CN104904049B - 二次电池用负极及包括该负极的锂二次电池 - Google Patents
二次电池用负极及包括该负极的锂二次电池 Download PDFInfo
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- CN104904049B CN104904049B CN201480001411.0A CN201480001411A CN104904049B CN 104904049 B CN104904049 B CN 104904049B CN 201480001411 A CN201480001411 A CN 201480001411A CN 104904049 B CN104904049 B CN 104904049B
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Abstract
本发明提供一种二次电池用负极,其包括:电极集电体;第一涂敷层,涂敷在所述电极集电体上,并包含负极活性物质、第一非水性粘合剂及导电材料;以及第二涂敷层,涂敷在所述第一涂敷层上,并包含第二非水性粘合剂。这种本发明的负极由于具有优良的缓解负极活性物质的体积变化的能力,因此,在使用该负极的情况下,能够改善锂二次电池的循环特性。
Description
技术领域
本发明涉及二次电池用负极及包括该负极的锂二次电池,具体地,涉及能够有效地改善在进行充放电时的体积变化大的硅类负极的退化的二次电池用负极和通过包括该二次电池用负极来改善循环特性的锂二次电池。
背景技术
最近,随着手机、可携式摄像机、笔记本电脑及电动汽车等的发达,对能量储存技术的关心越来越提高。其中,最受瞩目的领域为电化学元件领域,尤其,能够进行充放电的二次电池成为关心的对象。
尤其,使用锂和电解液的锂二次电池由于能够实现小型化、轻量化及高能量密度的可能性高,因此正得到积极的开发。
现有的锂二次电池作为负极活性物质,主要使用既能维持结构、电性质,又能进行可逆性的锂离子的嵌入(intercalation)及脱嵌的碳类化合物。最近,随着与锂发生化学反应的硅、锡或它们的合金被认为能够以可逆性的方式吸藏及放出大量的锂,正对此进行更多的研究。
由于上述硅的理论最大容量为约4020mAh/g(9800mAh/cc,比重为2.23),与石墨类物质相比非常大,因此,有望作为高容量负极材料。但所述硅或它的合金等由于在进行充放电时反复进行膨胀和收缩,并使负极退化,从而具有电池的循环寿命降低的缺点。即,当进行充放电时,若锂离子进入负极活性物质(硅)内,则负极活性物质的整个体积膨胀,使得具有更加紧密的结构。之后,当进行放电时,锂重新以离子状态脱嵌,负极活性物质的体积减少。此时,由于与所述负极活性物质一同混合的成分的膨胀率不同,因此,生成空间,甚至因空间而生成缝隙的部分得到电断开,使得电子的移动并不顺畅,从而降低电池的效率。并且,若与负极活性物质一同混合的粘合剂的弹性降低,发生龟裂,则电接触受到阻断,从而呈现出电阻增加的结果。这最终带来负极的退化,从而降低二次电池的循环特性。为了制造高能量密度的电池,作为高容量的负极活性物质的硅的含量越增加,这种现象越明显。
为了改善这种缺点,当制造负极时,为了提高负极活性物质之间的粘合力而试图进行过增加粘合剂含量的方法。但这种方法由于使导电材料或负极活性物质的含量相对降低,从而带来降低电池的电阻特性,或者降低传导度,或者降低电池的容量及功率的缺点。
为此,正急需开发能够使用适当量的粘合剂,改善锂金属氧化物与集电体之间的粘合力,同时提高导电性,从而改善二次电池的容量及功率特性等性能的技术。
发明内容
发明要解决的技术问题
