CN105453327B - 非水电解液和包含其的锂二次电池 - Google Patents
非水电解液和包含其的锂二次电池 Download PDFInfo
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- CN105453327B CN105453327B CN201580000321.4A CN201580000321A CN105453327B CN 105453327 B CN105453327 B CN 105453327B CN 201580000321 A CN201580000321 A CN 201580000321A CN 105453327 B CN105453327 B CN 105453327B
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- Prior art keywords
- lithium
- secondary battery
- electrolytic solution
- lithium secondary
- nonaqueous electrolytic
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 44
- -1 phosphorus compound Chemical class 0.000 claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 239000011258 core-shell material Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000001721 carbon Chemical group 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000006183 anode active material Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910008416 Li-Ti Inorganic materials 0.000 claims description 8
- 229910006861 Li—Ti Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003660 carbonate based solvent Substances 0.000 claims description 7
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 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 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011302 mesophase pitch Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 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
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- 241001614291 Anoplistes Species 0.000 claims description 2
- 229910001558 CF3SO3Li Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910018795 Li0.8Ti2.2O4 Inorganic materials 0.000 claims description 2
- 229910004174 Li1.14Ti1.71O4 Inorganic materials 0.000 claims description 2
- 229910009109 Li1.33Ti1.67O4 Inorganic materials 0.000 claims description 2
- 229910011957 Li2.67Ti1.33O4 Inorganic materials 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 2
- 229910012616 LiTi2O4 Inorganic materials 0.000 claims description 2
- 229910018671 Lix(NiaCobMnc)O2 Inorganic materials 0.000 claims description 2
- 229910018642 Lix(NiaCobMnc)O4 Inorganic materials 0.000 claims description 2
