CN101276939A - 锂离子电池电解液 - Google Patents
锂离子电池电解液 Download PDFInfo
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- CN101276939A CN101276939A CNA2008100874787A CN200810087478A CN101276939A CN 101276939 A CN101276939 A CN 101276939A CN A2008100874787 A CNA2008100874787 A CN A2008100874787A CN 200810087478 A CN200810087478 A CN 200810087478A CN 101276939 A CN101276939 A CN 101276939A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 61
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 79
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 38
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 38
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- -1 acetate methyl isobutyryl ester Chemical class 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- XESSXNRXAYFGSO-UHFFFAOYSA-N B([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] Chemical compound B([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] XESSXNRXAYFGSO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 4
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 4
- JBDIVCUIIIVNHR-UHFFFAOYSA-M [Li]F.OP(O)(O)=O Chemical compound [Li]F.OP(O)(O)=O JBDIVCUIIIVNHR-UHFFFAOYSA-M 0.000 claims description 4
- 125000000129 anionic group Chemical class 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002322 conducting polymer Substances 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 9
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 abstract 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 abstract 1
- HNNFDXWDCFCVDM-UHFFFAOYSA-N methyl 4-methyl-3-oxopentanoate Chemical compound COC(=O)CC(=O)C(C)C HNNFDXWDCFCVDM-UHFFFAOYSA-N 0.000 abstract 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910013872 LiPF Inorganic materials 0.000 description 8
