claims description 2
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- 229910007003 Li(C2F5SO2)2 Inorganic materials 0.000 claims description 2
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- 229910013089 LiBF3 Inorganic materials 0.000 claims description 2
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- 229910013884 LiPF3 Inorganic materials 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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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
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- APDDLLVYBXGBRF-UHFFFAOYSA-N [diethyl-(triethylsilylamino)silyl]ethane Chemical compound CC[Si](CC)(CC)N[Si](CC)(CC)CC APDDLLVYBXGBRF-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
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- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
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- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 2
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Abstract
本发明涉及一种锂离子电池电解液,主要解决了电解液不稳定,在高电压下易发生氧化分解的技术问题。本发明通过采用包括添加剂A、添加剂B、添加剂C中的至少一种的电解液较好的解决了该问题,使得正极材料的循环稳定性提高,正极材料在不同脱锂状态下的锂离子扩散系数增大,有效抑制电池阻抗增长,缓解三元锂离子电池在高温搁置初期电压下降速率。
Description
技术领域
本发明涉及电池技术领域,尤其涉及一种锂离子电池电解液及锂离子电池。
背景技术
锂离子电池具有能量密度高、循环性能好、储存时间长、自放电小等优点,作为理想的储能装置有望逐步替代传统的如铅酸电池、镍镉电池、镍氢电池等储能装置。随着锂离子电池应用的拓展,及现代信息技术的发展,高能量密度化的锂离子电池成为发展趋势,目前主要通过提高锂离子电池工作电压来提高电池能量密度。
而电池电压提高的同时,正极表面处于高氧化态下,容易催化电解液的氧化分解,电解液的分解产物容易在正极表面发生沉积,从而导致电池性能的劣化,因而电解液是影响电池综合性能的关键因素。目前,锂离子二次电池中广泛应用的电解液包括以六氟磷酸锂为电解质盐、以环状碳酸酯以及链状碳酸酯的混合物为有机溶剂,以碳酸亚乙烯酯、硫酸乙烯酯等为添加剂。然而上述电解液存在诸多不足,特别是应用在三元动力体系下,二次电池的循环性能、倍率性能和安全性能较差。