- 229910018700 LixCo1-yMnyO2 Inorganic materials 0.000 claims description 2
- 229910018708 LixCo1−yMnyO2 Inorganic materials 0.000 claims description 2
- 229910016717 LixCoPO4 Inorganic materials 0.000 claims description 2
- 229910015237 LixMn2-zCozO4 Inorganic materials 0.000 claims description 2
- 229910015260 LixMn2-zNizO4 Inorganic materials 0.000 claims description 2
- 229910015329 LixMn2O4 Inorganic materials 0.000 claims description 2
- 229910015286 LixMn2−zCozO4 Inorganic materials 0.000 claims description 2
- 229910015257 LixMn2−zNizO4 Inorganic materials 0.000 claims description 2
- 229910003007 LixMnO2 Inorganic materials 0.000 claims description 2
- 229910014212 LixNi1-yCoyO2 Inorganic materials 0.000 claims description 2
- 229910014220 LixNi1-yMnyO2 Inorganic materials 0.000 claims description 2
- 229910014322 LixNi1−yCoyO2 Inorganic materials 0.000 claims description 2
- 229910014344 LixNi1−yMnyO2 Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910006145 SO3Li Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-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
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 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
- JQQCMCDVLAZJHZ-UHFFFAOYSA-N lithium;methanesulfonic acid Chemical compound [Li].CS(O)(=O)=O JQQCMCDVLAZJHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000002296 pyrolytic carbon Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims 1
- 229910001246 LixFePO4 Inorganic materials 0.000 claims 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000011280 coal tar Substances 0.000 claims 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims 1
- 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 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 14
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 description 11
- 239000006258 conductive agent Substances 0.000 description 8
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- 238000000354 decomposition reaction Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