- 101150058243 Lipf gene Proteins 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003797 solvolysis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 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 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000862969 Stella Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 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 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/052—Li-accumulators
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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Abstract
本发明涉及锂离子电池电解液。可再充电的锂离子电池包括阳极、阴极和包含一种或多种分散的锂盐的电解液。该电解液由一种或多种溶剂材料组成。主要溶剂组分化合物是γ－戊内酯、乙酸甲基异丁酰基酯、乙酸2－甲氧基乙酯、乙酸2－乙氧基乙酯和草酸二乙酯中的至少一种。
Description
技术领域
本发明涉及锂离子电池。
背景技术
可再充电的锂离子电池广泛应用于便携式电池应用中，在静止和输送应用的大尺寸电池中也可以找到其应用。锂是具有高电正性(-3伏特对标准氢电极)的轻元素。电正性特征可以用于提供具有高开路电压的电池。此外，基于轻锂金属或锂基合金作为活性阳极材料的电池可以提供相对高水平的电能/单位电池重量或电能/单位电池体积的电池。
可再充电的锂离子电池具有不同的实施方案。一种实施方案包括在其结构或组成中包含锂金属或锂合金的阳极。这种电池进一步包含非水的含锂离子的电解液和包含例如LixMO2(其中M为过渡金属，例如钴、镍或锰)的阴极。在该电池元件组合的充电过程中，随着阴极中过渡金属组分(M)氧化态的增加，锂离子从阴极材料中除去。在阴极还原(电池放电)的过程中随着过渡金属组分的氧化态的降低，锂离子插入阴极。如上所述，这些电化学电池提供了较高的电压和较高的能量密度性能。
锂离子电池中的电解液可以是液体，包含非水溶剂，其中固体锂盐(例如六氟磷酸锂(LiPF6))溶解在有机溶剂(例如碳酸亚乙酯或碳酸亚丙酯)中。
为了适用于汽车应用，锂电池需要超出消费电子品和便携式计算机中对于小尺寸电池应用需求的性能特征。例如，其必须在较宽的温度范围内(包括相当低的温度)提供适合的电能。锂离子电池的汽车应用将受益于提供这种行性能特征的电解液材料。
发明内容
适用于锂离子电池电解液(lithium-ion battery electrolyte)(尤其对于车辆应用)的溶剂优选具有所有以下特征：对电解液中所用的特定锂盐(一种或多种)具有充分的溶解性；在这种锂盐(一种或多种)存在下的化学稳定性；大的电化学稳定性窗口(通常＞4V)；低温熔点(θM＜-20℃)；相对低的粘度(η＜4cP，当且仅当介电常数εr＞20时大于4cP)；高温沸点(θB＞+100℃)；高于常温的闪点(θFL＞+37℃)；低蒸汽压(在常温下通常＜1托)；适当的健康和可燃性等级；和低成本。
采用六氟磷酸锂(LiPF6)作为电解液的锂盐，对五种具有改进的低温性能的用于锂离子电池电解液的基本不含水的溶剂化合物进行了评价，发现组合了上述列出的性能需求。这些溶剂化合物是γ-戊内酯、乙酸甲基异丁酰基酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯或草酸二乙酯。这些化合物可以单独用作电解液溶剂。其可以相互混合使用，和/或与其它材料混合构成适用于锂离子电池应用的电解液组合物。但依照本发明，这五种化合物中的一种或多种往往用作电解液溶剂的主要组分(principal constituent)。例如，将适合的锂盐(例如六氟磷酸锂)以适当的浓度(例如约0.5M～约1M浓度)溶解在这些化合物中的至少一种中，以形成锂离子电池的电解液。已经发现这些化合物在含锂盐的电解液中性能良好。
