CN116315083B - 一种非水电解液及含有该非水电解液的锂离子电池 - Google Patents
一种非水电解液及含有该非水电解液的锂离子电池 Download PDFInfo
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- CN116315083B CN116315083B CN202111561440.0A CN202111561440A CN116315083B CN 116315083 B CN116315083 B CN 116315083B CN 202111561440 A CN202111561440 A CN 202111561440A CN 116315083 B CN116315083 B CN 116315083B
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- Prior art keywords
- carbonate
- sultone
- methyl
- additive
- electrolyte
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- -1 cyano, siloxane Chemical class 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 4
- 125000004438 haloalkoxy group Chemical group 0.000 claims abstract description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 39
- 230000000996 additive effect Effects 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 24
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 7
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 5
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 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 3
- 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 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- LXZHLNWWDDNIOJ-UHFFFAOYSA-N ethyl 2-piperidin-1-ylacetate Chemical compound CCOC(=O)CN1CCCCC1 LXZHLNWWDDNIOJ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- NCYNKWQXFADUOZ-UHFFFAOYSA-N 1,1-dioxo-2,1$l^{6}-benzoxathiol-3-one Chemical compound C1=CC=C2C(=O)OS(=O)(=O)C2=C1 NCYNKWQXFADUOZ-UHFFFAOYSA-N 0.000 claims description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-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 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
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 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