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- 101150058243 Lipf gene Proteins 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical class O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供一种非水电解液,其包含有机溶剂、锂盐和含有丙烯酰氧基的磷化合物,并提供一种包含所述非水电解液的锂二次电池。由于所述非水电解液包含在电池充电和放电期间在电极上形成稳定的固体电解液界面(SEI)磷化合物,所以可以提高电池在室温和低温下的初始电容和功率特性以及寿命特性。
Description
技术领域
本发明涉及一种非水电解液和包含其的锂二次电池。
背景技术
近年来,储能技术日益收到关注。随着储能技术的应用扩展至移动电话、便携式摄像机、笔记本电脑,甚至扩展电动车辆,已出现致力于电化学器件的研究和开发。
这些电化学器件中的可再充电二次电池的开发已成为人们关注的焦点。近年来,在二次电池的开发中,进行了对新电极和电池的设计的开发的研究以提高电容密度和比能。
在目前使用的二次电池中,20世纪90年代初开发的锂二次电池备受瞩目,这是因为锂二次电池可具有比利用水性电解液的传统电池更高的操作电压和显著更高的能量密度,所述传统电池例如Ni-MH电池、Ni-Cd电池和H2SO4-Pb电池。但是,锂二次电池可能具有以下局限性:因使用有机电解液而可导致发生着火和爆炸,并且锂二次电池的制造可能是困难的。因此,已开发出用于改善锂二次电池的局限性的锂离子聚合物电池。但是,锂离子聚合物电池的电容可能比锂二次电池的电容低。
在锂二次电池的初始充电期间,从正极活性材料(如锂金属氧化物)产生的锂离子向负极活性材料(如石墨)迁移,以插入负极活性材料中。此情况下,因为锂离子是高反应性的,所以锂离子与电解液和构成负极活性材料的碳在负极活性材料表面上反应形成化合物,如Li2CO3、Li2O或LiOH。这些化合物在负极活性材料的表面上形成一种稳定的膜(固态电解液界面,SEI)。负极活性材料表面上形成的膜通过发挥离子隧道的作用可以仅使锂离子通过,并且可以防止因具有高分子量的有机溶剂分子——其在电解液中随锂离子迁移——向负极活性材料的插入而导致的负极的结构的破坏。此外,因为该膜可以防止负极活性材料与电解液之间的接触,所以可能不会发生电解液的分解,并且可以可逆地维持电解液中的锂离子的量。因此,可以维持稳定的充电和放电。
但是,对于锂二次电池,由于碳材料会因碳的晶格参数变化和由随充电和放电过程的溶剂分解所导致的气体产生从电传输通道解吸,所以其电容会降低。因此,为克服这些局限性,存在开发一种提高电池的初始电容和功率的方法的持续需求。
发明内容
技术问题
本发提供一种非水电解液,其通过在电极上形成稳定的膜而可以改进电池的初始电容和功率特性以及寿命特性。
本发明还提供一种锂二次电池、一种电池模块和一种电池组,它们包含非水电解液。
技术方案
根据本发明的一个方面,提供一种非水电解液,其包含:有机溶剂;锂盐;和式1的磷化合物,
【式1】
其中,在式1中,
X1和X2各自独立地为氢原子或含有1至4个碳原子的烷基,
R选自含有1至20个碳原子的烷基、含有3至20个碳原子的环烷基、羟基和含有1至20个碳原子的烷氧基,
m为0至29的整数,且n为1或2的整数。
有益效果
因为本发明的一个实施方案的非水电解液包含含有丙烯酰氧基的磷化合物作为电解液添加剂,所以在电池中使用时,可以在充电和放电期间在电极上形成稳定的膜。因此,可以改善电池的室温和低温下的初始电容和功率特性以及寿命特性。
附图说明
以下说明书附图通过实例示出本发明的优选实施例,并且用于结合下文给出的对本发明的详细描述而使本发明的技术概念能够被进一步理解,因此,不应仅仅以这些附图中的内容解释本发明。
图1为示出实施例1和比较例1中制备的电池的电容对电压比(dQ/dV)的图。
图2为示出实施例1和比较例1中制备的电池的初始电容的图。
图3为示出实施例1和比较例1中制备的电池的功率的图。
图4为示出实施例1和比较例1中制备的电池的电阻的图。
图5为示出实施例1和比较例1中制备的电池的放电功率的图。
图6为示出当降低实施例1和比较例1中制备的电池的电阻时,电势随时间的变化的图。
具体实施方式
在下文中,将对本发明进行更加详细的描述以使本发明被更加清楚地理解。应理解的是,本说明书和权利要求书中使用的词语或术语不应理解为常规使用的字典中定义的含义。还应理解,基于发明人可以适当定义词语或术语的含义以最好地解释发明的原则,所述词语或术语应理解为具有与其在相关技术的上下文和本发明的技术构思中的含义相一致的含义。
根据本发明的一个实施方案,提供一种非水电解液,其包含:有机溶剂、锂盐和下式1的磷化合物。
【式1】
在式1中,X1和X2各自独立地为氢原子或含有1至4个碳原子的烷基。此情况下,烷基可具体为含有1至4个碳原子的线性或支化烷基,例如甲基、乙基、丙基、异丙基、正丁基或叔丁基。具体地,X可为氢原子或甲基。