依照本发明的优选的实施方案，这五种上述的酯化合物中的一种或多种是电解液溶剂的主要组分，构成了该电解液溶剂的至少50体积％，优选地构成电解液溶剂的90～95体积％。然而，可以将这些主要溶剂组分中的一种或多种与例如一种或多种碳酸酯化合物溶剂结合使用，以达到例如对于电池性能的优选总溶剂导电性或粘度。适合的碳酸酯溶剂的实例包括碳酸亚乙酯、碳酸亚丙酯、碳酸二甲酯、碳酸二乙酯和碳酸乙基甲基酯。较少量碳酸酯溶剂的添加可以例如促使在电极表面上形成所需的固体电解质界面(SEI)。在其它实施方案中，主要溶剂组分可以与凝胶或聚合组分在电解质空间中结合使用，但所述化合物中的至少一种是用于锂盐的主要溶剂组分。而且，该主要溶剂组分可以包含适合的阻燃剂添加剂等。
因此，在本发明的一种实施方案中，锂离子电池可以包括含锂金属的阳极、基本由以适当浓度溶解在上述五种溶剂化合物的一种或多种中的锂盐组成的非水电解液和与阳极和电解液一起运行的阴极。
从下面的实施方案详述中，本发明的其它目的和优点将变得更显而易见。
附图说明
图1是对于在γ-戊内酯中的1M LiPF6，采用铂工作电极和锂箔反和参考电极记录的循环伏安图(电流密度j，μA/cm2对电势E，V vs.Li/Li+)。
图2是对于在乙酸2-乙氧基乙酯中的1M LiPF6，采用铂工作电极和锂箔反和参考电极记录的循环伏安图(电流密度j，μA/cm2对电势E，V vs.Li/Li+)。
图3是描述对于在五种溶剂化合物中的1M LiPF6溶液，比电导率(specific conductivity)(κ，mS/cm)的温度依赖性的图表。
具体实施方式
提供了用于锂离子电池的电解质，其包含锂盐和改进的溶剂组合物。在本发明的一种实施方案中，该锂盐可以是六氟磷酸锂(LiPF6)。在另一实施方案中，该锂盐可以包括氟代磷酸锂、硼酸锂、酰亚胺锂(imide lithium)、氟代烷基磷酸锂、或具有氟化阴离子的锂盐中的至少一种。这些锂盐的实例包括六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、二(草酸)硼酸锂(lithium bis(oxalate)borate)、LiN(SO2CF3)2、LiN(SO2C2F5)2或Li(C2F5)PF3。
该锂盐通常以约0.5M～约1.5M的浓度使用。该溶剂包括主要组分，所述主要组分是γ-戊内酯、乙酸甲基异丁酰基酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯或草酸二乙酯中的至少一种，该主要组分构成了该溶剂的至少50体积％。在另一实施方案中，该主要组分可以构成该电解液溶剂的约90～约95体积％。该溶剂对溶解的锂盐(例如六氟磷酸锂)是稳定的，与含金属锂的阳极接触。所述包含至少一种溶剂的电解液在低至-30℃的温度下提供稳定的导电性。
在以下实验中测试了这五种溶剂化合物。第一组实验测试了溶剂化合物对LiPF6盐的溶解性和该溶剂的电化学稳定性窗口。制备各溶剂的1M LiPF6溶液，使溶液中的氧和水含量最小化。在氮气气氛下在氧含量低于1ppm的干燥箱中制备电解质溶液。在电解质溶液的制备过程中，干燥箱中的温度范围在27℃～29℃。所用的LiPF6盐可获自Stella ChmifaCorporation，Japan，具有99.99％纯度和20ppm的水含量。接收而未经后续处理的(as-received)溶剂纯度在大于99％～大于90％变化。接收而未经后续处理的溶剂中的水含量不超过0.1％，只要能够得到就使用无水溶剂。所有溶剂在干燥箱中的分子筛上干燥。
用3电极电池进行所有的电测量，其限定内浅圆柱电解液体积(22.2mm直径，3mm高)为1.2mL。工作电极由直径为1mm(0.7cm2面积)的99.99％中硬铂线构成，将其沿圆柱直径放置在电池电解液空间的中心面上。反电极和参考电极构成该圆柱空间的下底部和上底部；各自由金属锂箔构成，面积为4cm2。用3mm的电解液层隔开工作电极和反电极。用末端在2.5mm香蕉型插头座中的镍集电器将参考电极和反电极连接到测量电路中，同时用镀银的小弹簧夹进行工作电极连接。用Arbin多通道3电极电池周期计进行周期电势扫描。在每各系列的测试之前，用Keithley 2001DMM校准该Arbin周期计(cycler)的所有通道。
现在参考图1，提供了溶剂γ-戊内酯的循环伏安图。该循环伏安图是对于在γ-戊内酯中的1M LiPF6，用铂工作电极和锂金属箔反和参考电极记录的。电势在0伏特～5伏特之间循环。
最初的电解液颜色是水-白色(water-white)的，通过与金属铝接触或循环电势扫描无变化。图1中所见的在3.6伏特处的峰对应由于残余水的氧化造成氢氧化铂层的形成。在2.6V处的峰是由于铂氧化物的还原。