- 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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-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
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
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- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
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- 238000007599 discharging Methods 0.000 abstract description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
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Abstract
本发明涉及一种非水电解液及含有该非水电解液的锂离子电池。为了解决现有高压锂电池无法同时兼具高能量密度、高温循环和存储性、常温循环性及倍率充放性等综合性能的问题,本发明提出一种非水电解液,其含有或所示物质,其中,G1、G2独立地为键、氧、硫、氮、硅或磷,且G1和G2中至少一个为氧,R1为亚烷基、卤代亚烷基或硅基亚烷基,R2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基,R3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基或卤代烷氧基,X、Y、Z独立地为碳、氧、硫、氮或磷,且至少一个为氧、硫、氮或磷,n为2~6之间的整数,可同时改善锂电池的循环性能、高温性能和倍率性能。
Description
技术领域
本发明属于锂电池技术领域,具体涉及一种非水电解液及含有该非水电解液的锂离子电池。
背景技术
随着手机、平板电脑、智能穿戴以及ETC等新兴消费领域的出现,用电模块功耗的不断上升,常规的锂离子电池已经很难满足用户的使用需求。为提高市场发展及客户需求,锂电池目前主要从三个方面进行开发。一是寻求新的材料体系,如钴酸锂、富锂锰基、三元高镍等正极材料、硅碳等负极材料等;二是提高现有材料的截止充电电压,如4.4V、4.45V、4.6V高电压钴酸锂正极材料等;三是通过改变电池工艺,提高面密度和压实密度或使用更薄的集流体、胶带和铝塑壳等。
近年来,随着电池技术的发展飞速的提高,广阔的市场提供了更多发展机遇的同时也带来了更大的挑战,对电池使用环境适应性提出了更高的要求,需要电池在不同苛刻环境下均能保持较好的性能,因此,扩大电池使用温度范围成为了电池发展的一个重要课题。为了解决这一问题,人们在电池材料上需要取得更大的进步。电解液作为电池的血液,对电池的高低温性能影响非常大,根据文献,通常会通过在电池电解液中加入成膜添加剂来提高电池的循环性能。例如专利CN201610218844.2、专利CN201610518477.8和专利CN20121009386.5采用氟代碳酸乙烯酯、腈类化合物和其他添加剂等三类主要添加剂组合物来改善钴酸锂电池的高温存储性能。不过专利CN200580017212.X发现当电解液中加入含腈基化合物时,会导致电池存在在高温存储条件下电池溶胀现象和恢复容量显著降低的问题。
因此,为了促进高电压锂电池的发展,需要开发更多能够同时兼顾电池的循环及倍率性能和高温性能的非水电解液。
发明内容
本发明的目的在于提供一种在循环性、高温性和倍率性等方面综合性能平衡良好的非水电解液及高电压锂电池。
为实现上述目的,本发明采取的技术方案如下:
一种非水电解液,包括有机溶剂、电解质盐和添加剂,所述的添加剂包括第一添加剂,所述的第一添加剂选自通式(1)所示物质和通式(2)所示物质中的一种或多种,