此外,在式1中,R可选自:含有1至20个碳原子的烷基、含有3至20个碳原子的环烷基、羟基(-OH)和含有1至20个碳原子的烷氧基。此情况下,烷基可具体为含有1至20个碳原子的线性或支化的烷基,例如甲基、乙基、丙基、异丙基、正丁基、叔丁基、己基、庚基、辛基或癸基;环烷基可具体为环丙基、环丁基、环戊基、环己基、金刚烷基或降冰片基;且烷氧基可具体为甲氧基、乙氧基、丙氧基、丁氧基或叔丁氧基。具体地,R可为含有1至6个碳原子的线性或支化的烷基或羟基,且更具体地,可为羟基。
此外,在式1中,m为0至29的整数,特别地为0至3的整数,且更特别地为0或1的整数。
此外,在式1中,n为1或2的整数。
具体地,式1的磷化合物可为这样的化合物:其中式1中的X1和X2各自独立地为氢原子或者含有1至4个碳原子的线性或支化的烷基,且R为含有1至6个碳原子的线性或支化的烷基或羟基。具体地,式1中的磷化合物可为这样的化合物:其中X1和X2各自独立地为氢原子或者含有1至4个碳原子的线性或支化的烷基,R为羟基,m为0或1的整数,且n为1或2的整数。
此外,具体地,式1的磷化合物可为下式1a或1b的化合物。
【式1a】
【式1b】
在式1a和1b中,X1、X2和m与上文所定义的相同。
R1和R2各自独立地为含有1至20个碳原子的烷基或含有3至20个碳原子的环烷基,具体地为含有1至6个碳原子的线性或支化的烷基;且R3为羟基(-OH)或含有1至20个碳原子的烷氧基,具体地为羟基。此情况下,烷基、环烷基和烷氧基与上文所定义的相同。
更具体地,式1的磷化合物可为一个选自下式2a至2f的化合物。
式1的磷化合物可通过在电池的充电和放电期间在电极上形成稳定的固体电解液界面(SEI;钝化膜)而改善室温(23±5℃)和低温(-10℃±5℃)下且特别是低温下的寿命特性以及初始电容和功率特性。此外,对于锂二次电池中的锂钛氧化物基负极活性材料,因高电势而难以发生添加剂的还原分解反应,并且即使形成了SEI,也因锂钛氧化物的催化性能而使SEI的电阻高。相比之下,在将式1的磷化合物用作电解液添加剂的情况下,由于包含在磷化合物中的P=O基稳定锂钛氧化物的催化性能且丙烯酰氧基增进还原反应,所以SEI的电阻降低。因此,可以使电池的性能和寿命特性得到进一步提高。
上述式1的磷化合物可根据常规方法制备并使用,或者可以使用市售可得的产品。
此外,式1的磷化合物可以以基于非水电解液总重量计的0.05重量%至5.0重量%的量包含。在式1的磷化合物的量小于0.05重量%的情况下,难以在电极上形成稳定的膜,且因此因膜的形成而产生的效果会不充分。在式1的磷化合物的量大于5.0重量%的情况下,因为所形成的薄膜会起到电阻的作用,所以存在使电池的初始电容和功率降低的风险。
本发明的一个实施方案的非水电解液可包含有机溶剂和锂盐以及式1的磷化合物。
任意有机溶剂均可以没有特别限制地用作有机溶剂,条件是其可以发挥使参与电池的电化学反应的离子可通过其而移动的介质的功能。具体地,有机溶剂可包括碳酸酯基溶剂、酯基溶剂、醚基溶剂、酮基溶剂或芳族烃基溶剂,且可以使用其任意一种或者其两种或以上的混合物。
碳酸酯基溶剂具体地可包括:环状碳酸酯、线性碳酸酯或其混合物。环状碳酸酯的具体实例可为碳酸亚乙酯、碳酸亚丙酯、碳酸1,2-亚丁酯、碳酸2,3-亚丁酯、碳酸1,2-亚戊酯、碳酸2,3-亚戊酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯或其卤化物。此外,卤化物的具体实例可为氟代碳酸亚乙酯等,但是本发明不限于此。线性碳酸酯的具体实例可为碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸乙基甲酯、碳酸甲丙酯和碳酸乙丙酯,但是本发明不限于此。
此外,酯基有机溶剂具体地可包括:乙酸甲酯、乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、二甲亚砜、乙腈、二甲氧基乙烷、二乙氧基乙烷、环丁砜、γ-丁内酯、亚丙基硫或四氢呋喃,并且可以使用其任意一种或者其两种或以上的混合物。在这些材料中,考虑到改善低温性能的显著效果,酯基有机溶剂可为线性酯化合物,例如乙酸甲酯、乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯和丁酸乙酯。
此外,醚基溶剂可具体为二丁基醚或四氢呋喃,酮基溶剂可具体为环己酮,且芳族烃基溶剂可具体为苯或氟苯。
在上述有机溶剂中,由于环状碳酸酯基溶剂例如碳酸亚乙酯和碳酸亚丙酯是高粘性有机溶剂并且具有高介电常数,因此环状碳酸酯基溶剂可以使电解液中的锂盐良好地离解。此外,当上述环状碳酸酯基溶剂通过与酯基溶剂混合使用时,可以制备具有更高电导率的电解液。因此,有机溶剂可以包括上述环状碳酸酯和酯基溶剂的混合物,且可具体包含这样的混合物:其中上述酯基溶剂以比环状碳酸酯更高的浓度混合。具体地,有机溶剂可以包括混合物,在所述混合物中,环状碳酸酯基溶剂和酯基溶剂以5:5至2:8的体积比混合。当式1的磷化合物与以上述体积比混合的环状碳酸酯溶剂和酯基溶剂一起使用时,可以得到降低内部电阻和改善电池特性的进一步的改进效果。