如图1中所示，在电势扫描的整个5伏特范围上电流密度小于30μA/cm2，表明电化学活性杂质的浓度低。该电解液溶剂γ-戊内酯具有非常宽的电化学稳定性窗口，等于或大于5伏特，对于金属锂和LiPF6盐是化学稳定的。
现在参照图2，提供了溶剂乙酸2-乙氧基乙酯的循环伏安图。该循环伏安图是对于在乙酸2-乙氧基乙酯中的1M LiPF6，用铂工作电极和锂金属箔反和参考电极记录的。电势在0伏特～5伏特之间循环。
最初的电解液颜色是非常浅的，通过与金属铝接触或循环电势扫描无变化。在1.2V、2.0V和2.8V处非常小的氧化峰和在2.3V处的还原峰都是由于少量的残余有机杂质。该溶剂不含任何水。
在4.0V处溶剂乙酸2-乙氧基乙酯由于氧化开始溶剂分解，但仅在大于4.7V时电流密度才超过100μA/cm2。在低于0.8V时由于还原开始溶剂分解。该溶剂乙酸2-乙氧基乙酯具有约4.3V的电化学稳定性窗口，对于金属锂和LiPF6盐是化学稳定的。
这两种循环伏安图试验及其结果代表了用溶剂乙酸甲基异丁酰基酯、乙酸2-甲氧基乙酯、和草酸二乙酯所得到的类似数据。在类似的电势循环试验中，证明了这些溶剂中的每一种对金属锂和LiPF6盐都是化学稳定的。
另一组试验测试了对于LiPF6的1M电解液溶液的比电导率。使用具有阻挡电极的双电极电池用于电交流阻抗测试。该电池提供了如上所述的浅圆柱电解液空间，体积为1.2mL，朝向在该圆柱形电解液空间的上底面和下底面处的镍电极。所有电极的测量表面都用6μm、1μm、0.3μm和0.050μm的逐渐减小的粒径的氧化铝水悬浮液抛光到镜面光洁度。在组装之前，在超声清洗器中用甲醇清洗所有电池元件，用蒸馏水漂洗两次，并在真空下干燥。
用Solartron 1260频率响应分析仪(FRA)以100Hz≤f≤10MHz的频率使用四端子对(也称作虚拟接地)的测量连接收集电交流阻抗谱。交流电压振幅范围在0.12V～3.0V之间，取决于要测定的电解液的电阻值。使用装备有用于同轴电缆的入口的Tenney Jr.温度腔进行温度控制。在-50℃～+40℃的整个温度范围内，Tenney Jr腔的定点稳定性(set-pointstability)为±0.1℃。
测试了溶剂的各自溶液，发现在室温(约20℃)下产生了如下的比电导率：γ-戊内酯6.0mS/cm、乙酸甲基异丁酰基酯4.8mS/cm、乙酸2-甲氧基乙酯4.6mS/cm、乙酸2-乙氧基乙酯3.6mS/cm、草酸二乙酯3.0mS/cm。比较而言，广泛用于锂离子电池电解液中的有机碳酸酯——碳酸亚丙酯在室温下的的比电导率为5.3mS/cm。
现在参照图3，示出了描述对于在4种溶剂(γ-戊内酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯和乙酸甲基异丁酰基酯)以及作为现有技术比较的碳酸亚丙酯中1M LiPF6溶液的比电导率(mS/cm)的温度依赖性的图表。碳酸亚丙酯是现有技术中已知的用于锂离子电池电解液的溶剂。观察到γ-戊内酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯和乙酸甲基异丁酰基酯的电解液混合物(溶解在各溶剂化合物中的六氟磷酸锂)提供了可与碳酸亚丙酯相当或更好的比电导率值。如图3中的数据所观察到，溶剂γ-戊内酯、乙酸甲基异丁酰基酯和乙酸2-甲氧基乙酯可以特别适用于低温应用，比广泛用于锂离子电池电解液配方中的有机碳酸酯溶剂具有更好的电导性。例如，这三种溶剂比碳酸亚丙酯具有更好的低温性能。参照图3，在-50℃～+40℃的整个温度范围内γ-戊内酯都产生比碳酸亚丙酯更高的比电导率。而且如图3中所见，γ-戊内酯、乙酸2-甲氧基乙酯和乙酸甲基异丁酰基酯在低于0℃的温度下比碳酸亚丙酯的性能更好。
因此，γ-戊内酯、乙酸甲基异丁酰基酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯和草酸二乙酯被认为适用做在具有包含锂金属或锂合金的阳极的锂离子电池中的含锂盐电解液的主要溶剂组分。这些主要溶剂组分可以使用作为电解液中的唯一溶剂，或者与彼此混合使用，或者与少量比例(minor proportion)的多种其它溶剂中的一种混合使用。该其它溶剂可以是其它用于锂离子电池中的锂盐的电解液溶剂，例如碳酸亚乙酯、碳酸亚丙酯、碳酸二甲酯、碳酸二乙酯或碳酸乙基甲基酯。
本发明主题的溶剂化合物用作包括阳极、阴极和包含锂盐的电解液的锂离子电池中的主要电解液溶剂。期望一种或多种该主要溶剂组分可以构成该用于一种或多种选择的锂盐的溶剂材料的约90～约95体积％。