其中,G1、G2独立地为键、氧、硫、氮、硅或磷,且G1和G2中至少一个为氧,
R1为亚烷基、卤代亚烷基或硅基亚烷基((-Si-CH2-)(CH3)2),
R2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基,
R3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基((CH3)3(Si-O-))、烷氧基或卤代烷氧基,
X、Y、Z独立地为碳、氧、硫、氮或磷,且至少一个为氧、硫、氮或磷,
n为2~6之间的整数。
优选地,所述的G1和所述的G2中一个为氧,另一个为键。
优选地,所述的R1为C1~C5亚烷基或C1~C5卤代亚烷基。
进一步优选地,所述的R1为C1~C4亚烷基或C1~C4卤代亚烷基。
更进一步优选地,所述的R1为C1~C3亚烷基或C1~C3卤代亚烷基。
进一步优选地,所述的R1不含支链。
优选地,所述的R2为C1~C5烷基、C1~C5氟代烷基、C1~C5烯基或C1~C5氟代烯基。
进一步优选地,所述的R2为C1~C4烷基、C1~C4氟代烷基、C1~C4烯基或C1~C4氟代烯基。
更进一步优选地,所述的R2为C1~C3烷基、C1~C3氟代烷基、C1~C3烯基或C1~C3氟代烯基。
优选地,所述的R3为氢或C1~C5烷基。
例如,所述的R3为氢、甲基、乙基或丙基。
进一步优选地,所述的R3为氢或C1~C5直链烷基。
再进一步优选地,所述的R3为氢或未取代的C1~C5直链烷基。
优选地,X、Y、Z中任意一个为氮,其余为碳。
优选地,n为3、4或5。
优选地,所述的第一添加剂为1H-咪唑-1-乙酸乙酯、2-(3-甲基吡唑-1-基)乙酸乙酯、1-哌啶乙酸乙酯或2-(1H-咪唑-1-基)异丁烯酸乙酯中的一种或多种。
优选地,所述的第一添加剂的投料量为所述的电解液的总质量的0.01~5%。
进一步优选地,所述的第一添加剂的投料量为所述的电解液的总质量的0.1~5%。
再进一步优选地,所述的第一添加剂的投料量为所述的电解液的总质量的0.1~2%。
更进一步优选地,所述的第一添加剂的投料量为所述的电解液的总质量的0.1~1%。
优选地,所述的添加剂还包括第二添加剂,所述的第二添加剂为具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种。
进一步优选地,所述的具有碳-碳不饱和键的环状碳酸酯包括但不限于碳酸亚乙烯酯、甲基碳酸亚乙烯酯、4,5-二甲基碳酸亚乙烯酯、苯基碳酸亚乙烯酯、4,5-二苯基碳酸亚乙烯酯、乙烯基碳酸亚乙烯酯、4,5-二乙烯基碳酸亚乙烯酯、烯丙基碳酸亚乙烯酯、4,5-二烯丙基碳酸亚乙烯酯、4-氟碳酸亚乙烯酯、4-氟-5-甲基碳酸亚乙烯酯、4-氟-5-苯基碳酸亚乙烯酯、4-氟-5-乙烯基碳酸亚乙烯酯、4-烯丙基-5-氟碳酸亚乙烯;乙烯基碳酸亚乙酯、4,5-二乙烯基碳酸亚乙酯、4-甲基-5-乙烯基碳酸亚乙酯、4-烯丙基-5-乙烯基碳酸亚乙酯、乙炔基碳酸亚乙酯、4,5-二乙炔基碳酸亚乙酯、4-甲基-5-乙炔基碳酸亚乙酯、4-乙烯基-5-乙炔基碳酸亚乙酯、4-烯丙基-5-乙炔基碳酸亚乙酯、苯基碳酸亚乙酯、4,5-二苯基碳酸亚乙酯、4-苯基-5-乙烯基碳酸亚乙酯、4-烯丙基-5-苯基碳酸亚乙酯、烯丙基碳酸亚乙酯、4,5-二烯丙基碳酸亚乙酯、4-甲基-5-烯丙基碳酸亚乙酯等;碳酸亚乙烯酯、甲基碳酸亚乙烯酯、4,5-二甲基碳酸亚乙烯酯、乙烯基碳酸亚乙烯酯、4,5-二乙烯基碳酸亚乙烯酯、烯丙基碳酸亚乙烯酯、4,5-二烯丙基碳酸亚乙烯酯、乙烯基碳酸亚乙酯、4,5-二乙烯基碳酸亚乙酯、4-甲基-5-乙烯基碳酸亚乙酯、烯丙基碳酸亚乙酯、4,5-二烯丙基碳酸亚乙酯、4-甲基-5-烯丙基碳酸亚乙酯、4-烯丙基-5-乙烯基碳酸亚乙酯、乙炔基碳酸亚乙酯、4,5-二乙炔基碳酸亚乙酯、4-甲基-5-乙炔基碳酸亚乙酯或4-乙烯基-5-乙炔基碳酸亚乙酯种的一种或多种。
进一步优选地,所述的具有碳-碳不饱和键的环状碳酸酯为碳酸亚乙烯酯、乙烯基碳酸亚乙酯或苯基碳酸亚乙烯酯种的一种或多种。
