CN115398679A - 二次电池用负极和二次电池 - Google Patents
二次电池用负极和二次电池 Download PDFInfo
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- CN115398679A CN115398679A CN202180024713.XA CN202180024713A CN115398679A CN 115398679 A CN115398679 A CN 115398679A CN 202180024713 A CN202180024713 A CN 202180024713A CN 115398679 A CN115398679 A CN 115398679A
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- negative electrode
- secondary battery
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- active material
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Images
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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
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Abstract
二次电池用负极具备负极合剂,所述负极合剂包含:负极活性物质、添加剂和导电剂,前述负极活性物质包含含Si材料,前述添加剂包含碱金属硫酸盐,前述导电剂包含碳纳米管,前述负极合剂中的前述碱金属硫酸盐的含量相对于前述负极活性物质的总量为0.0025质量%以上且0.1质量%以下。
Description
技术领域
本公开涉及二次电池用负极和二次电池。
背景技术
含Si材料是与锂合金化的合金化材料,已知与石墨等碳系活性物质相比,每单位体积能吸藏大量的锂离子,可以期待在二次电池的负极活性物质中的利用。
然而,含Si材料的充放电时的体积变化(膨胀/收缩)大,因此,负极的导电性容易降低,其结果存在充放电循环特性降低的问题。
为了改善这种问题,有如下技术:在具有含Si材料的负极内添加碳纳米管,抑制伴有含Si剂的膨胀/收缩的负极的导电性降低,抑制充放电循环特的降低。
现有技术文献
专利文献
专利文献1:日本特开2005-310760号公报
发明内容
碳纳米管的比表面积大,因此,二次电池的初次充放电时与电解液发生反应,存在初次的充放电效率降低的问题。需要说明的是,初次的充放电效率是指:初次的放电容量相对于初次的充电容量的比率。
作为本公开的一方式的二次电池用负极具备负极合剂,所述负极合剂包含:负极活性物质、添加剂和导电剂,前述负极活性物质包含含Si材料,前述添加剂包含碱金属硫酸盐,前述导电剂包含碳纳米管,前述负极合剂中的前述碱金属硫酸盐的含量相对于前述负极活性物质的总量为0.0025质量%以上且0.1质量%以下。
作为本公开的一方式的二次电池具备:上述二次电池用负极、正极和非水电解液。
根据本公开,可以抑制初次的充放电效率的降低。
附图说明
图1为作为实施方式的一例的二次电池的剖视图。
具体实施方式
作为本公开的一方式的二次电池用负极具备负极合剂,所述负极合剂包含:负极活性物质、添加剂和导电剂,前述负极活性物质包含含Si材料,前述添加剂包含碱金属硫酸盐,前述导电剂包含碳纳米管,前述负极合剂中的前述碱金属硫酸盐的含量相对于前述负极活性物质的总量为0.0025质量%以上且0.1质量%以下。根据本公开,碱金属硫酸盐特异地大量存在于碳纳米管上,具有抑制碳纳米管与电解液的反应的性质,因此认为,二次电池中的初次的充放电效率的降低被抑制。但为了发挥上述效果,必须使负极合剂中的碱金属硫酸盐的含量为上述范围。碱金属硫酸盐的含量相对于负极活性物质的总量低于0.0025质量%的情况下,例如无法充分抑制碳纳米管与电解液的反应,得不到抑制初次的充放电效率降低的效果。另外,碱金属硫酸盐的含量相对于负极活性物质的总量超过0.1质量%的情况下,例如碱金属硫酸盐大量存在于碳纳米管以外的部位,源自碱金属硫酸盐的副反应的影响变大,得不到抑制初次的充放电效率降低的效果。