本发明的目的在于,为了有效地改善在进行充放电时体积变化大的硅类负极的退化,提供包括由非水性粘合剂组成的涂敷层的二次电池用负极。
并且,本发明的目的在于,提供因包括上述二次电池用负极而循环特性得到改善的锂电池。
解决技术问题的手段
以下,对本发明进行更详细的说明。
本发明为了有效地改善在进行充放电时体积变化大的硅类负极的退化,提供还包括由非水性粘合剂组成的第二涂敷层的二次电池用负极,上述非水性粘合剂形成于作为负极活性物质层的第一涂敷层的一部分表面或整面。
具体地,本发明提供二次电池用负极,包括:
电极集电体;
第一涂敷层,涂敷在上述电极集电体上,并包含负极活性物质、第一非水性粘合剂及导电材料;以及
第二涂敷层,涂敷在上述第一涂敷层上,并包含第二非水性粘合剂。
在本发明的负极中,作为上述电极集电体,可使用不锈钢、镍、铜、钛或它们的合金、利用碳、镍、钛或银对铜或不锈钢的表面进行表面处理的材料等,其中,优选为铜或铜合金。
并且,在本发明的负极中,作为上述第一涂敷层的主要成分的负极活性物质,可以举出天然石墨、人造石墨、膨胀石墨、碳纤维、难石墨化碳、炭黑、碳纳米管、富勒烯、活性炭等碳及石墨材料;能够与锂形成合金的金属氧化物,例如,Al、Si、Sn、Ag、Bi、Mg、Zn、In、Ge、Pb、Pd、Pt、Ti等金属及包含这类元素的化合物;金属及其化合物和碳及石墨材料的复合物;含锂氮化物;或它们的组合等。更具体地,作为负极活性物质,可以使用结晶质碳、非晶质碳、硅类活性物质(SiOx,0<x<2)、锡类活性物质及硅-碳类活性物质组成的组中的一种或两种以上的物质的组合,优选地,使用包含硅类活性物质的负极活性物质。
并且,在本发明的负极中,包含于上述第一涂敷层的第一非水性粘合剂,润湿性(wetting)优良,且沿着电极的深度方向的渗透性优良,因此是可以进一步提高负极活性物质和集电体整体的结合力的链状聚合物,可以举出例如,选自由聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、含丙烯腈的结合剂(X-linking agent)、聚乙烯醇、聚氯乙烯、聚乙烯吡咯烷酮、聚四氟乙烯、聚乙烯及聚丙烯组成的组中的一种或混合两种以上的非水性粘合剂。
上述第一非水性粘合剂作为有助于对负极活性物质和导电材料及集电体的结合的成分,以第一涂敷层的总重量为基准,可包含1至50重量百分比。若在上述第一非水性粘合剂的含量大于50重量百分比,则由于结合负极活性物质的粘合剂的面积增加,因而电阻会增加。
并且,上述导电材料,作为进一步提高电极活性物质的导电性的成分,以第一涂敷层的总重量为基准,可包含1至20重量百分比。这种导电材料只要是既不会对该电池引发化学变化,又能赋予导电性的材料,就不受特殊限制,例如,可以举出天然石墨哦或人造石墨等石墨;碳黑、乙炔黑、科琴黑、槽黑、炉黑、灯黑、热黑等碳黑;碳纤维或金属纤维等导电性纤维;氟化碳、铝、镍粉等金属粉末;氧化锌、钛酸钾等导电晶须;氧化钛等导电性金属氧化物;聚苯撑衍生物等导电性材料等。
除了上述成分之外,根据需要,上述第一涂敷层还可以包含其他添加剂等,具体例或含量等只要是通常所添加的水准,就很充分。
上述第一涂敷层,作为负极活性物质层,通过以下步骤来形成,即,在以混合第一非水性粘合剂、导电材料及溶剂的方式制备第一浆料之后,将上述第一浆料涂敷于集电体上,并进行干燥。
上述溶剂可使用能够溶解N-甲基吡咯烷酮(NMP)或非水性粘合剂的乙醇类、酮类等多种溶剂。
并且,上述第一涂敷层的厚度可根据所需的电池单元的容量设计来适当地进行改变,具体地,可以具有数十至数百微米的厚度。
此时,上述第一粘合剂可涂敷于负极活性物质粒子的整个表面,也可以仅涂敷于负极活性物质粒子之间的接触部位,具体优选地,以既能最小化电阻,又能维持适当的结合力的范围的面积涂敷。
