CN1577945A - 用于可再充电锂电池的电解液和可再充电锂电池 - Google Patents
用于可再充电锂电池的电解液和可再充电锂电池 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
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- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- UOZNXGJVAWDLQK-UHFFFAOYSA-N 1-(2,3-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(N2C(C=CC2=O)=O)=C1C UOZNXGJVAWDLQK-UHFFFAOYSA-N 0.000 claims description 6
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- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
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Classifications
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/42—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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- 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
- H01M10/0568—Liquid materials characterised by the solutes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开的是用于可再充电锂电池的电解液,其包括:包含式1所示的化合物且用于抑制过充电的添加剂、锂盐、非水有机溶剂,其中R1、R2和R3相同或不同,分别选自H、CH3、C2H5、CH=CH2、CH=CHCH3或有N、P或S的官能团。
Description
本申请基于于2003年7月1日提交在韩国知识产权局的申请No.2003-44405,其内容在此整体引入作为参考。
发明领域
本发明涉及一种用于可再充电锂电池的电解液(electrolyte)和包含该电解液的可再充电锂电池,更具体的是,涉及一种用于可再充电锂电池的能够提供表现出改善的安全性和延长的循环寿命特性的电池的电解液,以及包含该电解液的可再充电锂电池。
背景技术
随着更小、更轻和更高性能的通讯及其它电子设备的快速发展,需要开发高性能和大容量的电池来为这些设备提供电能。对大容量电池的需求促进了可再充电锂电池的研究。可再充电锂电池使用一种包含溶解于有机溶剂的锂盐的非水电解液。
为改善电池性能,已有一些有关用于在负极表面形成薄层的各种添加剂的研究。一种尝试是将吡咯、噻吩或碳酸亚乙烯酯添加到电解液中。这些化合物在充电和放电期间聚合,以在负极活性物质表面形成聚合物薄层,并改善电池的循环寿命特性。另一种尝试是将苯甲醚添加到电解液中以改善电池的安全特性。
然而,用于形成聚合物薄层的方法具有的缺点是难以控制该薄层,并且要考虑电池的体积膨胀。正极氧化后,苯甲醚在负极上形成高电阻聚合物层,导致循环寿命特性等电池性能因素的恶化。因此,尝试使用用于形成层的添加剂可以改善特定的电池性能因素,但其代价是一种或多种的不同性能因素的恶化。
另一些尝试通过添加乙基马来酰亚胺或甲基马来酰亚胺来解决这些缺点,但没有在电池中实际使用。
发明内容
本发明一方面提供一种用于可再充电锂电池的电解液,该电解液能够提供表现出改善的安全性和循环寿命特性的电池。
本发明另一方面提供一种包含该电解液的可再充电锂电池。
可以通过用于可再充电锂电池的电解液来实现这些及其它方面,该电解液包含用于抑制过充电的添加剂、锂盐以及有机溶剂,其中所述添加剂包含式1所示的化合物,
其中,R1、R2和R3相同或不相同,独立地为H、CH3、C2H5、CH=CH2、CH=CHCH3或有N、P或S的官能团。
本发明还提供一种包括该电解液、正极以及负极的可再充电锂电池。该正极和负极包括能够嵌入和脱出锂的活性物质。
附图说明
通过结合附图参考以下详细描述,本发明的更充分的评价及其诸多附加优点将变得更加显而易见和容易理解,其中:
图1是表示在本发明实施例1中使用的N-苯基马来酰亚胺的过充电试验结果的图表;
图2是表示本发明二次锂电池结构的实施例的示意图。
具体实施方式
本发明涉及在非水电解液中用于抑制过充电的添加剂。用于抑制过充电的该添加剂在正极上具有高于电池工作电压的氧化电位。此外,该添加剂在大约4.8V下分解,该电压比使正极活性物质分解的5.5V低,并且该添加剂的分解产物充当中断电池工作的阻抗因素(resistance factor),从而能够避免与正极活性物质分解有关的问题。该添加剂的分解产物不会不可逆地形成阻抗因素,因此没有损害电池的循环寿命特性。从而,用于抑制过充电的添加剂可以改善安全性而不会损坏电池的循环寿命特性。