此外,作为非水电解液中的锂盐,可以没有特别的限定地使用任意锂盐,条件是其为通常用于锂二次电池中且能够提供锂离子的化合物。具体地,锂盐可包括选自以下的任意一种:氯化锂(LiCl)、溴化锂(LiBr)、碘化锂(LiI)、高氯酸锂(LiClO4)、四氟硼酸锂(LiBF4)、六氟磷酸锂(LiPF6)、六氟砷酸锂(LiAsF6)、六氟锑酸锂(LiSbF6)、四氯铝酸锂(LiAlCl4)、甲磺酸锂(CH3SO3Li)、三氟甲磺酸锂(CF3SO3Li)、双(三氟甲基)磺酰亚胺锂(LiN(SO2CF3)2)、双(全氟乙基磺酰)亚胺锂(LiN(SO2C2F5)2)、氯硼烷锂、低级脂族羧酸酸锂和四苯基硼酸锂,或其两种或以上的混合物。
更具体地,锂盐可为六氟磷酸锂(LiPF6)。因为LiPF6离解度高,所以LiPF6可以增加非水电解液的导电性,且还可以抑制负极上的电解液的还原分解反应。因此,当将式1的磷化合物与作为锂盐的LiPF6一起使用时,可获得在室温和低温循环特性和低温电容特性方面的进一步改进效果。
此外,锂盐可以以0.6mol/L至2mol/L的浓度包含在非水电解液中。在锂盐的浓度小于0.6mol/L的情况下,因为非水电解液的电导率会降低,所以非水电解液的性能会变差。在锂盐的浓度大于2mol/L的情况下,非水电解液的粘度会增加,且因此锂离子的迁移率会减小。考虑到非水电解液的电导率和锂离子的迁移率,锂盐可具体以0.7mol/L至1.6mol/L的浓度包含在电解液中。
在本发明的实施方案的非水电解液中,除上述组分以外,非水电解液中还可以选择性地包含用于提高电池寿命特性、防止电池电容降低和提高电池的放电电容目的的添加剂。
具体地,添加剂可包括:吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚(n-glyme)、六磷三酰胺、硝基苯衍生物、硫、醌亚胺染料、N-取代的噁唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇或三氯化铝,且可以使用其任意一种或者其两种或以上的混合物。此外,添加剂的含有量可为基于非水电解液总重量计的0.1重量%至1重量%。
根据本发明的另一实施方案,提供一种包含上述非水电解液的锂二次电池。
具体地,所述锂二次电池包括负极、正极、隔膜和非水电解液。
锂二次电池可以根据本领域已知的常规方法制造,并且可以通过将多孔隔膜插入负极和正极之间并注入本发明的非水电解液制造。
在锂二次电池中,负极包括负极集电器(collector)和设置在负极集电器上的负极活性材料层。此外,负极活性材料层可包括负极活性材料并且可以选择性地另外包括导电剂和粘合剂。
在负极活性材料层中,可以将能够可逆地嵌入和脱嵌锂的化合物用作负极活性材料。作为一个具体实施例,可以使用碳材料、金属化合物或其混合物。低结晶碳和高结晶碳均可以用作碳材料。
低结晶碳的典型实例可为软碳和硬碳,高结晶碳的典型实例可为天然石墨、集结石墨、热解碳、中间相沥青基碳纤维、中间相碳微球、中间相沥青和高温烧结碳如石油或煤焦油沥青衍生的焦炭,且可没有限定地以使用任意通常用作用于锂二次电池的碳材料的材料。
此外,金属化合物可为包括至少一种金属元素的化合物,所述金属元素选自:硅(Si)、锗(Ge)、锡(Sn)、铅(Pb)、磷(P)、锑(Sb)、铋(Bi)、铝(Al)、镓(Ga)、铟(In)、钛(Ti)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、银(Ag)、镁(Mg)、锶(Sr)和钡(Ba)。这些金属化合物可以以任何形式使用,如以单质、合金、氧化物(TiO2、SnO2等)、氮化物、硫化物、硼化物或与锂的合金的形式使用,但是以单质、合金、氧化物、和与锂的合金的形式使用可以得到高电容电池。其中,化合物可以含有至少一种选自Si、Ge和Sn的元素,且当包含至少一种选自Si和Sn的元素时,可以得到具有更高电容的电池。
更具体地,负极活性材料可以包含锂钛氧化物(LTO)。具体地,锂钛氧化物可为Li0.8Ti2.2O4、Li2.67Ti1.33O4、LiTi2O4、Li1.33Ti1.67O4或Li1.14Ti1.71O4,且可以使用其任意一种或者其两种或以上的混合物。
在包含锂钛氧化物的负极的存在下,当将包含本发明实施方案的磷化合物的非水电解液注入锂二次电池中时,如上所述,电极表面上形成的SEI的电阻会减小。
此外,在负极中,使用导电剂以使负极具有导电性,并且可以没有特别限定地使用任何导电剂,条件是其具有不引起电池中逆化学变化的合适的电子电导率。导电剂的具体实例可为:碳基材料,如天然石墨或人工石墨、碳黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑、热炭黑或碳纤维;金属粉末或金属纤维,如铜、镍、铝或银;针状或树枝状导电晶须,如氧化锌晶须和碳酸钙晶须;导电金属氧化物,如氧化钛;或导电聚合物,如聚亚苯基衍生物;且可以使用其任意一种或者其两种或以上的混合物。包含的导电剂的量可为基于100重量份负极活性材料计的1重量份至30重量份。