CN103208653B专利公开了环磷腈化合物、含硼锂盐和环状醚类化合物的协同,能够提升电池的高温存储性能、低温存储性能和循环性能,作用机理是改善电解液的浸润性,降低三元材料首周的材料活性,在三元材料表面能够俘获电池在循环过程中产生的酸性副产物,降低酸性副产物对活性材料表面保护膜的腐蚀;CN108963337B专利中提到了氟代环状碳酸酯化合物、环磷腈化合物,以及环状硫酸酯化合物的协同,改善锂离子电池的循环性能、高温存储性能和安全性能,作用机理是使得电解液能够在正负极表面形成稳定的CEI与SEI膜,保护正负极界面,同时改善锂离子电池电解液的酸性氛围,减轻HF对正负极界面的破坏作用;CN105140564B专利利用环状酸酐化合物、锂盐型添加剂和甲烷二磺酸亚甲酯,提升电池的循环性能和高温性能;CN108258311B专利提出将马来酸酐共聚物和环状硫酸酯类化合物组合添加后,可以同时在锂离子电池的正、负极形成有效的钝化膜,降低电解液在正、负极之间的副反应,进而改善锂离子电池的高温存储性能。上述专利均未就高压下电解液易分解、锂离子扩散系数低及电池在高温搁置初期电压下降速率大的问题进行改善。
发明内容
本发明所要解决的技术问题是防止电解液在更高电压下发生氧化分解,提高正极材料在高电压下的循环稳定性,同时增大正极材料在不同脱锂状态下的锂离子扩散系数,抑制电池阻抗增长,缓解三元锂离子电池在高温搁置初期电压下降速率。
为达到上述目的,本发明采用的技术方案如下:
一种锂离子电池电解液,包括有机溶剂、锂盐和添加剂,所述添加剂包括添加剂A、添加剂B和添加剂C,所述添加剂A为磷腈化合物且结构通式为所述添加剂B为含有不饱和环键的酸酐,所述添加剂C为含硫化合物且结构通式为 其中,R1、R2选自卤原子、醚基、卤代醚基、烷胺基中的任意一种,R3选自醚基、卤代醚基、烷胺基中的任意一种,R1、R2可以相同,也可以不同,所述R1、R2、R3中含卤原子时,卤原子的个数需大于6且为偶数,R4、R5、R6中任意两个为氢原子且另外一个为碳原子数小于6的烷基,R7、R8分别为碳原子数小于6的烷基。
优选地,所述添加剂A的添加量占所述电解液总质量的0.5%~2%,优选为0.8~1.5%。
优选地,所述添加剂B的添加量占所述电解液总质量的0.1%~1.0%,优选为0.3~0.8%。
优选地,所述添加剂C的添加量占所述电解液总质量的1%~3%,优选为1.5~2.5%。
优选地,R1、R2独立的选自卤原子、具有1~6个碳原子的醚基、具有1~6个碳原子的卤代醚基,具有1~6个碳原子的烷胺基中的任意一种,R3选自具有1~6个碳原子的醚基、具有1~6个碳原子的卤代醚基,具有1~6个碳原子的烷胺基中的任意一种。
进一步优选地,R1、R2独立的选自卤原子、丙基醚基、三氟乙基醚基、四氟丙基醚基、二甲基叔氨基、甲基亚氨基中的任意一种,R3选自丙基醚基、三氟乙基醚基、四氟丙基醚基、二甲基叔氨基、甲基亚氨基中的任意一种,所述R1、R2、R3中含卤原子时,所述卤原子的个数大于6且小于30。
进一步优选地,R1选自卤原子、三氟乙基醚基、四氟丙基醚基、二甲基叔氨基中的一种,R2选自卤原子、三氟乙基醚基、丙基醚基、甲基亚氨基中的任意一种,R3三氟乙基醚基、丙基醚基、甲基亚氨基中的任意一种。
优选地,所述添加剂A为
优选地,所述添加剂B包括柠康酸酐、马来酸酐、衣康酸酐中的至少一种。
优选地,所述有机溶剂包括含有碳酸酯类化合物、羧酸酯类化合物、醚类化合物、砜类化合物、亚砜类化合物、苯类化合物的至少一种。
进一步优选地,所述的有机溶剂为氟代碳酸乙烯酯、二氟碳酸乙烯酯、三氟乙基碳酸酯、氟代乙砜、四氟乙基四氟丙醚,三氟乙基六氟丙基醚、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、碳酸甲乙酯、乙二醇二甲醚、r-丁内酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、环丁砜、甲基乙基砜、二甲亚砜、氟苯中的至少两种。
优选地,所述有机溶剂包括含有氟代碳酸酯类化合物、氟代羧酸酯类化合物、氟代醚类化合物、氟代砜类化合物、氟代亚砜类化合物、氟代苯类化合物的至少一种。
优选地,所述有机溶剂添加量占所述电解液总质量的70%~85%,优选为80%~85%。
优选地,所述锂盐包括LiPF6、NaPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiN(SO2F)2、LiPF3(C2F5)3中的至少一种。
优选地,所述锂盐的添加量占所述电解液总质量的10%~25%,优选为10%~15%。
进一步优选地,所述锂盐为LiPF6。
优选地,所述添加剂还包括其他添加剂,所述其他添加剂为碳酸酯类化合物、磺酸酯类化合物、硫酸酯类化合物、亚硫酸酯类化合物,酸酐类化合物、苯化合物、氟代苯类化合物、腈类化合物、环醚类化合物、磷酸酯类化合物、亚磷酸酯类化合物、硼类化合物、胺类化合物、含硅化合物、锂盐型添加剂中的至少一种。