需要说明的是,负极合剂中所含的碳纳米管追随伴有充放电的含Si材料的膨胀/收缩,因此,从负极合剂中的导电通路孤立的含Si材料的增加被抑制。因此,碳纳米管抑制伴有含Si材料的膨胀/收缩的负极的导电性降低,有利于抑制充放电循环特性降低的效果。
以下,边参照附图边对本公开的二次电池用负极和二次电池的实施方式进行详述。需要说明的是,本说明书中,“数值(1)~数值(2)”的记载是指数值(1)以上且数值(2)以下。
图1为作为实施方式的一例的二次电池的剖视图。图1所示的二次电池10具备:正极11和负极12隔着分隔件13卷绕而成的卷绕型的电极体14;非水电解质;分别配置于电极体14的上下的绝缘板18、19;收纳上述构件的电池外壳15。电池外壳15由有底圆筒形状的外壳主体16、和阻塞外壳主体16的开口部的封口体17构成。需要说明的是,也可以应用正极和负极隔着分隔件交替地层叠而成的层叠型的电极体等其他形态的电极体来代替卷绕型的电极体14。另外,作为电池外壳15,可以示例圆筒形、方型、硬币形、纽扣形等金属制壳体、将树脂片层压而形成的树脂制壳体(层压型电池)等。
外壳主体16例如为有底圆筒形状的金属制容器。在外壳主体16与封口体17之间设有垫片28,以确保电池内部的密闭性。外壳主体16例如具有侧面部的一部分向内侧突出的、用于支撑封口体17的鼓凸部22。鼓凸部22优选沿外壳主体16的圆周方向以环状形成,由其上表面支撑封口体17。
封口体17具有从电极体14侧起依次层叠有局部开口的金属板23、下阀体24、绝缘构件25、上阀体26和盖子27的结构。构成封口体17的各构件例如具有圆板形状或环形状,除绝缘构件25之外的各构件彼此被电连接。下阀体24与上阀体26在各自中央部彼此连接,在各自的周缘部之间夹设绝缘构件25。由于内部短路等所导致的发热而二次电池10的内压上升时,例如下阀体24以向盖子27侧推入上阀体26的方式发生变形而断裂,下阀体24与上阀体26之间的电流通路被阻断。内压进一步上升时,上阀体26断裂,气体从盖子27的开口部排出。
图1所示的二次电池10中,安装于正极11的正极引线20通过绝缘板18的贯通孔向封口体17侧延伸,安装于负极12的负极引线21通过绝缘板19的外侧向外壳主体16的底部侧延伸。正极引线20以焊接等连接于作为封口体17的底板的局部开口的金属板23的下表面,与局部开口的金属板23电连接的封口体17的顶板即盖子27成为正极端子。负极引线21以焊接等连接于外壳主体16的底部内面,外壳主体16成为负极端子。
以下,对构成二次电池10的正极11、负极12、分隔件13、非水电解质进行详述。
[正极]
正极11例如具备:正极集电体、和形成于正极集电体上的正极合剂层。正极集电体中可以使用铝、铝合金等在正极的电位范围内稳定的金属的箔、在表层配置有该金属的薄膜等。正极合剂层例如通过包含正极活性物质、粘结剂、导电剂等的正极合剂而构成。正极合剂层优选形成于正极集电体的两面。正极11例如可以如下制造:将包含正极活性物质、粘结剂、导电剂等的正极合剂的浆料涂布于正极集电体上,使涂膜干燥、压延,在正极集电体的两面形成正极合剂层,从而可以制造。
正极活性物质例如使用锂过渡金属复合氧化物等。作为锂过渡金属复合氧化物中含有的金属元素,可以举出Ni、Co、Mn、Al、B、Mg、Ti、V、Cr、Fe、Cu、Zn、Ga、Sr、Zr、Nb、In、Sn、Ta、W等。其中,优选含有Ni、Co、Mn中的至少1种。作为适合的复合氧化物的一例,可以举出含有Ni、Co、Mn的锂过渡金属复合氧化物、含有Ni、Co、Al的锂过渡金属复合氧化物。