此外,在负极中,粘合剂提高负极活性材料粒子之间的粘合性和负极活性材料与集电器之间的粘合性,并且可以没有特别限定地使用任何粘合剂,条件是其为用于形成负极的组合物中通常使用的。具体地,粘合剂可包括:氟化聚合物,如聚偏二氟乙烯(PVDF)、聚四氟乙烯、聚六氟丙烯或聚偏二氟乙烯-六氟丙烯共聚物(PVDF-共-HFP);聚亚烷基基聚合物,如聚乙烯或聚丙烯;聚(甲基)丙烯酸酯基聚合物,如聚甲基丙烯酸甲酯或聚丙烯酸酯;聚丙烯腈;纤维素基聚合物,如羧甲基纤维素(CMC);或各种橡胶,如苯乙烯-丁二烯橡胶或氟橡胶,并且可以使用其任意一种或者其两种或以上的混合物。
此外,粘合剂可为含有能够与负极活性材料表面上的羟基进行氢键和的官能团的氟化聚合物,所述官能团具体为羰基、羟基、磺酸基和缩水甘油基。因此,通过与存在于集电器或负极活性材料表面上的羟基形成氢键,包含在粘合剂中的官能团可以提高粘合性。此外,因为粘合剂可以在负极活性材料的表面上形成锂离子选择性渗透膜,所以粘合剂可以抑制锂化合物的形成,所述锂化合物通过初始放电期间电解液与负极活性材料表面上的锂离子之间的反应而合成。因此,即使电池中的温度因短路而增加,但由于热不稳定的锂化合物的量小,所以可以抑制放热分解并可以抑制电解液与负极材料中的锂离子之间的反应。粘合剂的含量可为基于100重量份负极活性材料计的1重量份至30重量份。
在锂二次电池中,正极包括正极集电器和设置在正极集电器上的正极活性材料层。此外,正极活性材料层可包括正极活性材料并且可选择性地另外包括导电剂和粘合剂。
在正极活性材料层中,可以将能够可逆地嵌入和脱嵌锂的化合物(锂化嵌入化合物)用作正极活性材料。具体地,正极活性材料可为包含锂和过渡金属如钴、锰、镍或铝的锂过渡金属氧化物,并且,具体地,可以使用选自以下的任意一种或者两种或以上的混合物:LixCoO2(0.5<x<1.3)、LixNiO2(0.5<x<1.3)、LixMnO2(0.5<x<1.3)、LixMn2O4(0.5<x<1.3)、Lix(NiaCobMnc)O2(0.5<x<1.3,0<a<1,0<b<1,0<c<1,a+b+c=1)、LixNi1-yCoyO2(0.5<x<1.3,0<y<1)、LixCo1-yMnyO2(0.5<x<1.3,0≤y<1)、LixNi1-yMnyO2(0.5<x<1.3,0≤y<1)、Lix(NiaCobMnc)O4(0.5<x<1.3,0<a<2,0<b<2,0<c<2,a+b+c=2)、LixMn2-zNizO4(0.5<x<1.3,0<z<2)、LixMn2- zCozO4(0.5<x<1.3,0<z<2)、LixCoPO4(0.5<x<1.3)和LixFePO4(0.5<x<1.3)。
此外,在正极中,导电剂和粘合剂可以与在负极中所描述的相同。
可以将在电池电压范围内具有高电导率且无反应性的任意金属——其中用于形成负极活性材料层和正极活性材料层的组合物可容易地粘附至其上——无限定地用作用在负极和正极中使用的集电器。具体地,正极集电器可包括:铝、镍或通过其结合物而制造的金属薄片,且负极集电器可包括:铜、金、镍或铜合金、或通过其结合而制造的金属薄片。此外,可以将两层或更多层由以上材料形成的基体材料堆叠并用作集电器。
此外,可以通过选择性地将负极活性材料和正极活性材料与导电剂和粘合剂混合并分散在溶剂中而分别制备的电极材料混合物,然后可以通过分别在集电器的至少一个表面上涂布、干燥和辊压电极材料混合物而制造负极和正极。此外,辊压以后,可以在真空下在约50℃至约250℃的温度下另外进行约2个小时的热处理。
通过上述方法制造的正极活性材料层的厚度(对于集电器的一个表面)可以在30μm至120μm或50μm至100μm的范围内,且负极活性材料层的厚度可以在1μm至100μm或3μm至70μm的范围内。在正极和负极满足以上厚度范围的情况下,因为各个电极活性材料层中的活性材料的量可得到充分的保证,所以可以防止电池电容的降低,并可以提高循环特性或比电容。
此外,锂二次电池中的正极和负极通过隔膜被分离,并且用作锂二次电池的隔膜的常规多孔聚合物膜可单独地或以层压的形式用作隔膜,所述多孔聚合物膜为例如由聚烯烃基聚合物制备的多孔聚合物膜,所述聚烯烃基聚合物如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物和乙烯/甲基丙烯酸酯共聚物。此外,可以使用常规多孔无纺织物,例如,由高熔点玻璃纤维或聚对苯二甲酸乙二酯纤维形成的无纺织物,但是本发明不限于此。
本发明的锂二次电池的形状没有特别的限定,并且例如可以使用采用罐的圆柱型、棱型、袋(pouch)型或硬币(coin)型。可以使用圆柱状电池,且例如,圆柱状电池可以包括电流中断装置(CID)。
因为本发明的实施方案的锂二次电池通过包含式1的磷化合物作为非水电解液添加剂而稳定地表现出改善的寿命特性以及室温和低温下且具体地在低温下(-10±5℃)的改善的初始电容和功率特性,所以该锂二次电池适用于便携装置,如移动电话、笔记本电脑和数码相机,以及电动车,如混合动力电动车。
根据本发明的另一实施方案,提供包括锂二次电池作为单元电池的电池模块和包括电池模块的电池组。