并且,在本发明的负极中,包含于上述第二涂敷层的第二非水性粘合剂可以使用与包含于第一涂敷层的第二非水性粘合剂相同或不同的粘合剂。例如,上述第二非水性粘合剂可以举出选自由聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、含丙烯腈的结合剂(X-linkingagent)、聚乙烯醇、聚氯乙烯、聚乙烯吡咯烷酮、聚四氟乙烯、聚乙烯及聚丙烯组成的组中的一种或混合两种以上的非水性粘合剂。
上述第二涂敷层作为粘合剂涂敷层,通过以下步骤来形成,即,在以混合第二粘合剂及溶剂的方式制备第二浆料之后,将上述第一浆料涂敷于被干燥的第一涂敷层涂敷的电极的一部分或整个表面,并进行干燥。
上述溶剂可使用能够溶解N-甲基吡咯烷酮(NMP)或非水性粘合剂的乙醇类、酮类等多种溶剂。
上述第二涂敷层利用普通的涂敷方法来形成,其形成方法不受特殊限制,可以利用常规的浸涂法或喷涂法等来涂敷。
包含上述第二粘合剂15的第二涂敷层可涂敷于形成有第一涂敷层的电极的整面,或者,包含上述第二粘合剂15的第二涂敷层可选择性地涂敷于与相邻的负极活性物质11的点接触部位相结合的第一粘合剂13上(参照图1)。
具体地,上述第二涂敷层以形成有上述第一涂敷层的电极的总重量为基准,可利用约100重量百分比以下的量,具体地,利用约1至50重量百分比的量,更具体地,利用约1至10重量百分比的量,更具体地,利用约1至5重量百分比的量来涂敷。
为了提高传导性,上述第二涂敷层还可以包含导电材料及其他添加剂。
并且,本发明提供通过包括本发明的负极、正极、电解液及隔膜来提高充放电特性及循环特性的锂二次电池。
上述正极利用与上述正极的制备方法相同的方法,将包含正极活性物质、导电材料及粘合剂的浆料涂敷于正极集电体上,并通过干燥来制备。根据需要,还可以在上述正极用浆料包含填充剂。
上述正极集电体只要是对上述电池不会引起化学变化,且具有高的导电性,就不受特殊限制。例如,可使用不锈钢、铝、镍、钛、煅烧碳或利用碳、镍、钛、银等对铝或不锈钢的表面进行表面处理的材料。正极集电体能够通过在表面形成细微的凹凸来提高与正极活性物质之间的粘合力。正极集电体能够以膜、薄片、箔、网、多孔质体、发泡体及无纺布体等多种形态使用。
并且,上述正极活性物质可使用例如锂钴氧化物(LiCoO2)、锂镍氧化物(LiNiO2)等层状化合物或被一种或一种以上的过渡金属取代的化合物;LiNi1-x-yCox(Al)yO2(其中,x=0.15,Y=0.05)氧化物或化学式Li1+xMn2-xO4(其中,x为0至0.33)、LiMnO3、LiMn2O3、LiMnO2等锂锰氧化物;锂铜氧化物(Li2CuO2);LiV3O8、LiFe3O4、V2O5、Cu2V2O7等钒氧化物;由化学式LiNi1-xMxO2(其中,M=Co、Mn、Al、Cu、Fe、Mg、B或Ga,x=0.01至0.3)表示的Ni位点型锂镍氧化物;由化学式LiMn2-xMxO2(其中,M=Co、Ni、Fe、Cr、Zn或Ta,x=0.01至0.1)或Li2Mn3MO8(其中,M=Fe、Co、Ni、Cu或Zn)表示的锂锰复合氧化物;化学式的Li的一部分被碱土金属离子取代的LiMn2O4;二硫化合物;Fe2(MoO4)3等,但优选地,可使用LiNixMn2-xO4(x=0.01至0.6),更优选地,可使用LiNi0.5Mn1.5O4或LiNi0.4Mn1.6O4。即,在本发明中,优选地,使用由于负极活性物质的高的电位而具有相对高电位的LiNixMn2-xO4(x=0.01至0.6)的尖晶石锂锰复合氧化物作为正极活性物质。
以正极用浆料的总重量为基准,上述导电材料可添加1至10重量百分比,上述导电材料只要是对上述电池不会引发化学变化,且具有导电性,就不受特殊限制。例如,可使用天然石墨或人造石墨等石墨;碳黑、乙炔黑、科琴黑、槽黑、炉黑、灯黑及热黑等碳黑;碳纤维或金属纤维等导电性纤维;氟化碳、铝及镍粉等金属粉末;氧化钛等导电性金属氧化物;聚苯撑衍生物等导电性材料等。