进一步优选地,所述的具有氟原子的环状碳酸酯包括但不限于单氟碳酸亚乙酯、4,4-二氟碳酸亚乙酯、4,5-二氟碳酸亚乙酯、4-氟-4-甲基碳酸亚乙酯、4,5-二氟-4-甲基碳酸亚乙酯、4-氟-5-甲基碳酸亚乙酯、4,4-二氟-5-甲基碳酸亚乙酯、4-(氟甲基)-碳酸亚乙酯、4-(二氟甲基)-碳酸亚乙酯、4-(三氟甲基)-碳酸亚乙酯、4-(氟甲基)-4-氟碳酸亚乙酯、4-(氟甲基)-5-氟碳酸亚乙酯、4-氟-4,5-二甲基碳酸亚乙酯、4,5-二氟-4,5-二甲基碳酸亚乙酯、4,4-二氟-5,5-二甲基碳酸亚乙酯等。
进一步优选地,所述的具有氟原子的环状碳酸酯为氟代碳酸乙烯酯和/或4,5-二氟碳酸乙烯酯。
进一步优选地,所述的环状磺酸酯化合物包括但不限于1,3-丙磺酸内酯、1-氟-1,3-丙磺酸内酯、2-氟-1,3-丙磺酸内酯、3-氟-1,3-丙磺酸内酯、1-甲基-1,3-丙磺酸内酯、2-甲基-1,3-丙磺酸内酯、3-甲基-1,3-丙磺酸内酯、1-丙烯-1,3-磺酸内酯、2-丙烯-1,3-磺酸内酯、1-氟-1-丙烯-1,3-磺酸内酯、2-氟-1-丙烯-1,3-磺酸内酯、3-氟-1-丙烯-1,3-磺酸内酯、1-氟-2-丙烯-1,3-磺酸内酯、2-氟-2-丙烯-1,3-磺酸内酯、3-氟-2-丙烯-1,3-磺酸内酯、1-甲基-1-丙烯-1,3-磺酸内酯、2-甲基-1-丙烯-1,3-磺酸内酯、3-甲基-1-丙烯-1,3-磺酸内酯、1-甲基-2-丙烯-1,3-磺酸内酯、2-甲基-2-丙烯-1,3-磺酸内酯、3-甲基-2-丙烯-1,3-磺酸内酯、1,4-丁磺酸内酯、1-氟-1,4-丁磺酸内酯、2-氟-1,4-丁磺酸内酯、3-氟-1,4-丁磺酸内酯、4-氟-1,4-丁磺酸内酯、1-甲基-1,4-丁磺酸内酯、2-甲基-1,4-丁磺酸内酯、3-甲基-1,4-丁磺酸内酯、4-甲基-1,4-丁磺酸内酯、1-丁烯-1,4-磺酸内酯、2-丁烯-1,4-磺酸内酯、3-丁烯-1,4-磺酸内酯、1-氟-1-丁烯-1,4-磺酸内酯、2-氟-1-丁烯-1,4-磺酸内酯、3-氟-1-丁烯-1,4-磺酸内酯、4-氟-1-丁烯-1,4-磺酸内酯、1-氟-2-丁烯-1,4-磺酸内酯、2-氟-2-丁烯-1,4-磺酸内酯、3-氟-2-丁烯-1,4-磺酸内酯、4-氟-2-丁烯-1,4-磺酸内酯、1-氟-3-丁烯-1,4-磺酸内酯、2-氟-3-丁烯-1,4-磺酸内酯、3-氟-3-丁烯-1,4-磺酸内酯、4-氟-3-丁烯-1,4-磺酸内酯、1-甲基-1-丁烯-1,4-磺酸内酯、2-甲基-1-丁烯-1,4-磺酸内酯、3-甲基-1-丁烯-1,4-磺酸内酯、4-甲基-1-丁烯-1,4-磺酸内酯、1-甲基-2-丁烯-1,4-磺酸内酯、2-甲基-2-丁烯-1,4-磺酸内酯、3-甲基-2-丁烯-1,4-磺酸内酯、4-甲基-2-丁烯-1,4-磺酸内酯、1-甲基-3-丁烯-1,4-磺酸内酯、2-甲基-3-丁烯-1,4-磺酸内酯、3-甲基-3-丁烯-1,4-磺酸内酯、4-甲基-3-丁烯-1,4-磺酸内酯、1,5-戊磺酸内酯、1-氟-1,5-戊磺酸内酯、2-氟-1,5-戊磺酸内酯、3-氟-1,5-戊磺酸内酯、4-氟-1,5-戊磺酸内酯、5-氟-1,5-戊磺酸内酯、1-甲基-1,5-戊磺酸内酯、2-甲基-1,5-戊磺酸内酯、3-甲基-1,5-戊磺酸内酯、4-甲基-1,5-戊磺酸内酯、5-甲基-1,5-戊磺酸内酯、1-戊烯-1,5-磺酸内酯、2-戊烯-1,5-磺酸内酯、3-戊烯-1,5-磺酸内酯、4-戊烯-1,5-磺酸内酯、1-氟-1-戊烯-1,5-磺酸内酯、2-氟-1-戊烯-1,5-磺酸内酯、3-氟-1-戊烯-1,5-磺酸内酯、4-氟-1-戊烯-1,5-磺酸内酯、5-氟-1-戊烯-1,5-磺酸内酯、1-氟-2-戊烯-1,5-磺酸内酯、2-氟-2-戊烯-1,5-磺酸内酯、3-氟-2-戊烯-1,5-磺酸内酯、4-氟-2-戊烯-1,5-磺酸内酯、5-氟-2-戊烯-1,5-磺酸内酯、1-氟-3-戊烯-1,5-磺酸内酯、2-氟-3-戊烯-1,5-磺酸内酯、3-氟-3-戊烯-1,5-磺酸内酯、4-氟-3-戊烯-1,5-磺酸内酯、5-氟-3-戊烯-1,5-磺酸内