电池模块或电池组可用作中等尺寸和大尺寸装置的电源,例如用作电动工具、电动车(如电动汽车(EV)、混合动力电动车(HEV)或可外接充电(plug-in)混合动力电动车(PHEV))或蓄电系统的电源。
在下文中,将根据具体实施例对本发明进行更加详细的描述。但是,提供以下实施例仅是为了更加清楚地理解本发明,并非为了限定本发明的范围。
【实施例1】
(1)制备非水电解液
制备混合溶剂,其中将碳酸亚乙酯(EC)和丙酸丙酯(PP)以3:7的重量比混合;然后通过向混合溶剂中加入作为锂盐的LiPF6制备溶液,以得到1M的LiPF6浓度。随后,通过向溶液中加入下式2b的甲基丙烯酸磷酸酯制备非水电解液。此处,加入甲基丙烯酸磷酸酯至基于非水电解液总重量计的0.5重量%。
(2)制备正极
通过以2:1的重量比混合LiCoO2和LiNi0.56Co0.2Mn0.27O2制备正极活性材料。随后,通过以96:2:2的重量比混合正极活性材料、作为导电剂的炭黑和作为粘合剂的聚偏二氟乙烯(PVDF)制备正极材料混合物,接着通过用正极材料混合物涂布铝(Al)箔集电器并干燥经涂布的集电器制备正极。
(3)制备负极
通过以98:1:1的重量比混合作为负极活性材料的Li0.8Ti2.2O4(LTO)、苯乙烯-丁二烯橡胶(SBR)粘合剂和作为增稠剂的羧甲基纤维素(CMC)制备负极材料混合物,然后通过用负极材料混合物涂布铜(Cu)箔集电器并干燥经涂布的集电器而制备负极。
(4)制备锂二次电池
使用已制备的非水电解液和借由将多孔聚乙烯膜置于已制备的正极和负极之间而制备的电极组件通过常规方法制备币型电池。
【实施例2】
以与实施例1相同的方式制造锂二次电池,不同之处在于,使用下式2a的磷化合物替代甲基丙烯酸磷酸酯。
【实施例3】
以与实施例1相同的方式制造锂二次电池,不同之处在于,使用下式2c的磷化合物替代甲基丙烯酸磷酸酯。
【实施例4】
以与实施例1相同的方式制造锂二次电池,不同之处在于,使用下式2f的磷化合物替代甲基丙烯酸磷酸酯。
【比较例1】
以与实施例1相同的方式制造锂二次电池,不同之处在于,在实施例1的(1)非水电解液的制备中不添加甲基丙烯酸磷酸酯。
【实验实施例1:室温下电池性能的评估】
通过以下方法评估实施例1和比较例1中制造的电池的性能。每种测试重复三次,且其结果分别以三次测量的平均值表示。
将实施例1和比较例1中制备的电池在室温(23℃)下以1.2V至2.0V的驱动电压在0.1C下充电,直至充电状态(state of chage,SOC)达到20%,并观察电容相对于电压的变化。其结果示于图1。
如图1所示,对于包含含有甲基丙烯酸磷酸酯的非水电解液的实施例1的电池,在1.5V至1.8V的电压范围内观察到对应于还原反应的峰(参见虚线圆圈)。该结果是由于通过包含在实施例1的电池中的甲基丙烯酸磷酸酯在LTO负极表面上的反应形成了稳定的固体电解液界面(SEI)。
此外,将实施例1和比较例1中制备的锂二次电池在室温(23℃)下在0.3C下充电并在0.3C下放电,并测量电池的初始电容。其结果示于图2。
如图2所示,实施例1的电池——其包含含有甲基丙烯酸磷酸酯的非水电解液——表现出540mAh或以上的初始电容,较电解液中不包含甲基丙烯酸磷酸酯的比较例1的电池的初始电容(535至537mAh)提高了约0.9%。
此外,为评估在实施例1和比较例1中制备的锂二次电池的功率特性,在50%SOC下测量在23℃下充电和放电的电池的5C下的功率和电阻。其结果示于图3和图4。
如图3和图4所示,与比较例1相比,实施例1的电池——其包含含有甲基丙烯酸磷酸酯的非水电解液——的电阻降低了约11%,因此,功率特性得到提高。具体地,与比较例1相比,实施例1中制备的电池的功率提高了11%。
【实验实施例2:低温下电池性能的评估】
测量实施例1和比较例1中制备的电池在低温(-10℃)下以1.2V至2.0V的驱动电压在5C下的相对于SOC的放电功率和随着电阻降低的单位时间(脉冲:0.5秒)的功率(powerper time),各自测量三次。其结果示于图5和图6。
图5为示出实施例1和比较例1中制备的电池的放电功率的图。如图5所示,即使在-10℃的低温下,实施例1的电池——其包含含有甲基丙烯酸磷酸酯的非水电解液——表现出比比较例1中制备的电池更高的功率,具体地,表现出提高了约25%的功率。此外,电阻特性提高了约20%。
图6为示出当降低实施例1和比较例1中制备的电池的电阻时,电势随时间的变化(即功率)的图。如图6所示,可以确定,在电阻降低过程中,实施例1中制备的电池比比较例1中制备的电池具有更高的单位时间的功率。应理解,即使在低温(-10℃)下,实施例1中制备的电池的功率仍提高了约0.7%。
Claims (20)
1.一种非水电解液,其包含:
有机溶剂;
锂盐;和
式1的磷化合物,
【式1】
其中,在式1中,
X1和X2各自独立地为氢原子或含有1至4个碳原子的烷基,
R选自含有1至20个碳原子的烷基、含有3至20个碳原子的环烷基、羟基和含有1至20个碳原子的烷氧基,
m为0至29的整数,且n为1或2的整数;
其中,磷化合物的含量为基于非水电解液总重量计的0.05重量%至5.0重量%。