并且,上述粘合剂作为用于改善对活性物质、导电材料及集电体的结合的成分,通常以包含正极活性物质的混合物的总重量为基准,添加1至50重量百分比的上述粘合剂。作为这种粘合剂的例,可以举出作为非水性粘合剂的聚偏氟乙烯(PVDF)等。
上述填充剂作为用于抑制正极的膨胀的成分,以选择性的方式使用,只要是对上述电池不会引起化学变化,且为纤维状材料,就不受特殊限制,例如,使用聚乙烯、聚丙烯等烯烃类聚合物及玻璃纤维、碳纤维等纤维状物质。
并且,上述电解液作为含锂盐的电解液,虽然使用非水性有机溶剂、有机固体电解质、无机固体电解质等,但并不局限于此。
上述锂盐作为容易溶解于上述非水性电解质的物质,例如,可以使用LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂肪族羧酸锂、四苯基硼酸锂及酰亚胺锂等。
并且,作为上述非水性有机溶剂,可使用例如,N-甲基-2-吡咯烷酮、碳酸丙烯酯、碳酸乙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、γ-丁内酯、1,2-二甲氧基乙烷、四羟基呋喃、2-甲基四氢呋喃、二甲基亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、二氧环戊烷、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧环戊烷衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑啉酮、碳酸丙烯酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯及丙酸乙酯等非质子有机溶剂。
作为上述有机固体电解质,可使用例如,聚乙烯衍生物、聚环氧乙烷衍生物、聚环氧丙烷衍生物、磷酸酯聚合物、多聚赖氨酸(agitationlysine)、聚酯硫醚、聚乙烯醇、聚偏氟乙烯及包含离子性解离基的聚合物等。
作为上述无机固体电解质,可使用例如,Li3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH及Li3PO4-Li2S-SiS2等Li的氮化物、卤化物、硫酸盐等。
并且,上述隔膜介于正极和负极之间,并使用具有高的离子渗透度和机械强度的绝缘性的薄膜。作为这种隔膜,使用耐化学性及疏水性的聚丙烯等烯烃类聚合物、由玻璃纤维或聚乙烯等制成的薄片或无纺布等。在使用聚合物等固体电解质作为电解质的情况下,可由固体电解质兼作分离膜。
并且,本发明提供包括上述二次电池作为单位电池的电池模块、包括上述电池模块的电池组,并提供包括上述电池组的装置。
如上所述,虽然现有的负极因在进行充放电时,与负极活性物质相混合的粘合剂的弹性降低,从而在缓解负极活性物质的体积变化的能力方面不足,但本发明的负极在形成有包含第一非水性粘合剂的活性物质层的电极的表面还涂敷包含上述第二非水性粘合剂的涂敷层,从而不仅维持第一涂敷层和集电体之间的适当的结合力,而且在进行电极的充放电时,缓解负极活性物质的体积变化,能够有效地防止负极的退化,因此,能够在不会增加电极的电阻的情况下,制备出循环寿命及充放电特性得到改善的锂二次电池。
发明的效果
在本发明中,通过在负极活性物质层上追加形成含有非水性粘合剂的粘结性涂敷层,能够防止在进行充放电时的体积变化大的硅类负极的退化,从而能够改善锂二次电池的充放电特性及循环特性。
附图说明
图1为本发明的负极活性物质结构的模式图。
图2为表示本发明一实施例的循环持有率的测定结果的图表。