这种用于抑制过充电的添加剂包括式1所示的化合物。该化合物是式2所示化合物与式3所示化合物的脱水产物。
式中,R1、R2和R3相同的或不同,独立地为H、CH3、C2H5、CH=CH2、CH=CHCH3或有N、P或S的官能团。有N、P或S的官能团优选为氨基、磷酸酯基、硫酸酯基或亚硫酸酯基。
该脱水产物优选为N-苯基马来酰亚胺、N-甲苯基(toluidyl)马来酰亚胺或N-二甲苯基(xylidyl)马来酰亚胺。
本发明的电解液包括如传统电解液成份的非水有机溶剂和锂盐,以及用于抑制过充电的添加剂。
基于锂盐和有机溶剂的重量,用于抑制过充电的添加剂优选为0.1至20重量%,更优选为0.5至5重量%。如果添加剂的量小于0.1重量%,就无法得到添加剂的添加效果。如果添加剂的量大于20重量%,OCV(开路电压)就降低,电池的循环寿命特性就恶化。
锂盐作为电池中提供锂离子的来源,并促进电池的工作。另外,锂盐激活正极和负极之间的锂离子转移。该锂盐是选自LiPF6、LiBF4、LiAsF6、LiCF3SO3、LiN(CF3SO2)3、Li(CF3SO2)2N、LiC4F9SO3,、LiClO4、CF3SO3Li、LiN(SO2C2F5)2、LiSbF6,、LiAlO4、LiAlCl4、LiN(CxF2x+1SO2)(CxF2y+1SO2)(其中x和y是自然数)、LiCl或Lil中的至少一种。电解液中锂盐的浓度适宜在0.6到2.0M之间。如果锂盐的浓度小于0.6M,电解液的导电率就降低,损害电解液的性能。如果锂盐的浓度大于2.0M,电解液的粘度就增大,降低锂离子的流动性。
非水有机溶剂充当可以运送参与电化学反应的离子的介质。该有机溶剂包括至少一种环状碳酸酯、链状碳酸酯、酯或酮。如本领域所公知的,如果采用它们的混合物,可以根据所要求的电池性能来适当地控制混合比率。环状碳酸酯可以是选自碳酸亚乙酯、碳酸亚丙酯或其混合物中的至少一种。链状碳酸酯可以是选自碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或碳酸甲酯中的至少一种。酯可以是γ-丁内酯、戊内酯、癸内酯(decanolide)或甲羟戊内酯(mevalolactone)中的至少一种。酮可以聚甲基乙烯酮。
具有本发明高分子电解液的可再充电锂电池包含正极和负极。
正极包括在其中可逆地嵌入锂的正极活性物质。正极活性物质的例子是LiCoO2、LiNiO2,、LiMnO2、LiMn2O4或LiNi1-x-yCoxMyO2(其中0≤x≤1,0≤y≤1,0≤x+y≤1;M是Al、Sr、Mg或La等金属或稀土元素)等锂过渡金属氧化物。
负极包括在其中可逆地嵌入锂的负极活性物质。负极活性物质的例子是晶体或非晶体含碳材料或者碳复合材料。
正极活性物质和负极活性物质被分别涂覆到集电器上以制备电极,将电极与隔板一起卷绕或在隔板上叠层以制造电极元件。电极元件被插入到例如罐的电池盒中,而电解液被注入到该外壳中以制造可再充电锂电池。隔板可以是聚乙烯或聚丙烯等树脂。
图2表示本发明可再充电锂电池的一个实施例。该可再充电锂电池包括:正极3,负极2,插在正极3和负极2之间的隔板4,其中浸有正极3、负极2和隔板4的电解液,圆柱形电池外壳5以及密封部件6。正如本领域所公知的,可再充电锂电池的结构不局限于图2表示的结构,可以容易地将其修改成棱形或袋式电池。
下列例子进一步详细地描述了本发明,但是本发明范围不受其限制。
比较例1
将LiCoO2正极活性物质、石墨导电剂以及聚偏氟乙烯粘合剂以91∶6∶3的重量比混合到N-甲基-2-吡咯烷酮溶剂中以制备正极活性物质浆料,然后将该正极活性物质浆料涂覆到铝箔集电器上并干燥,随后用滚压机进行压模,由此制造正极。
将石墨负极活性物质和聚偏氟乙烯粘合剂以90∶10的重量比混合到N-甲基-2-吡咯烷酮溶剂中以制备负极活性物质浆料,然后将该负极活性物质浆料涂覆到铜箔集电器上并干燥,用滚压机进行压模,由此制造负极。
通过将LiPF6溶解到碳酸亚乙酯和碳酸亚丙酯(2∶8体积比)的混合溶剂来制备1M的LiPF6锂盐溶液,以制备电解液。
利用该正极、该负极和该电解液,通过常规方法来制造可再充电锂电池。
实施例1
除将N-苯基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液之外,通过与比较例1中相同的工序来制造可再充电锂电池。N-苯基马来酰亚胺的含量占电解液的3重量%。
实施例2
除将N-苯基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液之外,通过与比较例1中相同的工序来制造可再充电锂电池。N-苯基马来酰亚胺的量占电解液的0.1重量%。
实施例3
除将N-苯基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液之外,通过与比较例1中相同的工序来制造可再充电锂电池。N-苯基马来酰亚胺的量占电解液的20重量%。
实施例4
除将N-甲苯基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液外,通过与比较例1中相同的工序来制造可再充电锂电池。N-甲苯基马来酰亚胺的量占电解液的3重量%。
实施例5