作为正极合剂层中所含的导电剂,可以示例炭黑、乙炔黑、科琴黑、石墨烯、碳纳米管、石墨等碳材料。作为正极合剂层中所含的粘结剂,可以举出聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVDF)等氟树脂、聚丙烯腈(PAN)、聚酰亚胺、丙烯酸类树脂、聚烯烃、羧甲基纤维素(CMC)或其盐、聚环氧乙烷(PEO)等。
[负极]
负极12例如具备:负极集电体、和形成于集电体上的负极合剂层。负极集电体中可以使用例如铜、铜合金等在负极的电位范围内稳定的金属的箔、在表层配置有该金属的薄膜等。负极合剂层通过包含负极活性物质、添加剂、导电剂等的负极合剂而构成。负极合剂除上述物质之外适合地还包含粘结剂。负极12例如可以如下制造:将包含负极活性物质、添加剂、导电剂、粘结剂等的负极合剂的浆料涂布于负极集电体,使涂膜干燥、压延,在负极集电体的两面形成负极合剂层,从而可以制造。
负极活性物质包含含Si材料。含Si材料只要为能吸藏/释放锂离子的材料即可,从二次电池的高容量化等的观点出发,优选如下含Si材料:其包含锂离子导电相、和分散于锂离子导电相的Si颗粒,锂离子导电相为选自硅氧化物相、硅酸盐相和碳相中的至少1种。
硅酸盐相例如从锂离子传导性高等方面出发,优选包含选自锂、钠、钾、铷、铯、钫、铍、镁、钙、锶、钡、镭中的至少1种元素E1。
硅酸盐相例如从初次的充放电效率的降低被抑制等方面出发,优选还包含选自锆、铌、钽、镧、钒、钛、磷、铋、锌、锡、铅、锑、钴、氟、钨、铝、硼中的至少1种元素E2。
优选在含Si材料的颗粒表面形成由导电性高的材料构成的导电覆膜。作为导电覆膜的构成材料,可以示例选自碳材料、金属、和金属化合物中的至少1种。其中,优选无定形碳等碳材料。碳覆膜例如可以以如下方法等形成:使用了乙炔、甲烷等的CVD法;将煤炭沥青、石油沥青、酚醛树脂等与硅系活性物质混合并进行热处理的方法。另外,使用炭黑等导电填料作为粘结材料,固着于含Si材料的颗粒表面,从而也可以形成导电覆膜。
作为具体的含Si材料,可以举出含有硅酸盐相和分散于硅酸盐相的Si颗粒的复合材料A、含有硅氧化物相和分散于硅氧化物相的Si颗粒的复合材料B、含有碳相和分散于碳相的Si颗粒的复合材料C等。它们可以单独使用1种,也可以并用2种以上。
复合材料A的硅酸盐相优选包含前述元素E1,更优选还包含前述元素E2。其中,从锂离子传导性高、初次的充放电效率的降低被抑制等方面出发,优选包含锂的硅酸盐相(以下,有时称为硅酸锂相)。即,复合材料A优选包含硅酸锂相、和分散于硅酸锂相内的Si颗粒(以下,有时称为LSX)。
在高容量化、充放电循环特性改善等方面,复合材料A中的硅颗粒的含量优选30质量%以上且80质量%以下、优选35质量%以上且75质量%以下、更优选55质量%以上且70质量%以下。
硅颗粒的含量可以通过Si-NMR而测定。以下,示出Si-NMR的理想的测定条件。
测定装置:Varian公司制、固体核磁共振光谱测定装置(INOVA-400)
探针:Varian 7mm CPMAS-2
MAS:4.2kHz
MAS速度:4kHz
脉冲:DD(45°脉冲+信号收集时间1H解耦)
重复时间:1200秒
观测幅度:100kHz
观测中心:-100ppm附近
信号收集时间:0.05秒
累积次数:560
试样量:207.6mg
分散于硅酸盐相内的Si颗粒具有Si单质的颗粒状的相,单独构成或由多个微晶构成。例如在充放电循环特性改善等方面,Si颗粒的微晶尺寸优选30nm以下。Si颗粒的微晶尺寸的下限值没有特别限定,例如为5nm。
另外,Si颗粒的微晶尺寸更优选10nm以上且30nm以下、进一步优选15nm以上且25nm以下。Si颗粒的微晶尺寸由Si颗粒的X射线衍射(XRD)谱图的归属于Si(111)面的衍射峰的半值宽度、根据谢勒公式而算出。
对于Si颗粒的平均粒径,例如从抑制Si颗粒本身的龟裂等方面出发,在初次充电前,优选500nm以下、更优选200nm以下、进一步优选50nm以下。在初次充电后,Si颗粒的平均粒径优选400nm以下、更优选100nm以下。