图3a及图3b为表示从实验例4中取得的本发明的锂二次电池的容量维持率结果的图表。
图4a及图4b为表示从实验例4中取得的本发明的锂二次电池的电阻特性实验的结果的图表。
附图标记的说明
11:负极活性物质
13:第一粘合剂
15:第二粘合剂
具体实施方式
以下,为了对本发明进行具体说明而举出实施例及比较例进行详细说明。但本发明的实施例能够变形为多种不同的形态,本发明的范围不应解释为局限于以下所述的实施例。本发明的实施例为了向本发明所属技术领域的普通技术人员更加完整地说明本发明而提供。
实施例
I.本发明的涂敷层用浆料的制备
(制备例1)
在将聚丙烯腈(PAN)(2g)溶解于100mL的N-甲基吡咯烷酮(NMP)之后,搅拌1小时,制备了第二涂敷层用浆料。
(制备例2)
除了使用聚偏氟乙烯(PVDF)来代替上述聚丙烯腈(PAN)之外,以与上述制备例1相同的方法制备了第二涂敷层用浆料。
(制备例3)
除了使用含丙烯腈的结合剂(X-linking agent)来代替上述聚丙烯腈(PAN)之外,以与上述制备例1相同的方法制备了第二涂敷层用浆料。
II.负极的制备
(实施例1)
使用机械搅拌器,均匀地混合了14g(10重量百分比)的聚偏氟乙烯溶液和作为导电材料的12g(5重量百分比)的碳纳米管溶液。以约1:2的比率向上述混合溶液添加作为高容量的负极活性物质的SiOx(0<x<2)和呈现出稳定的充放电举动的石墨,并使用机械搅拌器使活性物质分散,从而制备了第一涂敷层用浆料。
然后,使用缺角轮涂布机(comma coater),以100μm的厚度将上述浆料涂敷于铜(Cu)集电体上,并进行干燥之后,在真空及110℃的条件下重新进行一次干燥,从而制成了形成有第一涂敷层的负极板。
接着,利用浸涂(dip coating)法,将在上述制备例1中制备的第二涂敷层用浆料涂敷于上述负极板(第一涂敷层)之后,进行干燥,从而制备了包括第二涂敷层的负极板。
然后,混合45重量百分比的LiNi1-x-yCox(Al)yO2(其中,x=0.15,y=0.05)(NCA,户田(TODA)公司)、2.5重量百分比的碳黑(Super-P,特密高(Timcal)公司)、2.5重量百分比的偏二氟乙烯/六氟丙烯共聚物(Solef6020,索尔未(Solvey)公司)及50重量百分比的N-甲基吡咯烷酮,制备了正极活性物质组合物,并以200μm的厚度将其涂敷于铝集电体上,并进行干燥,制备了正极板。
然后,在以3:4:3的体积比混合碳酸乙烯酯、碳酸二甲酯及碳酸甲乙酯的溶剂中添加LiPF6,从而制备了锂盐的浓度为1.2M的有机电解液溶液。
之后,在上述负极板及正极板之间配置作为隔膜的聚乙烯,来形成电极组装体之后,将上述电极组装体放入电池外壳,并注入上述电解液,制备了锂二次电池。
(实施例2)
除了涂敷制备例2的第二涂敷层用浆料来代替上述制备例1的第二涂敷层用浆料之外,以与上述实施例1相同的方法制成了负极板及包括该负极板的二次电池。
(实施例3)
除了使用制备例3的第二涂敷层用浆料来代替上述制备例1的第二涂敷层用浆料之外,以与上述实施例1相同的方法制成了负极板及包括该负极板的二次电池。
(比较例1)
使用机械搅拌器,均匀地混合了14g(10重量百分比)的聚偏氟乙烯溶液和作为导电材料的12g(5重量百分比)的碳纳米管溶液。以约1:2的比率向上述混合溶液添加作为高容量的负极活性物质的SiOx和呈现出稳定的充放电举动的石墨,并使用机械搅拌器使活性物质分散,从而制备了第一涂敷层用浆料。
然后,使用缺角轮涂布机(comma coater),以100μm的厚度将上述浆料涂敷于铜(Cu)集电体上,并进行干燥之后,在真空及110℃的条件下重新进行一次干燥,制成了形成有第一涂敷层的负极板。
