CN104247134A - 锂离子二次电池用电解液及锂离子二次电池 - Google Patents
锂离子二次电池用电解液及锂离子二次电池 Download PDFInfo
- Publication number
- CN104247134A CN104247134A CN201380017625.2A CN201380017625A CN104247134A CN 104247134 A CN104247134 A CN 104247134A CN 201380017625 A CN201380017625 A CN 201380017625A CN 104247134 A CN104247134 A CN 104247134A
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- Prior art keywords
- ion secondary
- lithium
- lithium ion
- electrolyte solution
- aliphatic compound
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- Granted
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 150000007824 aliphatic compounds Chemical class 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
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- 229910007226 Li(2-0.5x)Mn1-xM1.5xO3 Inorganic materials 0.000 claims description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
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- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 1
- TXXJUGKQQAFZKH-UHFFFAOYSA-N 3-(2-phenylphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=CC=C1C1=CC=CC=C1 TXXJUGKQQAFZKH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910007593 Li1.85Ni0.18Co0.10Mn0.87O3 Inorganic materials 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
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Classifications
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- 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
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- H—ELECTRICITY
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- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H—ELECTRICITY
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- H01M10/052—Li-accumulators
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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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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- Y02E60/10—Energy storage using batteries
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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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种锂离子二次电池用电解液,其含有锂盐电解质、有机溶剂以及1分子内具有3个以上羧酸基的脂肪族化合物。一种锂离子二次电池,其具备由以能嵌入脱嵌锂的锰(Mn)作为主要过渡金属种类的正极活性物质构成的正极、负极以及非水电解液。作为电解液使用上述物质。脂肪族化合物的分子量为50,000~500,000。
Description
技术领域
本发明涉及锂离子二次电池用电解液及锂离子二次电池,进一步具体而言,涉及能够增大锂离子二次电池的充电容量且能够提高循环特性的锂离子二次电池用的非水电解液、以及使用其的锂离子二次电池。
背景技术
以往,作为锂离子二次电池的正极,一直使用以有助于高容量的Li2MnO3作为母结构的锂过量层状正极(例如参见专利文献1)。
现有技术文献
专利文献
专利文献1:日本特表2009-517836号公报
发明内容
发明要解决的问题
然而,对于上述锂过量层状正极而言,有时作为构成成分的过渡金属(锰)会溶出,引起负极上的锰吸附等,电池性能降低。
本发明是鉴于这种现有技术中存在的问题而作出的,其目的在于提供能够抑制负极劣化、增大充电容量且可提高循环特性的锂离子二次电池用电解液、以及使用其的锂离子二次电池。
用于解决问题的方案
本发明人为了实现上述目的而进行了大量深入研究,结果发现,通过含有一分子内具有3个以上羧酸基的脂肪族化合物,能够实现上述目的,从而完成了本发明。
即,本发明的锂离子二次电池用电解液的特征在于,其含有锂盐电解质、有机溶剂以及1分子内具有3个以上羧酸基的脂肪族化合物。
此外,本发明的锂离子二次电池是具备由以能嵌入脱嵌锂的锰(Mn)作为主要过渡金属种类的正极活性物质构成的正极、负极以及非水电解液的锂离子二次电池。
上述非水电解液的特征在于,其含有有机溶剂、锂盐电解质以及1分子内具有3个以上羧酸基的脂肪族化合物。
发明的效果
根据本发明,由于含有一分子内具有3个以上羧酸基的脂肪族化合物,因此可以提供能够抑制负极劣化、增大充电容量且可提高循环特性的锂离子二次电池用电解液、以及使用其的锂离子二次电池。
附图说明
图1是示出化合物1分子中的羧酸基数量与使用了含有该化合物的电解液的电池的100次循环时容量保持率的关系的图表。
具体实施方式
以下对本发明的锂离子二次电池用电解液进行说明。
本发明的锂离子二次电池用电解液是含有锂盐电解质、有机溶剂以及1分子内具有3个以上羧酸基的脂肪族化合物的非水性的电解液。
在此,作为锂盐电解质,可列举出含有六氟磷酸锂(LiPF6)的碱金属盐。
此外,作为有机溶剂,可例示出:碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)、碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸氟亚乙酯(FEC)等,这些可以单独或组合使用。
这些有机溶剂用于溶解上述锂盐电解质。
进而,作为1分子内具有3个以上羧酸基的脂肪族化合物,可列举出各种脂肪族化合物,可以优选地使用柠檬酸、环丁烷四羧酸、环戊烷四羧酸及聚丙烯酸等。
其中,在本发明中,上述脂肪族化合物中不含氨基羧酸。
另外,作为上述这种脂肪族化合物,还可以使用聚丙烯酸、聚谷氨酸等高分子化合物,其分子量优选为50,000~500,000,进一步优选为100,000~450,000。
可认为这是由于为低分子量时,存在酸度升高的倾向。并且可认为这是由于为高分子量时,难以溶解于构成电池的电解液中,且配置在高分子侧链的羧酸基难以溶剂化,因而无法发挥作为添加剂的效果。
在本发明中,通过使用上述脂肪族化合物而获得良好效果的机理的细节并不清楚,但现阶段可作出如下推断。
即,由于自正极溶出的过渡金属离子的氧化还原电位要比锂离子(Li+)高,因此会先于Li+到达负极,对电池性能产生不良影响。
1分子内具有多个羧酸基的多元酸选择性捕捉多价阳离子先于一价阳离子,因此通过预先将所述脂肪族化合物溶解到电解液中,能够从含有Li+的电解液中选择性捕集自正极溶出的Mn等过渡金属离子(多价阳离子)。
根据以上这种机理,认为本发明能够抑制过渡金属离子到达负极层,能够抑制负极性能的劣化。因此,能够增大该电池的充电容量,并且还能够提高循环特性。
在本发明的锂离子二次电池用电解液中,对上述脂肪族化合物的含量并没有特别限定,相对于全部电解液,优选设为0.1~3质量%。
小于0.1质量%时,由于量过少而有时无法完全捕捉溶出的过渡金属离子,超过3质量%时,有时会妨碍电解液中的锂离子的离子化、离子移动,诱发副反应而降低电池性能。
另外,在本发明的锂离子二次电池用电解液中,除了上述构成成分以外还可以含有添加剂等。