酯、1-氟-4-戊烯-1,5-磺酸内酯、2-氟-4-戊烯-1,5-磺酸内酯、3-氟-4-戊烯-1,5-磺酸内酯、4-氟-4-戊烯-1,5-磺酸内酯、5-氟-4-戊烯-1,5-磺酸内酯、1-甲基-1-戊烯-1,5-磺酸内酯、2-甲基-1-戊烯-1,5-磺酸内酯、3-甲基-1-戊烯-1,5-磺酸内酯、4-甲基-1-戊烯-1,5-磺酸内酯、5-甲基-1-戊烯-1,5-磺酸内酯、1-甲基-2-戊烯-1,5-磺酸内酯、2-甲基-2-戊烯-1,5-磺酸内酯、3-甲基-2-戊烯-1,5-磺酸内酯、4-甲基-2-戊烯-1,5-磺酸内酯、5-甲基-2-戊烯-1,5-磺酸内酯、1-甲基-3-戊烯-1,5-磺酸内酯、2-甲基-3-戊烯-1,5-磺酸内酯、3-甲基-3-戊烯-1,5-磺酸内酯、4-甲基-3-戊烯-1,5-磺酸内酯、5-甲基-3-戊烯-1,5-磺酸内酯、1-甲基-4-戊烯-1,5-磺酸内酯、2-甲基-4-戊烯-1,5-磺酸内酯、3-甲基-4-戊烯-1,5-磺酸内酯、4-甲基-4-戊烯-1,5-磺酸内酯、5-甲基-4-戊烯-1,5-磺酸内酯;硫酸亚甲酯、硫酸亚乙酯、硫酸亚丙酯、甲烷二磺酸亚甲酯或甲烷二磺酸亚乙酯中的一种或多种。
进一步优选地,所述的环状磺酸酯化合物为1,3-丙磺酸内酯、1-氟-1,3-丙磺酸内酯或甲烷二磺酸亚甲酯中的一种或多种。
进一步优选地,所述的具有氰基的化合物包括但不限于乙腈、丙腈、丁腈、异丁腈、戊腈、异戊腈、月桂腈、2-甲基丁腈、三甲基乙腈、己腈、环戊甲腈、环己甲腈、丙烯腈、甲基丙烯腈、巴豆腈、3-甲基巴豆腈、2-甲基-2-丁烯腈、2-戊烯腈、2-甲基-2-戊烯腈、3-甲基-2-戊烯腈、2-己烯腈、氟乙腈、二氟乙腈、三氟乙腈、2-氟丙腈、3-氟丙腈、2,2-二氟丙腈、2,3-二氟丙腈、3,3-二氟丙腈、2,2,3-三氟丙腈、3,3,3-三氟丙腈、3,3’-氧联二丙腈、3,3’-硫联二丙腈、1,2,3-丙三甲腈、1,3,5-戊三甲腈、五氟丙腈;丙二腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、壬二腈、癸二腈、十一烷二腈、十二烷二腈、甲基丙二腈、乙基丙二腈、异丙基丙二腈、叔丁基丙二腈、甲基丁二腈、2,2-二甲基丁二腈、2,3-二甲基丁二腈、2,3,3-三甲基丁二腈、2,2,3,3-四甲基丁二腈、2,3-二乙基-2,3-二甲基丁二腈、2,2-二乙基-3,3-二甲基丁二腈、联环己烷-1,1-二腈、联环己烷-2,2-二腈、联环己烷-3,3-二腈、2,5-二甲基-2,5-己烷二腈、2,3-二异丁基-2,3-二甲基丁二腈、2,2-二异丁基-3,3-二甲基丁二腈、2-甲基戊二腈、2,3-二甲基戊二腈、2,4-二甲基戊二腈、2,2,3,3-四甲基戊二腈、2,2,4,4-四甲基戊二腈、2,2,3,4-四甲基戊二腈、2,3,3,4-四甲基戊二腈、顺丁烯二腈、反丁烯二腈、1,4-二氰基戊烷、2,6-二氰基庚烷、2,7-二氰基辛烷、2,8-二氰基壬烷、1,6-二氰基癸烷、1,2-二氰基苯、1,3-二氰基苯、1,4-二氰基苯、3,3’-(亚乙基二氧)二丙腈、3,3’-(亚乙基二硫)二丙腈;环己三甲腈、三氰基乙胺、三氰基乙氧基丙烷、三氰基乙烯、戊三甲腈、丙三甲腈或庚三甲腈中的一种或多种。
进一步优选地,所述的具有氰基的化合物为丁二腈和/或己二腈。
根据一些具体且优选的实施例,所述的第二添加剂为碳酸亚乙烯酯、丁二腈、氟代碳酸亚乙烯酯、硫酸乙烯酯、1,3-丙烷磺内酯、1,4-丁磺酸内酯、亚硫酸乙烯酯、1,3-(1-丙烯)磺内酯、2-磺基苯甲酸酐、甲烷二磺酸亚甲酯、乙烯基亚硫酸乙烯酯、硫酸丙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯中的一种或多种。
优选地,所述的第一添加剂和所述的第二添加剂的投料量比为1:1~5。
优选地,所述的电解质盐为LiBF4、LiPF6、LiAsF6、LiClO4、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiSO3CF3、LiC2O4BC2O4、LiFC6F5BC2O4、Li2PO2F2、LiBOB或LiODFB中的一种或多种。