2.根据权利要求1所述的非水电解液,其中,X1和X2各自独立地为氢原子或含有1至4个碳原子的烷基,且
R为含有1至6个碳原子的烷基或羟基。
3.根据权利要求1所述的非水电解液,其中,X1和X2各自独立地为氢原子或含有1至4个碳原子的烷基,
R为羟基,
m为0或1的整数,且
n为1或2的整数。
4.根据权利要求1所述的非水电解液,其中,有机溶剂包括混合物,所述混合物中,环状碳酸酯基溶剂与酯基溶剂以5:5至2:8的体积比混合;
所述酯基溶剂包括任意一种选自以下的溶剂:乙酸甲酯、乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯和丁酸乙酯,或包括其两种或以上的混合物。
5.根据权利要求4所述的非水电解液,其中,环状碳酸酯基溶剂包括任意一种选自以下的溶剂:碳酸亚乙酯、碳酸亚丙酯、碳酸1,2-亚丁酯、碳酸2,3-亚丁酯、碳酸1,2-亚戊酯、碳酸2,3-亚戊酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯和氟代碳酸亚乙酯,或包括其两种或以上的混合物。
6.根据权利要求1所述的非水电解液,其中,锂盐包括任意一种选自以下的锂盐:氯化锂(LiCl)、溴化锂(LiBr)、碘化锂(LiI)、高氯酸锂(LiClO4)、四氟硼酸锂(LiBF4)、六氟磷酸锂(LiPF6)、六氟砷酸锂(LiAsF6)、六氟锑酸锂(LiSbF6)、四氯铝酸锂(LiAlCl4)、甲磺酸锂(CH3SO3Li)、三氟甲磺酸锂(CF3SO3Li)、双(三氟甲基)磺酰亚胺锂(LiN(SO2CF3)2)、双(全氟乙基磺酰)亚胺锂(LiN(SO2C2F5)2)、氯硼烷锂、脂族羧酸锂和四苯基硼酸锂,或包括其两种或以上的混合物。
7.一种锂二次电池,其包括:
正极;
负极;
隔膜;和
权利要求1所述的非水电解液。
8.根据权利要求7所述的锂二次电池,其中,负极包括选自碳材料、金属化合物及其混合物的负极活性材料。
9.根据权利要求8所述的锂二次电池,其中,碳材料包括任意一种选自以下的碳材料:软碳、硬碳、天然石墨、集结石墨,或包括其两种或以上的混合物。
10.根据权利要求8所述的锂二次电池,其中,碳材料包括任意一种选自以下的碳材料:热解碳、中间相沥青基碳纤维、中间相碳微球、中间相沥青和石油或煤焦油沥青衍生的焦炭,或包括其两种或以上的混合物。
11.根据权利要求8所述的锂二次电池,其中,金属化合物为包括任意一种选自以下金属元素或其混合物的化合物:锗(Ge)、锡(Sn)、铅(Pb)、磷(P)、锑(Sb)、铋(Bi)、铝(Al)、镓(Ga)、铟(In)、钛(Ti)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、银(Ag)、镁(Mg)、锶(Sr)和钡(Ba)。
12.根据权利要求8所述的锂二次电池,其中,所述负极活性材料包括硅(Si)。
13.据权利要求7所述的锂二次电池,其中,负极包含锂钛氧化物基负极活性材料。
14.根据权利要求13所述的锂二次电池,其中,锂钛氧化物基负极活性材料包括任意一种选自以下的材料:Li0.8Ti2.2O4、Li2.67Ti1.33O4、LiTi2O4、Li1.33Ti1.67O4和Li1.14Ti1.71O4,或包括其两种或以上的混合物。
15.根据权利要求7所述的锂二次电池,其中,正极包含正极活性材料层,所述正极活性材料层含有含锂过渡金属氧化物。
16.根据权利要求15所述的锂二次电池,其中,含锂过渡金属氧化物包括任意一个选自的化合物:LixMnO2,0.5<x<1.3;LixMn2O4,0.5<x<1.3;Lix(NiaCobMnc)O2,0.5<x<1.3,0<a<1,0<b<1,0<c<1,a+b+c=1;LixNi1-yCoyO2,0.5<x<1.3,0<y<1;LixCo1-yMnyO2,0.5<x<1.3,0≤y<1;LixNi1-yMnyO2,0.5<x<1.3,0≤y<1; Lix(NiaCobMnc)O4,0.5<x<1.3,0<a<2,0<b<2,0<c<2,a+b+c=2;LixMn2-zNizO4,0.5<x<1.3,0<z<2;LixMn2-zCozO4,0.5<x<1.3,0<z<2;LixCoPO4,0.5<x<1.3和LixFePO4,0.5<x<1.3;或包括其两种或以上的混合物。
17.根据权利要求7所述的锂二次电池,其中,隔膜包括任意一种选自以下的物质:乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物、乙烯/甲基丙烯酸酯共聚物和多孔无纺纤维,或包括其两层或以上的堆叠物。
18.一种电池模块,其包括权利要求7所述的锂二次电池作为单元电池。
19.一种电池组,其包括权利要求18所述电池模块。
20.根据权利要求19所述电池组,其中,所述电池组用作中等尺寸和大尺寸装置的电源,所述中等尺寸和大尺寸装置选自电动汽车、混合动力电动车和蓄电系统。
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