作为这种添加剂,有能够在负极活性物质的表面形成覆膜(SEI覆膜)的添加剂,可例示出:有机砜类化合物、有机二砜类化合物、碳酸亚乙烯酯衍生物、碳酸亚乙酯衍生物、酯衍生物、二元酚衍生物、三联苯衍生物或磷酸酯衍生物、以及它们的组合。
在此,作为有机砜类化合物,有磺内酯衍生物和环状磺酸酯,可列举出:1,3-丙烷磺内酯(饱和磺内酯)、1,3-丙烯基磺内酯(不饱和磺内酯)。
此外,作为有机二砜类化合物,有二磺内酯衍生物和环状二磺酸酯,可举出甲烷二磺酸亚甲酯。
作为碳酸亚乙烯酯衍生物,可举出碳酸亚乙烯酯(VC),作为碳酸亚乙酯衍生物,可举出碳酸氟亚乙酯(FEC)。
作为酯衍生物,可例示出:4-联苯基乙酸酯、4-联苯基苯甲酸酯、4-联苯基苄基羧酸酯和2-联苯基丙酸酯。
作为二元酚衍生物,可例示出:1,4-二苯氧基苯和1,3-二苯氧基苯。
作为乙二醇衍生物,有1,2-二苯氧基乙烷、1-(4-联苯氧基)-2-苯氧基乙烷和1-(2-联苯氧基)-2-苯氧基乙烷。
作为三联苯衍生物,有邻三联苯、间三联苯、对三联苯、2-甲基-邻三联苯和2,2-二甲基-邻三联苯,作为磷酸酯衍生物,有磷酸三苯酯等。
接着,对本发明的锂离子二次电池进行说明。
<正极>
只要是含有以能嵌入脱嵌锂的锰(Mn)作为主要过渡金属种类的正极活性物质的正极即可,可以使用各种正极。
在本发明中,作为正极活性物质,优选使用下述化学式(1)所表示的材料。
Li(2-0.5x)Mn1-xM1.5xO3…(1)
(式中的x满足0.1≤x≤0.5,M表示NiαCoβMnγ(在此,α、β、γ和σ的范围为0<α≤0.5、0≤β≤0.33、0<γ≤0.5,满足α+β+γ=1。)。)
此外,作为正极活性物质,也可以使用下述化学式(2)所表示的材料。
Li(2-0.5x)Mn1-xM1.5xO3…(2)
(式中的x满足0.1≤x≤0.5,M表示NiαCoβMnγM1 σ(在此,M1表示选自由铝(Al)、铁(Fe)、铜(Cu)、镁(Mg)和钛(Ti)组成的组中的至少1种,α、β、γ和σ的范围为0<α≤0.5、0≤β≤0.33、0<γ≤0.5、0≤σ≤0.1,满足α+β+γ+σ=1。)。)
<负极>
只要是含有以硅(Si)或碳(C)作为主要构成元素的负极活性物质的负极即可,可以使用各种负极。
<非水电解液等>
关于非水电解液,使用上述本发明的锂离子二次电池用电解液。
此外,关于隔离体等,为公知的隔离体即可,对于电池元件的储存容器等也没有特别限制,作为电池形态,可以采用所谓的层压型电池、纽扣电池型电池和双极型电池等各种形态。
实施例
以下通过实施例和比较例进一步对本发明进行详细说明,但本发明并不限定于这些实施例。
(实施例1~7)
[负极的制作]
分别将石墨粉末、作为导电助剂的乙炔黑以及作为粘结剂的PVDF配混成90:5:5的质量比,向其中添加N-甲基吡咯烷酮作为溶剂并混合,制得负极浆料。使用铜箔作为集电体,将上述得到的负极浆料分别涂布为30μm的厚度,充分干燥。在真空下干燥24小时,得到目标负极。
[正极的制作]
按以下方法制得正极。
作为正极活性物质,使用Li1.85Ni0.18Co0.10Mn0.87O3(x=0.3、α=0.40、β=0.22、γ=0.38),与作为导电助剂的乙炔黑和作为粘结剂的PVDF配混成90:5:5的质量比,向其中添加N-甲基吡咯烷酮作为溶剂并混合,制得正极浆料。使用铝箔作为集电体,将上述得到的正极浆料分别涂布为30μm的厚度,充分干燥,得到目标正极。
[电解液的制备]
如表1所示,使用规定的脂肪族化合物,相对于溶解有1M的LiPF6的EC:DEC(1:2v/v%)溶液,将其混合溶解至1质量%,得到各例的电解液。
[电池的制作]
使以上得到的负极与正极相对,在其间配置聚烯烃制的厚度20μm的隔离体。将该负极·隔离体·正极的层叠体配置在不锈钢(SUS316)制的CR2032型纽扣电池中,接着,将各例的电解液注入纽扣电池内,然后密闭,得到各例的锂离子二次电池。
(比较例1)
未向电解液中加入脂肪族化合物,除此之外重复与实施例1同样的操作,得到本例的电池。
(比较例2~7)
使用表1所示的各例的化合物,相对于溶解有1M的LiPF6的EC:DEC(1:2v/v%)溶液,混合溶解至1质量%,得到各例的电解液。
除此之外重复与实施例1同样的操作,得到各例的锂离子二次电池。
<性能评价>
[电极的充放电试验]
循环特性评价
针对各例的锂离子二次电池,进行充放电循环试验,调查放电容量保持率。即,在30℃的气氛下以恒定电流方式(CC电流:0.1C)充电至4.6V,停歇10分钟,然后以恒定电流(CC、电流:0.1C)放电至2V。100次循环后的容量维持率一并记于表1。
[表1]
添加剂种类和100次循环后的维持率
化合物名 | 种类 | 酸性基团数 | 100次循环后的维持率 | |
比较例1 | 无 | 无 | 72% | |
比较例2 | EDTA | 氨基羧酸 | 4 | 0% |
比较例3 | 乙酸 | 脂肪族低分子 | 1 | 0% |