优选地,所述的电解质盐的摩尔浓度为0.5~2mol/L。
进一步优选的,所述的电解质盐的摩尔浓度为0.5~1.5mol/L。
优选地,所述的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、碳酯甲乙酯、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酯丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酯甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯的一种或多种。
本发明还提供一种锂离子电池,其包括正极、负极和非水电解液,所述的非水电解液为所述的非水电解液。
优选地,所述的正极活性物质为层状过渡态金属氧化物,橄榄石型磷酸盐化合物或尖晶石型含锰化合物。
优选地,所述的负极活性物质为石墨。优选地,所述的锂离子电池的电压范围为4.35-4.6V。
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:
本发明的电解液通过使用通式(1)和通式(2)所示的具有含氮杂环化合物作为添加剂,能够综合提高高电压锂电池的常温循环性能、倍率性能、高温性能,进一步地,通过与具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种联用,进一步提高其综合性能。
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。
近年来对于3C数码等领域使用的锂离子电池特性要求越来越高,锂离子要电池需要同时具有高能量密度、高温循环、高温存储性、循环性、倍率充放性等所有性能,但尚未实现。
为解决上述技术问题,本发明的发明人进行了深入研究和大量实验,得以提出一种锂离子非水电解液及使用该非水电解液的锂离子二次电池。该非水电解质电池使用具有含氮杂环化合物的非水电解液、能够吸留和放出金属离子的正极及负极,并且负极具有包含石墨粒子和能够与Li形成合金的金属粒子的负极活性物质,电压范围在4.35-4.6V之间。
根据本发明,一种非水电解液,包括有机溶剂、电解质盐和添加剂,所述的添加剂包括第一添加剂,所述的第一添加剂选自通式(1)所示物质和通式(2)所示物质中的一种或多种,
其中,G1、G2独立地为键、氧、硫、氮、硅或磷,且G1和G2中至少一个为氧,
R1为亚烷基、卤代亚烷基或硅基亚烷基,
R2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基,
R3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基或卤代烷氧基,
X、Y、Z独立地为碳、氧、硫、氮或磷,且至少一个为氧、硫、氮或磷,
n为2~6之间的整数。
根据本发明,所述的添加剂还包括第二添加剂,所述的第二添加剂选自具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种。
根据本发明,所述的第一添加剂和所述的第二添加剂的投料量分别为所述的电解液的总质量的0.01~5%。
根据本发明,所述的第一添加剂和所述的第二添加剂的投料量比为1:1~5。
根据本发明,所述的电解质盐为锂盐。
根据本发明,所述的电解质盐的摩尔浓度为0.5~2mol/L。
根据本发明,所述的有机溶剂为碳酸酯类化合物。
根据本发明,能够吸留和放出金属离子的正极为层状过渡金属氧化合物为LiCoO2,尤其是电压范围在4.35-4.6V之间的高电压钴酸锂正极材料。
本发明的非水电解液通过在含有电解质及非水溶剂的同时还含有通式(1)所示的具有含氮杂环化合物或进一步与第二添加剂配合使用,在提高非水电解质电池的循环性能和倍率放电性能的同时,提高高温保存性,可以减少气体产生量、避免电池膨胀。这里,非水电解质电池的所述的“电池膨胀”是指,在进行电池的初始调节之后,将初期的电池厚度与高温循环试验后的电池厚度进行比较,其厚度增加,即表明发生了“电池膨胀”。