Si颗粒的平均粒径通过观察复合材料A的截面SEM(扫描型电子显微镜)照片而测定。具体而言,Si颗粒的平均粒径是将任意的100个Si颗粒的最大直径平均而求出的。
硅酸锂相例如用式:Li2zSiO2+z(0<z<2)表示。从稳定性、制作容易性、锂离子传导性等的观点出发,z优选满足0<z<1的关系,更优选z=1/2。
硅氧化物相中分散有Si颗粒的复合材料B例如用通式SiOx(优选0<x<2的范围,更优选0.5≤x≤1.6的范围)表示。碳相中分散有Si颗粒的复合材料C例如用通式SixC1y(优选0<x≤1和0<y≤1的范围,更优选0.3≤x≤0.45和0.7≤y≤0.55的范围)表示。复合材料B和C中的Si颗粒的含量、微晶尺寸、平均粒径可以与复合材料A的情况同样。
对于负极活性物质中的含Si材料的含量,例如在二次电池的高容量化、抑制充放电循环特性的降低等方面,相对于负极活性物质的总量,优选1质量%以上且15质量%以下。
负极活性物质优选还包含电化学上吸藏/释放锂离子的碳材料作为与含Si材料相比充放电时的膨胀和收缩的程度小的其他负极材料。对于负极活性物质中的碳材料的含量,例如在抑制二次电池的充放电循环特性的降低等方面,相对于负极活性物质的总量,优选85质量%以上且99质量%以下。
作为碳材料,例如可以示例石墨、易石墨化碳(软碳)、难石墨化碳(硬碳)等。其中,优选充放电的稳定性优异、不可逆容量也少的石墨。石墨是指:具有石墨型晶体结构的材料,例如可以举出天然石墨、人造石墨、石墨化中间相碳颗粒等。
负极合剂中的负极活性物质的含量例如相对于负极合剂的总量,优选85质量%以上、更优选90质量%以上、更优选95质量%以上。
负极合剂中所含的作为导电剂的碳纳米管可以举出单层碳纳米管、2层碳纳米管、多层碳纳米管。单层碳纳米管(SWCNT)是石墨烯片为1层、构成1根圆筒形状的碳纳米结构体,2层碳纳米管是石墨烯片为2层、以同心圆状层叠构成1根圆筒形状的碳纳米结构体,多层碳纳米管是石墨烯片为3层以上、以同心圆状层叠构成1根圆筒形状的碳纳米结构体。需要说明的是,石墨烯片是指:构成石墨(石墨)的晶体的sp2杂化轨道的碳原子位于正六方型的顶点的层。碳纳米管的形状无限定。作为上述形状,可以举出包含针状、圆筒管状、鱼骨状(鱼骨或杯子层叠型)、扑克牌状(薄片)和线圈状的各种形态。
对于碳纳米管的纤维长度,例如在抑制充放电循环特性的降低等方面,优选500nm以上且200μm以下、优选1μm以上且100μm以下。需要说明的是,碳纳米管的纤维长度可以如下求出:利用场发射型扫描显微镜(FE-SEM),测定任意的碳纳米管50个的长度,根据算术平均,从而求出。
对于碳纳米管的最外周直径(即,纤维直径),例如在抑制充放电循环特性的降低等方面,优选0.5nm以上且20nm以下、更优选1nm以上且10nm以下。碳纳米管的最外周直径可以如下求出:利用场发射型扫描显微镜(FE-SEM)或透射型电子显微镜(TEM),测定任意的碳纳米管50个的外径,根据算术平均,从而求出。
对于负极合剂中的碳纳米管的含量,例如在抑制充放电循环特性的降低等方面,相对于负极活性物质的总量,优选0.01质量%以上且1.0质量%以下、更优选0.1质量%以上且0.8质量%以下。
负极合剂中所含的导电剂除碳纳米管之外还可以包含颗粒状的导电剂。颗粒状的导电剂例如可以示例炭黑、乙炔黑、科琴黑、石墨等碳材料。使用颗粒状的导电剂的情况下,优选其1次粒径为5nm以上100nm以下,优选长宽比低于10。
负极合剂中所含的作为添加剂的碱金属硫酸盐可以举出硫酸锂、硫酸钠、硫酸钾、硫酸铷、硫酸铯、硫酸钫等。其中,在进一步抑制二次电池的初次的充放电效率的降低等方面,碱金属硫酸盐优选包含选自硫酸锂、硫酸钠、硫酸钾中的至少1种。
对于负极合剂中的碱金属硫酸盐的含量,在抑制二次电池的初次的充放电效率降低的方面,相对于负极活性物质的总量,只要为0.0025质量%以上且0.1质量%以下即可,优选0.01质量%以上且0.1质量%以下、更优选0.02质量%以上且0.08质量%以下。