进一步优选地,所述其他添加剂为含有双键的环状碳酸酯类化合物、含有卤素的环状碳酸酯类化合物、磺酸酯类化合物、硫酸酯类化合物、亚硫酸酯类化合物,酸酐类化合物、苯化合物、氟代苯类化合物、腈类化合物、环醚类化合物、磷酸酯类化合物、亚磷酸酯类化合物、硼类化合物、胺类化合物、含硅化合物、锂盐型添加剂中的至少一种。
进一步优选地,所述其他添加剂包括碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲烷二磺酸亚甲酯、硫酸乙烯酯、亚硫酸乙烯酯、1,3-丙磺酸内酯、1,3-二氧六环、联苯、环己基苯、叔丁基苯、叔戊基苯、间氟甲苯、3,4-二氟甲苯、4-溴2-氟苯甲醚、对氟甲苯、对二甲苯、1,2-二甲氧基-4-硝基苯、N-苯基马来酰亚胺、五氟苯甲醚、2,5-二叔丁基、1,4-二甲氧基苯、己二腈、己烷三腈、丁二腈、1,2,3-三(2-氰乙氧基)丙烷、正丁胺、甲醇胺、乙醇胺、N,N-二环己基碳二亚胺、N,N-二乙胺三甲基硅烷、六甲基二硅氮烷、六乙基二硅氮烷或六丙基二硅氮烷、磷酸三苯酯、己二腈、庚二腈、二氟磷酸锂、二氟双草酸磷酸锂、三(三甲基硅烷)硼酸酯、三(1,1,1,3,3,3-六氟-2-丙基)亚磷酸、三(三甲基硅烷)磷酸酯中的至少一种。
优选地,所述其他添加剂的添加量为所述电解液的总质量的0.5%~5%,优选为0.5%~3%,更优选为1~2%。
本发明的一个方面是提供所述电解液在4.2V及以上的三元锂离子电池上的应用。
本发明的另一个方面是提供一种锂离子电池,包括所述电解液、壳体,以及容纳于壳体内的电芯,所述电芯包括正极、负极、介于所述正极和所述负极之间的隔膜。
优选地,所述正极包括正极集流体,以及位于正极集流体表面的正极材料,所述的正极材料包括正极活性物质、正极导电剂、正极粘结剂。
优选地,所述正极活性物质是高电压型LiNixCoyMn1-x-yO2或LiNixCoyAl1-x-yO2,所述正极导电剂为乙炔黑或碳纳米管,所述正极粘结剂为聚偏氟乙烯。
优选地,所述负极包括负极集流体、位于所述负极集流体表面的负极材料,所述负极材料包括负极活性物质、负极粘结剂,所述负极材料还可以选择性的包括负极导电剂,所述负极导电剂与所述正极导电剂可以相同也可以不相同。所述负极活性物质是金属锂、金属氧化物、锂铝合金、石墨以及改性碳材料中的任意一种,优选为石墨。
需要说明的是,所述导电剂为本领域常规使用的导电剂,所述负极粘结剂为本领域常规使用的负极粘结剂,所述负极活性物质为本领域常规使用的负极活性物质。
优选地,所述的隔膜层为本领域常规使用的隔膜层。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:本发明制备得到的电解液在更高电压下不易氧化分解,使得正极材料的循环稳定性提高,正极材料在不同脱锂状态下的锂离子扩散系数增大,有效抑制电池阻抗增长,缓解三元锂离子电池在高温搁置初期电压下降速率。
具体实施方式
下面结合实施例对本发明作进一步描述。但本发明并不限于以下实施例。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整,未注明的实施条件为本行业中的常规条件。本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
电解液的配置
本发明中的具体实施方式按照表1所述的配方在手套箱中配制电池电解液。其中,表1中涉及到的物质名称为草酸二氟硼酸锂(LiODFB)、氟代碳酸乙烯酯(FEC)、双氟磺酰亚胺锂(LiFSI)、碳酸乙烯酯(EC)、碳酸二甲酯(DEC)和碳酸甲乙酯(EMC)。
表1实施例和对比例中电解液的不同组分及其质量含量
表1中涉及的添加剂A1、A2、A3、A4、B1、B2、B3结构如下:
电池的制备
将对比例1-7和实施例1-20得到的电解液注入到同批次的LiNi0.6Co0.2Mn0.1O2(NCM622)/Li扣式电池中,测试前首先将电池充电到100%SOC,然后按照0.1C放电15min,然后静置30min,如此循环40周后放电结束,选取第四周和第二十周下的电压,分别计算出两种状态下(90%SOC/50%SOC)的锂离子扩散系数,如表2所示。
表2不同充电状态下的锂离子扩散系数
由表2可见,电池在90%SOC状态下的扩散系数可提高至1.395*10-11cm2/s,50%SOC状态下的扩散系数提高至5.048*10-11cm2/s,电池内阻下降至21.05Ω。