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。
正极:活性物质4.35V(或4.45V)LiCoO2的质量含量95%,作为导电材料的乙炔黑3%,及作为粘结材料聚偏氟乙烯烯(PVDF)2%在N-甲基吡咯烷酮溶剂中利用分散混合器进行混合,制作浆料。将该浆料均匀涂布在铝箔的两面并进行干燥之后中,进行压制制作正极。
负极:活性物质人造石墨的质量含量95%,作为导电材料的SP 2%,及作为粘结材料的羧甲基纤维素钠(CMC)3%,利用分散混合器进行混合,制作浆料。将该浆料均匀涂布在铜箔的两面并进行干燥之后中,进行压制制作负极。
非水电解液的制备:
在充氩气的手套箱中(H2O含量<10ppm),将EC和EMC以30:70的体积比混合均匀或将DEC,EC和EMC以20:30:50的体积比混合均匀,在混合溶液中加入终浓度为1mol/L的LiPF6,制得电解液,将其称为基准电解液并作为对比例1,其他实施例和对比例的非水电解液配方见表1和表2。
非水电解质电池的制备:
将上述正极、负极、聚烯烃隔膜按照正负、隔膜、负极的顺序叠层。利用铝膜包装由此得到电池元件,注入非水电解液之后进行真空密封,制作了非水电解质二次电池。
非水电解液二次电池的评价:
电池常温测试:正极采用4.35V钴酸锂,组装好的电池首先进行化成,化成条件为:常温25℃条件下,以0.1C恒流充电至4.35V,以4.35V恒压充电2h,静置10min,再以0.2C恒流放电至3.0V。常温25℃条件下,以1C恒流充电至4.35V,再以4.35V恒压充电2h,静置10min,以1C恒流放电至3.0V,记录第一周放电容量为W1,静置10min。循环次数设定为300周,第300周放电容量记录为W300。第300周容量保持率=(W300-W1)/W1*100%.
电池倍率测试:正极采用4.35V钴酸锂,组装好的电池首先进行化成,化成条件为:常温25℃条件下,以0.1C恒流充电至4.35V,接着以4.35V恒压充电2h,静置10min,再以0.2C恒流放电至3.0V,放电容量记录为W0.2c。然后以0.2C恒流充电至4.35V,接着以4.35V恒压充电2h,静置10min,再以3.0C恒流放电至3.0V,放电容量记录为W3.0c;然后以0.2C恒流充电至4.35V,接着以4.35V恒压充电2h,静置10min,再以5.0C恒流放电至3.0V,放电容量记录为W5.0C。3C倍率放电保持率=W3.0C/W0.2c*100%;5C倍率放电保持率=W5.0C/W0.2c*100%。
电池高温测试:正极采用4.45V钴酸锂,组装好的电池首先进行化成,化成条件为:常温25℃条件下,以0.1C恒流充电至4.45V,接着以4.45V恒压充电2h,静置10min,再以0.2C恒流放电至3.0V。锂离子电池高温循环性能的测试条件为:高温45℃条件下,以1C恒流充电至4.45V,再以4.45V恒压充电2h,静置10min,以1C恒流放电至3.0V,放电容量记录为W0,静置10min,电池厚度记录为L0。循环次数设定为300周,第300周放电容量记录为W1,电池厚度记录为L1。第300周容量保持率=(W1-W0)/W0;第300周的电池膨胀率=(L1-L0)/L0。
表1非水电解液锂电池(4.35V)的常温循环及倍率性能
表2非水电解液锂离子电池(4.45V)的高温性能
A1:1H-咪唑-1-乙酸乙酯(17450-34-9);
A2:2-(3-甲基吡唑-1-基)乙酸乙酯(934172-61-9);/>
A3:1-哌啶乙酸乙酯(23853-10-3,);
A4:2-(1H-咪唑-1-基)异丁烯酸乙酯(62037-81-4
DEC:碳酸二乙酯;
EC:碳酸乙烯酯;
PC:碳酸丙烯酯;
EMC:碳酸甲乙酯;
EP:丙酸乙酯;
PP:丙酸丙酯;
VC:碳酸亚乙烯酯;
PS:1,3-丙磺酸内酯;
FEC:氟代碳酸亚乙烯酯;
SN:丁二腈。