比较例4 | 丁二酸 | 脂肪族低分子 | 2 | 22% |
比较例5 | 对苯二甲酸 | 芳香族低分子 | 2 | 0% |
比较例6 | 1,3,5-苯三羧酸 | 芳香族低分子 | 3 | 15% |
比较例7 | 均苯四酸 | 芳香环低分子 | 4 | 30% |
实施例1 | 柠檬酸 | 脂肪族低分子 | 3 | 78% |
实施例2 | 环丁烷四羧酸 | 脂肪环低分子 | 4 | 74% |
实施例3 | 环戊烷四羧酸 | 脂肪环低分子 | 4 | 76% |
实施例4 | 聚丙烯酸Mw10万 | 脂肪族高分子 | 2000 | 81% |
实施例5 | 聚丙烯酸Mw45万 | 脂肪族高分子 | 5000 | 79% |
实施例6 | 多酸Mw45万 | 脂肪族高分子 | 10000 | 80% |
实施例7 | 多酸Mw100万 | 脂肪族高分子 | 20000 | 76% |
表1示出各种化合物(添加剂)的分子内羧酸基数量与使用了含有这些添加剂的电解液的电池的100次循环时容量保持率的关系。
根据该表可确认到,1分子内的羧酸基数为3以上且为脂肪族化合物时,100次循环时容量维持率提高。
图1示出化合物(添加剂)1分子中的羧酸基数量与使用了含有这些化合物的电解液的电池的100次循环时容量保持率的关系。
图中,方点表示脂肪族羧酸化合物,圆点表示芳香族羧酸化合物。此外,不含添加剂的电池的100次循环时维持率以虚线表示。
根据该图可确认到,1分子内的羧酸基数为3以上且为脂肪族化合物时,100次循环时容量维持率提高。此外,在尖晶石系正极中,使用了已知作为Mn溶出用添加剂的EDTA时的结果表示为三角点。可见,如现有技术这样使用EDTA时,电池性能与添加前相比大幅度降低,并不是说能够应用于尖晶石正极就一定能够应用于固溶体正极。
以上通过若干实施方式和实施例对本发明进行了说明,但本发明不限定于它们,可在本发明的主旨范围内进行各种变形。
例如,实施例以锂离子二次电池为例进行了说明,但并不限定于此,显然也能够应用于电容器等其他电气装置。
Claims (7)
1.一种锂离子二次电池用电解液,其特征在于,其含有锂盐电解质、有机溶剂以及1分子内具有3个以上羧酸基的脂肪族化合物。
2.根据权利要求1所述的锂离子二次电池用电解液,其特征在于,所述脂肪族化合物的分子量为50,000~500,000。
3.根据权利要求1或2所述的锂离子二次电池用电解液,其特征在于,所述脂肪族化合物的含量为0.1~3质量%。
4.一种锂离子二次电池,其具备由以能嵌入脱嵌锂的锰(Mn)作为主要过渡金属种类的正极活性物质构成的正极、负极以及非水电解液,其特征在于,
所述非水电解液含有:有机溶剂、锂盐电解质以及1分子内具有3个以上羧酸基的脂肪族化合物。
5.根据权利要求4所述的锂离子二次电池,其特征在于,所述正极活性物质用下述化学式(1)表示:
Li(2-0.5x)Mn1-xM1.5xO3… (1)
式中的x满足0.1≤x≤0.5,M表示NiαCoβMnγ,其中,α、β、γ和σ的范围为0<α≤0.5、0≤β≤0.33、0<γ≤0.5,满足α+β+γ=1。
6.根据权利要求4所述的锂离子二次电池,其特征在于,所述正极活性物质用下述化学式(2)表示:
Li(2-0.5x)Mn1-xM1.5xO3… (2)
式中的x满足0.1≤x≤0.5,M表示NiαCoβMnγM1 σ,其中,M1表示选自由铝(Al)、铁(Fe)、铜(Cu)、镁(Mg)和钛(Ti)组成的组中的至少1种,α、β、γ和σ的范围为0<α≤0.5、0≤β≤0.33、0<γ≤0.5、0≤σ≤0.1,满足α+β+γ+σ=1。
7.根据权利要求4~6中任一项所述的锂离子二次电池,其特征在于,所述负极由以硅(Si)或碳(C)作为主要构成元素的负极活性物质构成。
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CN101682084A (zh) * | 2007-06-07 | 2010-03-24 | 株式会社Lg化学 | 锂离子二次电池的非水电解质溶液和具有该溶液的锂离子二次电池 |
CN101714460A (zh) * | 2009-10-29 | 2010-05-26 | 华侨大学 | 聚吡咯/聚丙烯酸系复合凝胶电解质的制备方法 |
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JPH0678492B2 (ja) * | 1986-11-27 | 1994-10-05 | 昭和電工株式会社 | 高電導性重合体組成物及びその製造方法 |
US5665492A (en) * | 1995-02-08 | 1997-09-09 | Matsushita Electric Industrial Co., Ltd. | Composite Electrode including organic disulfide compound, method of producing the same, and lithium secondary battery utilizing the same |