接着,混合45重量百分比的LiNi1-x-yCox(Al)yO2(其中,x=0.15,y=0.05)(NCA,户田(TODA)公司)、2.5重量百分比的碳黑(Super-P,特密高(Timcal)公司)、2.5重量百分比的偏二氟乙烯/六氟丙烯共聚物(Solef6020,索尔未(Solvey)公司)及50重量百分比的N-甲基吡咯烷酮,制备了正极活性物质组合物,并以200μm的厚度将上述正极活性物质组合物涂敷于铝集电体上,并进行干燥,制备了正极板。
然后,在以3:4:3的体积比混合碳酸乙烯酯、碳酸二甲酯及碳酸甲乙酯的溶剂中添加LiPF6,从而制备了锂盐的浓度为1.2M的有机电解液溶液。
之后,在上述负极板及正极板之间配置作为隔膜的聚乙烯,来形成电极组装体之后,将上述电极组装体放入电池外壳,并注入上述电解液,制备了锂二次电池。
III.粘合力及功率实验
(实验例1)
以10nm的间隔裁剪在上述实施例1中制备的负极板之后,进行180°的剥离试验(peel test),从而测定涂敷有第二涂敷层和第一涂敷层的电极的粘合力(adhesionforce),并将其结果示于以下表1及图2中。
(实验例2)
除了使用实施例2的负极板来代替实施例1的负极板之外,以与上述实验例1相同的方法测定粘合力,并将其结果示于以下表1及图2中。
(实验例3)
除了使用实施例3的负极板来代替实施例1的负极板之外,以与上述实验例1相同的方法测定粘合力,并将其结果示于以下表1及图2中。
(比较实验例1)
除了使用比较例1的负极板来代替实施例1的负极板之外,以与上述实验例1相同的方法测定粘合力,并将其结果示于以下表1及图2中。
表1
负极板 | 第二涂敷层的涂敷量(重量百分比) | 粘合力(gf/10mm) |
实施例1 | 2.0 | 218.2 |
实施例2 | 3.9 | 223.5 |
实施例3 | 3.9 | 265.4 |
比较例1 | - | 101.1 |
如上述表1及图2所示,在实施例1至实施例3的形成有第二涂敷层的负极板的情况下,第二涂敷层和形成有第一涂敷层的电极之间的粘合力得到改善,均上升为200以上,并在长时间的循环之后,在循环保有(cycle retention)值方面没有太大差异,相反,在仅单独形成有比较例1的第一涂敷层的负极板的情况下,不仅粘合力约为100,非常低,而且在长时间的循环之后,呈现出循环保有值降低的结果。当比较图2所示的循环之后的残余容量时,在上述比较例1的情况下,300循环之后的容量维持率为80%水准,非常低,但在实施例1至实施例3的情况下,在300循环之后,容量维持率为82%以上的水准,可知寿命得到了改善。
实验例4
利用HPPC(Hybrid pulse power characterization,混合脉冲功率特性)方法来测定了在上述实施例1至实施例3及比较例1中制成的二次电池的功率及电阻。
以0.1C(4mA)充电至4.3V,直到从SOC 10至完全充电(SOC=100),在将电池分别稳定化1小时之后,根据HPPC实验方法测定了锂二次电池的功率及电阻。并且,以每次放电SOC10的方式将电池从SOC 100放电至SOC 10,并将电池分别稳定化1小时之后,通过HPPC实验方法,在每个SOC阶段测定了锂二次电池的功率及电阻。
接着,将初始充放电及进行300次充放电之后的容量维持率的结果示于图3a及图3b,并将初始充放电及进行300次充放电之后的容量(电阻特性结果)示于图4a及图4b。
即,如图3a及图3b所示,在上述比较例1的情况下,在进行300次循环之后的功率值,与初期相比,在SOC的整个区域降低,但在实施例的情况下,进行300次循环之后,与比较例1相比,功率降低幅度得到了改善。并且,如图4a及图4b所示,在比较例1的情况下,在进行300次循环之后的电阻值,与初期相比,在SOC的整个区域降低,但在实施例1的情况下,即使在进行300次循环之后,电阻幅度与比较例1相比得到了改善。