负极合剂中所含的粘结剂可以与正极11中使用的粘结剂同样。负极合剂中的粘结剂的含量例如相对于负极活性物质的总量,优选0.5质量%~10质量%、更优选1质量%~5质量%。
[分隔件]
分隔件13使用具有离子透过性和绝缘性的多孔片。作为多孔片的具体例,可以举出微多孔薄膜、机织布、无纺布等。作为分隔件13的材质,适合的是,聚乙烯、聚丙烯、包含乙烯和丙烯中的至少一者的共聚物等烯烃系树脂、纤维素等。分隔件13可以为单层结构、层叠结构,均可。可以在分隔件13的表面形成有耐热层等。
[非水电解质]
非水电解质包含非水溶剂和电解质盐。非水电解质不限定于液体电解质,也可以为使用了凝胶状聚合物等的固体电解质。电解质盐中使用例如LiFSI、LiTFSI、LiBF4、LiPF6等锂盐。溶剂中使用例如碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、乙酸甲酯(MA)、丙酸甲酯(MP)等酯类、醚类、腈类、酰胺类、和它们的2种以上的混合溶剂等。非水溶剂也可以含有将上述这些溶剂的氢的至少一部分用氟等卤素原子取代而成的卤素取代物。
作为卤素取代物,例如可以举出氟代碳酸亚乙酯(FEC)等氟代环状碳酸酯、氟代链状碳酸酯、氟代丙酸甲酯(FMP)等氟代链状羧酸酯等。
<实施例>
以下,根据实施例,对本公开进一步进行说明,但本公开不限定于这些实施例。
<实施例1>
[含Si材料(LSX)的调整]
将二氧化硅与碳酸锂以原子比Si/Li成为1.05的方式进行混合,将混合物以950℃、在空气中焙烧10小时,从而得到式Li2Si2O5所示的硅酸锂。将得到的硅酸锂以平均粒径成为10μm的方式进行粉碎。
将上述硅酸锂与原料硅(平均粒径10μm)以70:30的质量比混合。将该混合物填充至有制球磨机(Fritsch公司制、P-5)的罐(SUS制、容积500mL)中,在罐中放入SUS制球(直径20mm)24个,关闭盖子,在非活性气氛中、以200rpm对混合物进行粉碎处理50小时。然后,在非活性气氛中取出粉末状的混合物,在非活性气氛中利用热压机施加了压力的状态下,以800℃焙烧4小时,得到混合物的烧结体(LSX)。
将得到的LSX粉碎,通过40μm的筛后,将得到的LSX颗粒与煤炭沥青混合,将混合物在非活性气氛中以800℃焙烧,用导电性碳覆盖LSX颗粒的表面,形成导电层。导电层的覆盖量相对于LSX颗粒与导电层的总质量为5质量%。之后,使用筛子,得到具有导电层的平均粒径5μm的LSX颗粒。根据Si-NMR测定的Li2Si2O5的含量为70质量%(Si颗粒的含量为30质量%)。
[负极的制作]
将具有导电层的LSX颗粒与石墨以5:95的质量比混合,将该混合物作为负极活性物质。将负极活性物质与硫酸钠(添加剂)与碳纳米管(导电剂)与羧甲基纤维素钠与丁苯橡胶以100:0.0025:0.3:1.3:1.0的质量比混合,加入适量的水,调整负极合剂的浆料。
在由铜箔形成的负极集电体的两面上涂布上述负极合剂的浆料,使涂膜干燥后,用辊将涂膜压延,制作在负极集电体的两面形成有负极合剂层的负极。
[非水电解液]
使LiPF6以1.2摩尔/L的比率溶解于以20:40:40的体积比混合有碳酸亚乙酯(EC)与碳酸二甲酯(DMC)与乙酸甲酯(MA)的混合溶剂中,制备非水电解液。
[试验电池单元]
将正极与负极隔着分隔件以彼此对置的方式进行层叠,将其卷绕,制作电极体。然后,将电极体和上述非水电解液收纳于有底圆筒形状的电池外壳主体,注入上述电解液后,通过垫片和封口体将电池外壳主体的开口部封口,制作试验电池单元。
<实施例2>
负极的制作中,将负极活性物质与硫酸钠(添加剂)与碳纳米管(导电剂)与羧甲基纤维素钠与丁苯橡胶以100:0.025:0.3:1.3:1.0的质量比混合,除此之外与实施例1同样地制作试验电池单元。
<实施例3>
负极的制作中,将负极活性物质与硫酸钠(添加剂)与碳纳米管(导电剂)与羧甲基纤维素钠与丁苯橡胶以100:0.05:0.3:1.3:1.0的质量比混合,除此之外与实施例1同样地制作试验电池单元。