在一种实施方案中，一种或多种该主要溶剂组分可以与碳酸酯溶剂(例如碳酸亚乙酯)混合使用。该碳酸亚乙酯可以用作电极上的成膜组分。该膜称作“固体电解质中间相”(solid electrolyte interphase，SEI)，是电绝缘且导离子的，其有助于防止电池自放电。在另一实施方案中，当至少一种主要溶剂组分和至少一种其它溶剂组分混合时，可以获得具有更高电导性的低温性能。该其它溶剂组分碳酸二甲酯、碳酸二乙酯或碳酸乙基甲基酯可以作为进一步提高低温电导性的低粘度组分。
在本发明的另一实施方案中，阳极可以包括锂金属、锂合金或碳质材料中的至少一种。阴极可以包括过渡金属氧化物、掺杂的过渡金属氧化物、过渡金属氧化物的混合物、金属磷酸盐、磷酸锂铁或金属硫化物中的至少一种。锂离子电池中的锂盐可以包括氟代磷酸锂、硼酸锂、酰亚胺锂、氟代烷基磷酸锂、或具有氟化阴离子的锂盐中的至少一种。该锂盐可以包括六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、二(草酸)硼酸锂、LiN(SO2CF3)2、LiN(SO2C2F5)2或Li(C2F5)PF3中的至少一种。锂盐的浓度可以为约0.5M～约1.5M。在本发明的另一实施方案中，该锂离子电池可以进一步包括适当量的阻燃剂，例如磷酸酯/盐(phosphate)溶剂或膦酸酯/盐(phosphonate)溶剂。
在本发明的另一种实施方案中，该锂离子电池可以包括形成凝胶的导电聚合物，以占据一部分电解液空间，且包含(类似海绵)液体电解液。该形成凝胶的导电聚合物可以由例如聚丙烯腈、聚甲基丙烯酸甲酯或聚环氧乙烷的聚合物形成。
本发明的上述某些实施方案的描述实质上仅是示例性的，因此，对其变化、改进和/或代替不应当认为是对本发明的精神和范围的脱离。
Claims (30)
1.用于锂离子电池的电解液，其包含锂盐和溶剂，其中该溶剂包含主要组分，所述主要组分是γ-戊内酯、乙酸甲基异丁酰基酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯或草酸二乙酯中的至少一种，该主要组分构成了该溶剂的至少50体积％。
2.如权利要求1所述的电解液，其中该主要组分构成该溶剂的约90～约95体积％。
3.如权利要求1所述的电解液，其中该锂盐包含氟代磷酸锂、硼酸锂、酰亚胺锂、氟代烷基磷酸锂、或具有氟化阴离子的锂盐中的至少一种。
4.如权利要求1所述的电解液，其中该锂盐包含六氟磷酸锂、四氟硼酸锂、二(草酸)硼酸锂、LiN(SO2CF3)2、LiN(SO2C2F5)2或Li(C2F5)PF3中的至少一种。
5.如权利要求1所述的电解液，其中锂盐的浓度为约0.5M～约1.5M。
6.如权利要求3所述的电解液，其中锂盐的浓度为约0.5M～约1.5M。
7.如权利要求4所述的电解液，其中锂盐的浓度为约0.5M～约1.5M。
8.如权利要求1所述的电解液，其中该溶剂基本由γ-戊内酯组成。
9.如权利要求1所述的电解液，其中该溶剂基本由乙酸甲基异丁酰基酯组成。
10.如权利要求1所述的电解液，其中该溶剂基本由乙酸2-甲氧基乙酯组成。
11.如权利要求1所述的电解液，其中该溶剂基本由乙酸2-乙氧基乙酯组成。
12.如权利要求1所述的电解液，其中该溶剂基本由草酸二乙酯组成。
13.如权利要求1所述的电解液，进一步包含分散在该电解液中的阻燃剂，其中该阻燃剂包含磷酸酯溶剂或膦酸酯溶剂中的至少一种。
14.如权利要求1所述的电解液，其中该溶剂进一步包含碳酸酯，其是碳酸亚丙酯、碳酸亚乙酯、碳酸二甲酯、碳酸二乙酯或碳酸乙基甲基酯中的至少一种。
15.如权利要求1所述的电解液，其中该电解液包含在形成凝胶的导电聚合物中。
16.锂离子电池，包含：
阳极；
阴极；和
包含分散在溶剂中的锂盐的电解液，其中该溶剂包含主要组分，其是γ-戊内酯、乙酸甲基异丁酰基酯、乙酸2-甲氧基乙酯、乙酸2-乙氧基乙酯或草酸二乙酯中的至少一种，该主要组分构成了该溶剂的至少50体积％。
17.如权利要求16所述的锂离子电池，其中该主要组分构成该溶剂的约90～约95体积％。
18.如权利要求16所述的锂离子电池，其中该阳极包含锂金属、锂合金或碳质材料中的至少一种。
19.如权利要求16所述的锂离子电池，其中该锂盐包含氟代磷酸锂、硼酸锂、酰亚胺锂、氟代烷基磷酸锂、或具有氟化阴离子的锂盐中的至少一种。
20.如权利要求16所述的锂离子电池，其中该锂盐包含六氟磷酸锂、四氟硼酸锂、二(草酸)硼酸锂、LiN(SO2CF3)2、LiN(SO2C2F5)2或Li(C2F5)PF3中的至少一种。