KR100337889B1 (ko) * | 2000-06-22 | 2002-05-24 | 김순택 | 리튬 2차전지 |
JP4554911B2 (ja) * | 2003-11-07 | 2010-09-29 | パナソニック株式会社 | 非水電解質二次電池 |
KR20070057405A (ko) * | 2005-12-02 | 2007-06-07 | 주식회사 엘지화학 | 킬레이트제를 포함하는 리튬 이차 전지용 전해액 및 이를사용한 리튬 이차 전지 |
FR2933240B1 (fr) | 2008-06-25 | 2010-10-22 | Commissariat Energie Atomique | Electrolyte non-aqueux pour accumulateur au lithium a tension elevee |
EP2367226A4 (en) * | 2008-12-12 | 2012-07-11 | Panasonic Corp | ALKALINE DRY BATTERY |
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JP2011085622A (ja) * | 2009-10-13 | 2011-04-28 | Konica Minolta Holdings Inc | 電解液および電気化学デバイス |
JP2012089402A (ja) * | 2010-10-21 | 2012-05-10 | Hitachi Maxell Energy Ltd | リチウムイオン二次電池 |
JP5594241B2 (ja) * | 2011-07-01 | 2014-09-24 | 株式会社豊田自動織機 | 電解液及びリチウムイオン二次電池 |
EP2710651A4 (en) | 2011-05-19 | 2015-01-21 | Basf Se | ELECTROCHEMICAL CELLS COMPRISING POLYIMIDES |
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EP1142834A1 (en) * | 1999-11-15 | 2001-10-10 | Mitsubishi Chemical Corporation | Lithium-manganese composite oxide, positive electrode material for lithium secondary cell, positive electrode and lithium secondary cell, and method for preparing lithium-manganese composite oxide |
JP2005072182A (ja) * | 2003-08-22 | 2005-03-17 | Asahi Kasei Chemicals Corp | 電解コンデンサ用電解液 |
CN101682084A (zh) * | 2007-06-07 | 2010-03-24 | 株式会社Lg化学 | 锂离子二次电池的非水电解质溶液和具有该溶液的锂离子二次电池 |
CN101714460A (zh) * | 2009-10-29 | 2010-05-26 | 华侨大学 | 聚吡咯/聚丙烯酸系复合凝胶电解质的制备方法 |
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CN104247134B (zh) | 2017-03-01 |
KR20140124017A (ko) | 2014-10-23 |
US20150155595A1 (en) | 2015-06-04 |
EP2835856A1 (en) | 2015-02-11 |
EP2835856B1 (en) | 2017-05-03 |
EP2835856A4 (en) | 2015-03-11 |
JP2013232402A (ja) | 2013-11-14 |
WO2013150850A1 (ja) | 2013-10-10 |
US9825332B2 (en) | 2017-11-21 |
JP6206639B2 (ja) | 2017-10-04 |
KR101530157B1 (ko) | 2015-06-18 |
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