<实施例4>
负极的制作中,将负极活性物质与硫酸钠(添加剂)与碳纳米管(导电剂)与羧甲基纤维素钠与丁苯橡胶以100:0.1:0.3:1.3:1.0的质量比混合,除此之外与实施例1同样地制作试验电池单元。
<比较例1>
负极的制作中,不使用作为添加剂的硫酸钠,将负极活性物质与碳纳米管(导电剂)与羧甲基纤维素钠与丁苯橡胶以100:0.3:1.3:1.0的质量比混合,除此之外与实施例1同样地制作试验电池单元。
<比较例2>
负极的制作中,将负极活性物质与硫酸钠(添加剂)与碳纳米管(导电剂)与羧甲基纤维素钠与丁苯橡胶以100:0.3:0.3:1.3:1.0的质量比混合,除此之外与实施例1同样地制作试验电池单元。
[初次的充放电效率的评价]
对于试验电池单元,在25℃的温度环境下、以0.3C的恒定电流进行充电直至电池电压成为4.2V后,以0.3C的恒定电流进行恒定电流放电直至电池电压成为2.5V。测定该初次的充电容量和初次的放电容量,根据以下式子,求出初次的充放电效率。
初次的充放电效率=(初次的放电容量/初次的充电容量)×100
表1中示出各实施例和比较例中的初次的充放电效率的评价结果。其中表1的评价结果如下:将比较例1的初次的充放电效率作为基准,以相对于上述基准的增加率表示其他实施例和比较例的初次的充放电效率。增加率为正的情况下,表示初次的充放电效率的降低被抑制。
[表1]
负极合剂中的碱金属硫酸盐的含量相对于包含含Si材料的负极活性物质的总量为0.0025质量%以上且0.1质量%以下的实施例1~4的初次的充放电效率示出高于不含碱金属硫酸盐的比较例1的初次的充放电效率的值。即,根据实施例1~4,可以说初次的充放电效率的降低被抑制。
附图标记说明
10 二次电池
11 正极
12 负极
13 分隔件
14 电极体
15 电池外壳
16 外壳主体
17 封口体
18、19 绝缘板
20 正极引线
21 负极引线
22 鼓凸部
23 局部开口的金属板
24 下阀体
25 绝缘构件
26 上阀体
27 盖子
28 垫片
Claims (10)
1.一种二次电池用负极,其具备负极合剂,所述负极合剂包含:负极活性物质、添加剂和导电剂,
所述负极活性物质包含含Si材料,所述添加剂包含碱金属硫酸盐,所述导电剂包含碳纳米管,
所述负极合剂中的所述碱金属硫酸盐的含量相对于所述负极活性物质的总量为0.0025质量%以上且0.1质量%以下。
2.根据权利要求1所述的二次电池用负极,其中,所述碱金属硫酸盐包含选自硫酸钠、硫酸锂和硫酸钾中的至少1种。
3.根据权利要求1或2所述的二次电池用负极,其中,所述负极合剂中的所述碳纳米管的含量相对于所述负极活性物质的总量为0.01质量%以上且1.0质量%以下。
4.根据权利要求1~3中任一项所述的二次电池用负极,其中,所述碳纳米管的最外周直径为0.5nm以上且20nm以下。
5.根据权利要求1~4中任一项所述的二次电池用负极,其中,所述碳纳米管的纤维长度为500nm以上且200μm以下。
6.根据权利要求1~5中任一项所述的二次电池用负极,其中,所述含Si材料包含:锂离子导电相、和分散于所述锂离子导电相的Si颗粒,
所述锂离子导电相为选自硅氧化物相、硅酸盐相和碳相中的至少1种。
7.根据权利要求6所述的二次电池用负极,其中,所述硅酸盐相包含选自锂、钠、钾、铷、铯、钫、铍、镁、钙、锶、钡、镭中的至少1种元素E1。
8.根据权利要求7所述的二次电池用负极,其中,所述硅酸盐相包含选自锆、铌、钽、镧、钒、钛、磷、铋、锌、锡、铅、锑、钴、氟、钨、铝、硼中的至少1种元素E2。
9.根据权利要求1~8中任一项所述的二次电池用负极,其中,所述碱金属硫酸盐比在所述负极活性物质上还多地偏在于所述碳纳米管上。
10.一种二次电池,其具备:权利要求1~9中任一项所述的二次电池用负极、正极和非水电解液。
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