这种结果说明,通过第二涂敷层,在反复进行的充放电时,也由第二涂敷层维持与形成有第一涂敷层的电极的结合,缓解了负极活性物质的体积变化,从而能够防止金属活性物质和集电体导致电断开,能够维持锂离子的可逆性的吸藏/放出,从而能够带来提高的二次电池的循环特性。
Claims (3)
1.一种二次电池用负极,其特征在于,包括:
电极集电体;
第一涂敷层,涂敷在上述电极集电体上,并包含硅类负极活性物质、第一非水性粘合剂及导电材料;以及
第二涂敷层,涂敷在上述第一涂敷层上,并由第二非水性粘合剂组成,
其中所述第一非水性粘合剂为选自由聚偏氟乙烯、聚丙烯腈、聚乙烯醇、聚氯乙烯、聚乙烯吡咯烷酮、聚四氟乙烯、聚乙烯及聚丙烯组成的组中的一种或两种以上的非水性粘合剂,
其中所述第二非水性粘合剂为选自由聚偏氟乙烯、聚丙烯腈、聚乙烯醇、聚氯乙烯、聚乙烯吡咯烷酮、聚四氟乙烯、聚乙烯及聚丙烯组成的组中的一种或两种以上的非水性粘合剂,
其中所述第一非水性粘合剂仅存在于相邻的负极活性物质粒子的点接触部位,用于使负极活性物质粒子相结合,
其中所述第二涂敷层选择性地涂敷于形成在相邻的负极活性物质粒子的点接触部位的第一涂敷层上,以及
其中以形成有第一涂敷层的电极的总重量为基准,以1至5重量百分比的量涂敷所述第二涂敷层。
2.根据权利要求1所述的负极,其特征在于,所述第二非水性粘合剂为与所述第一非水性粘合剂同种的粘合剂或不同种的粘合剂。
3.一种锂二次电池,其特征在于,包括权利要求1所述的负极、正极、电解液及隔膜。
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CN106876778B (zh) * | 2017-02-21 | 2019-04-02 | 张家港金盛莲能源科技有限公司 | 一种锂离子二次电池 |
TWI694633B (zh) * | 2017-07-07 | 2020-05-21 | 美商片片堅俄亥俄州工業公司 | 用於鋰離子蓄電裝置之電極黏結漿料組合物 |
US10038193B1 (en) | 2017-07-28 | 2018-07-31 | EnPower, Inc. | Electrode having an interphase structure |
JP7029921B2 (ja) * | 2017-10-10 | 2022-03-04 | 日産自動車株式会社 | 非水電解質二次電池用電極 |
JP7119363B2 (ja) * | 2017-10-13 | 2022-08-17 | トヨタ自動車株式会社 | 全固体電池 |
US20190296332A1 (en) * | 2018-03-23 | 2019-09-26 | EnPower, Inc. | Electrochemical cells having one or more multilayer electrodes |
TWI735017B (zh) | 2019-08-05 | 2021-08-01 | 輝能科技股份有限公司 | 活性材料球複合層 |
CN112331820B (zh) * | 2019-08-05 | 2022-03-04 | 辉能科技股份有限公司 | 活性材料球复合层 |
US10998553B1 (en) | 2019-10-31 | 2021-05-04 | EnPower, Inc. | Electrochemical cell with integrated ceramic separator |
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