除将N-二甲苯基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液外,通过与比较例1中相同的工序来制造可再充电锂电池。N-二甲苯基马来酰亚胺的量占电解液的20重量%。
比较例2
除将N-环己基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液外,通过与比较例1中相同的工序来制造可再充电锂电池。N-环己基马来酰亚胺的量占电解液的3重量%。
比较例3
除将N-甲基马来酰亚胺添加到碳酸亚乙酯和碳酸亚丙酯(2∶8的体积比)与1M LiPF6锂盐的混合物中以制备电解液外,通过与比较例1中相同的工序来制造可再充电锂电池。N-甲基马来酰亚胺的量占电解液的3重量%。
对比较例1至3以及实施例1的可再充电锂电池进行了标准容量、400个周期之后的容量保持率以及2C下的过充电测试。测量标准容量:在0.5C下充电至4.2V和0.02C的截止电压,以0.5C和3.0V的截止电压进行放电;测量容量保持率:在0.5C下充电至4.2V和0.02C的截止电压,以1C和2.75V的截止电压进行放电。结果如表1所示。
表1
标准容量 | 400次循环后的容量保持率 | 2C下的过充电 | |
比较例1 | 320wh/l | 80% | 着火 |
实施例1 | 325wh/l | 83% | 完好 |
实施例2 | 319wh/l | 84% | 完好 |
实施例3 | 326wh/l | 80% | 完好 |
实施例4 | 320wh/l | 83% | 完好 |
实施例5 | 323wh/l | 82% | 完好 |
比较例2 | 323wh/l | 82% | 着火 |
比较例3 | 320wh/l | 78% | 着火 |
如表1所示,与比较例1相比较时,依照实施例1至5的电池在2C下表现出更好的安全特性和更高的容量保持率。结果表明马来酰亚胺可以提供表现出较好安全性和改进的循环寿命特性的可再充电锂电池。
此外,不能从在比较例2中使用的N-环己基马来酰亚胺和在比较例3中使用的N-甲基马来酰亚胺获得在实施例1至5种使用的添加剂N-苯基马来酰亚胺、N-甲苯基马来酰亚胺和N-二甲苯基马来酰亚胺的效果,即使这三种化合物具有类似的马来酰亚胺结构。认为产生这些结果的原因是由N-苯基马来酰亚胺、N-甲苯基马来酰亚胺或N-二甲苯基马来酰亚胺在大约4.8V产生的氧化峰(其表示由正极的氧化和分解引起的电子损失),该电压远高于普通电池的上限电压4.3V而低于出现安全问题的5.5V。因此,即使将很高的电压施加到电池,N-苯基马来酰亚胺添加剂可以使电池在正极分解之前停止运行。从而,改善了安全特性。此外,该添加剂保持稳定,直到电压达到高于上限电压的4.8V,这样该添加剂不会引起电池的循环寿命特性的退化,而这种退化会在使用用于抑制过充电的传统添加剂时发生。
从而,本发明可以提供用于抑制过充电的添加剂,该添加剂能够改善可再充电锂电池的安全特性而不引起电池循环寿命特性的退化。
虽然已经根据优选实施例详细描述了本发明,在不脱离附加权利要求书中陈述的本发明的精神和范围的情况下,本领域的技术人员可以领会对其进行的改动和替换。
Claims (12)
2.权利要求1所述的电解液,其中用于抑制过充电的添加剂的量是该电解液重量的0.1~20重量%。
3.权利要求1所述的电解液,其中所述化合物是式2所示的化合物与式3所示的化合物的脱水产物:
式中,R1、R2和R3相同或不同,独立地选自H、CH3、C2H5、CH=CH2、CH=CHCH3或有N、P或S的官能团。
4.权利要求1所述的电解液,其中所述化合物选自N-苯基马来酰亚胺、N-甲苯基马来酰亚胺或N-二甲苯基马来酰亚胺。
5.权利要求1所述的电解液,其中非水有机溶剂是选自环状碳酸酯类、链状碳酸酯类、酯类、醚类和酮类中的至少一种。
6.权利要求1所述的电解液,其中锂盐选自LiPF6、LiBF4、LiAsF6、LiCF3SO3、LiN(CF3SO2)3、Li(CF3SO2)2N、LiC4F9SO3,、LiClO4、CF3SO3Li、LiN(SO2C2F5)2、LiSbF6,、LiAlO4、LiAlCl4、LiN(CxF2x+1SO2)(CxF2y+1SO2)(其中x和y是自然数)、LiCl和Lil。
8.权利要求7所述的可再充电锂电池,其中用于抑制过充电的添加剂的量是该电解液重量的0.1~20重量%。
10.权利要求7所述的可再充电锂电池,其中所述化合物选自N-苯基马来酰亚胺、N-甲苯基马来酰亚胺和N-二甲苯基马来酰亚胺。
11.权利要求7所述的可再充电锂电池,其中非水有机溶剂是选自环状碳酸酯类、链状碳酸酯类、酯类、醚类和酮类中的至少一种。
12.权利要求7所述的可再充电锂电池,其中锂盐选自LiPF6、LiBF4、LiAsF6、LiCF3SO3、LiN(CF3SO2)3、Li(CF3SO2)2N、LiC4F9SO3、LiClO4、CF3SO3Li、LiN(SO2C2F5)2、LiSbF6、LiAlO4、LiAlCl4、LiN(CxF2x+1SO2)(CxF2y+1SO2)(其中x和y是自然数)、LiCl和Lil。
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Cited By (6)