21.如权利要求16所述的锂离子电池，其中锂盐的浓度为约0.5M～约1.5M。
22.如权利要求19所述的锂离子电池，其中锂盐的浓度为约0.5M～约1.5M。
23.如权利要求20所述的锂离子电池，其中锂盐的浓度为约0.5M～约1.5M。
24.如权利要求16所述的锂离子电池，其中该溶剂基本由γ-戊内酯组成。
25.如权利要求16所述的锂离子电池，其中该溶剂基本由乙酸甲基异丁酰基酯组成。
26.如权利要求16所述的锂离子电池，其中该溶剂基本由乙酸2-甲氧基乙酯组成。
27.如权利要求16所述的锂离子电池，其中该溶剂基本由乙酸2-乙氧基乙酯组成。
28.如权利要求16所述的锂离子电池，其中该溶剂基本由草酸二乙酯组成。
29.如权利要求16所述的锂离子电池，进一步包含阻燃剂，其中该阻燃剂包含磷酸酯溶剂或膦酸酯溶剂中的至少一种。
30.如权利要求16所述的锂离子电池，其中该电解液进一步包含碳酸酯，其是碳酸亚丙酯、碳酸亚乙酯、碳酸二甲酯、碳酸二乙酯或碳酸乙基甲基酯中的至少一种。
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| Application Number | Priority Date | Filing Date | Title |
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| US11/692399 | 2007-03-28 | ||
| US11/692,399 US7722994B2 (en) | 2007-03-28 | 2007-03-28 | Lithium-ion battery non-aqueous electrolytes |
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| CN101276939A true CN101276939A (zh) | 2008-10-01 |
| CN101276939B CN101276939B (zh) | 2011-04-06 |
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| US (1) | US7722994B2 (zh) |
| EP (1) | EP1978588A1 (zh) |
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| CN112331914A (zh) * | 2019-08-05 | 2021-02-05 | 杉杉新材料（衢州）有限公司 | 一种不含碳酸乙烯酯溶剂的锂离子电池非水电解液及电池 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807720A (zh) * | 2010-03-31 | 2010-08-18 | 张家港市国泰华荣化工新材料有限公司 | 阻燃型电解质溶液及其应用 |
| CN101807720B (zh) * | 2010-03-31 | 2012-08-15 | 张家港市国泰华荣化工新材料有限公司 | 阻燃型电解质溶液及其应用 |
| CN112331914A (zh) * | 2019-08-05 | 2021-02-05 | 杉杉新材料（衢州）有限公司 | 一种不含碳酸乙烯酯溶剂的锂离子电池非水电解液及电池 |
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| Publication number | Publication date |
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| CN101276939B (zh) | 2011-04-06 |
| KR101015589B1 (ko) | 2011-02-17 |
| KR20080088489A (ko) | 2008-10-02 |
| US7722994B2 (en) | 2010-05-25 |
| EP1978588A1 (en) | 2008-10-08 |
| US20080241699A1 (en) | 2008-10-02 |
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