将对比例1-7和实施例1-20得到的电解液注入到同批次的LiNi0.6Co0.2Mn0.1O2(NCM622)的3Ah聚合物软包电池中,分别测试电池在4.4V下的高温(70℃)搁置不同天数的电压,见表3;测试电池在常温下(800周,1C/1C)的循环放电容量保持率,见表4。
表3电池的电压测试
表4常温下电池的循环放电容量保持率
本案发明人通过研究发现,添加剂A、添加剂B和添加剂C的协同组合,结合电解液中的有机溶剂、锂盐和其他添加剂,形成非水电解液,应用在高电压型的三元锂离子电池上,与现有技术相比,能将电池在90%SOC状态下的扩散系数提高至1.395*10-11cm2/s,50%SOC状态下的扩散系数提高至5.148*10-11cm2/s,电池内阻下降至21.05Ω,高温70℃搁置2天荷电电压提升至4.380V,高温70℃搁置7天电压保持在4.327V,常温800周循环电容量保持率达86.47%。
以上对本发明做了详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明的精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围内。
Claims (9)
2.如权利要求1所述的锂离子电池电解液,其特征在于:所述添加剂A的添加量占所述电解液总质量的0.5%~2%,所述添加剂B的添加量占所述电解液总质量的0.1%~1.0%,所述添加剂C的添加量占所述电解液总质量的1%~3%。
4.如权利要求1所述的锂离子电池电解液,其特征在于:所述有机溶剂包括碳酸酯类化合物、羧酸酯类化合物、醚类化合物、砜类化合物、亚砜类化合物、苯类化合物的至少一种,所述有机溶剂添加量占所述电解液总质量的70%~85%。
5.如权利要求4所述的锂离子电池电解液,其特征在于:所述有机溶剂包括氟代碳酸乙烯酯、二氟碳酸乙烯酯、三氟乙基碳酸酯、氟代乙砜、四氟乙基四氟丙醚,三氟乙基六氟丙基醚、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、碳酸甲乙酯、乙二醇二甲醚、r-丁内酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、环丁砜、甲基乙基砜、二甲亚砜、氟苯中的两种以上的混合物。
6.如权利要求1所述的锂离子电池电解液,其特征在于:所述锂盐包括LiPF6、NaPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiN(SO2F)2、LiPF3(C2F5)3中的至少一种,所述锂盐的添加量占所述电解液总质量的10%~25%。
7.如权利要求1所述的锂离子电池电解液,其特征在于:所述添加剂还包括碳酸酯类化合物、磺酸酯类化合物、硫酸酯类化合物、亚硫酸酯类化合物,酸酐类化合物、苯类化合物、氟代苯类化合物、腈类化合物、环醚类化合物、磷酸酯类化合物、亚磷酸酯类化合物、硼类化合物、胺类化合物、含硅化合物、锂盐型添加剂中的至少一种,且添加量为所述电解液的总质量的0.5%~5%。
8.如权利要求7所述的锂离子电池电解液,其特征在于:所述其他添加剂包括碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲烷二磺酸亚甲酯、硫酸乙烯酯、亚硫酸乙烯酯、1,3-丙磺酸内酯、1,3-二氧六环、联苯、环己基苯、叔丁基苯、叔戊基苯、间氟甲苯、3,4-二氟甲苯、4-溴2-氟苯甲醚、对氟甲苯、对二甲苯、1,2-二甲氧基-4-硝基苯、N-苯基马来酰亚胺、五氟苯甲醚、2,5-二叔丁基、1,4-二甲氧基苯、己二腈、己烷三腈、丁二腈、1,2,3-三(2-氰乙氧基)丙烷、正丁胺、甲醇胺、乙醇胺、N,N-二环己基碳二亚胺、N,N-二乙胺三甲基硅烷、六甲基二硅氮烷、六乙基二硅氮烷或六丙基二硅氮烷、磷酸三苯酯、己二腈、庚二腈、二氟磷酸锂、二氟双草酸磷酸锂、三(三甲基硅烷)硼酸酯、三(1,1,1,3,3,3-六氟-2-丙基)亚磷酸酯、三(三甲基硅烷)磷酸酯中的至少一种。
9.一种如权利要求1至8中任一项所述的电解液在4.2V及其以上的三元锂离子电池上的应用。
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