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CN101210073B (zh) * | 2006-12-30 | 2010-12-08 | 财团法人工业技术研究院 | 含二马来酰亚胺寡聚物的组合物及其制备方法 |
US8124282B2 (en) | 2006-12-29 | 2012-02-28 | Industrial Technology Research Institute | Nonaqueous electrolyte having maleimide additives and secondary cells employing the same |
CN101685875B (zh) * | 2008-09-27 | 2012-07-04 | 财团法人工业技术研究院 | 锂电池 |
CN102569886A (zh) * | 2010-12-29 | 2012-07-11 | 财团法人工业技术研究院 | 非水性电解液与包含此非水性电解液的锂二次电池 |
WO2015003560A1 (zh) * | 2013-07-12 | 2015-01-15 | 江苏华东锂电技术研究院有限公司 | 电解液添加剂及含该添加剂的电解液及锂离子电池 |
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KR100536252B1 (ko) * | 2004-03-29 | 2005-12-12 | 삼성에스디아이 주식회사 | 리튬 전지용 전해질, 그의 제조 방법 및 그를 포함하는리튬 전지 |
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JP3369947B2 (ja) * | 1998-01-30 | 2003-01-20 | 三洋電機株式会社 | 非水系電解液電池 |
JP4463333B2 (ja) * | 1998-03-11 | 2010-05-19 | 三井化学株式会社 | 非水電解液及び非水電解液二次電池 |
JP2000294272A (ja) * | 1999-04-02 | 2000-10-20 | Mitsui Chemicals Inc | 非水電解液およびそれを用いた二次電池 |
EP1075005B1 (en) * | 1999-08-04 | 2006-04-26 | Fuji Photo Film Co., Ltd. | Electrolyte composition, and photo-electro-chemical cell |
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US8124282B2 (en) | 2006-12-29 | 2012-02-28 | Industrial Technology Research Institute | Nonaqueous electrolyte having maleimide additives and secondary cells employing the same |
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CN102569886A (zh) * | 2010-12-29 | 2012-07-11 | 财团法人工业技术研究院 | 非水性电解液与包含此非水性电解液的锂二次电池 |
CN102569886B (zh) * | 2010-12-29 | 2015-08-05 | 财团法人工业技术研究院 | 非水性电解液与包含此非水性电解液的锂二次电池 |
US9136559B2 (en) | 2010-12-29 | 2015-09-15 | Industrial Technology Research Institute | Non-aqueous electrolyte and lithium secondary battery including the same |
WO2015003560A1 (zh) * | 2013-07-12 | 2015-01-15 | 江苏华东锂电技术研究院有限公司 | 电解液添加剂及含该添加剂的电解液及锂离子电池 |
US9923241B2 (en) | 2013-07-12 | 2018-03-20 | Jiangsu Huadong Institute Of Li-Ion Battery Co. Ltd. | Electrolyte additive, electrolyte and lithium ion battery using the same |
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US7736812B2 (en) | 2010-06-15 |
JP4105127B2 (ja) | 2008-06-25 |
KR20050005354A (ko) | 2005-01-13 |
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US20050019671A1 (en) | 2005-01-27 |
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