表1显示,单独使用A1、A2、A3、A4或将A1、A2、A3或A4与第二添加剂(VC、PS、FEC和SN中的任一一个或两个)组合使用,可以改善非水电解液锂电池(4.35V)的常温循环及倍率性能,表2显示,将A1、A2、A3或A4与第二添加剂(VC、PS、FEC和SN中的任意一种或多种)组合使用,非水电解液锂电池(4.45V)高温性能显著提高。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围,凡根据本发明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之内。
Claims (10)
1.一种用于锂离子电池的非水电解液,包括有机溶剂、电解质盐和添加剂,其特征在于,所述的添加剂包括第一添加剂,所述的第一添加剂选自通式(1)所示物质和通式(2)所示物质中的一种或多种,
,
,
其中,G1和G2中一个为氧,另一个为键,
R1为亚烷基,
R2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基,
R3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基或卤代烷氧基,
X、Y、Z中Z为氮,其余为碳,
n为2~6之间的整数。
2.根据权利要求1所述的非水电解液,其特征在于,
所述的R1为C1~ C5亚烷基;
和/或,所述的R2为C1~ C5烷基、C1~ C5氟代烷基、C1~ C5烯基或C1~ C5氟代烯基;
和/或,所述的R3为氢或C1~ C5烷基;
和/或,n为3、4或5。
3.根据权利要求1所述的非水电解液,其特征在于,所述的第一添加剂选自1H-咪唑-1-乙酸乙酯、1-哌啶乙酸乙酯或2-(1H-咪唑-1-基) 异丁烯酸乙酯中的一种或多种。
4.根据权利要求1所述的非水电解液,其特征在于,所述的第一添加剂的投料量为所述的电解液的总质量的0.01~5%。
5.根据权利要求1所述的非水电解液,其特征在于,所述的添加剂还包括第二添加剂,所述的第二添加剂选自具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种;所述的第二添加剂的投料量为所述的电解液的总质量的0.01~5%。
6.根据权利要求5所述的非水电解液,其特征在于,所述的第二添加剂选自碳酸亚乙烯酯、丁二腈、氟代碳酸亚乙烯酯、硫酸乙烯酯、1-3丙烷磺内酯、1,4-丁磺酸内酯、亚硫酸乙烯酯、1,3-(1-丙烯)磺内酯、2-磺基苯甲酸酐、甲烷二磺酸亚甲酯、乙烯基亚硫酸乙烯酯、硫酸丙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯中的一种或多种。
7.根据权利要求1所述的非水电解液,其特征在于,所述的电解质盐选自LiBF4、LiPF6、LiAsF6、LiClO4、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiSO3CF3、LiPO2F2、LiBOB或LiODFB中的一种或多种;
和/或,所述的电解质盐的摩尔浓度为0.5~2 mol/L。
8.根据权利要求1所述的非水电解液,其特征在于,所述的有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酯甲乙酯、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酯丁酯、乙酸甲 酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酯甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯的一种或多种。
9.一种锂离子电池,其包括正极、负极和非水电解液,其特征在于,所述的非水电解液为权利要求1至8中任一项所述的非水电解液。
10.根据权利要求9所述的锂离子电池,其特征在于,正极活性物质为层状过渡态金属氧化物,橄榄石型磷酸盐化合物或尖晶石型含锰化合物,
和/或,负极活性物质为石墨,
和/或,所述的锂离子电池的电压范围为4.35-4.6V。
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