CN104704663B - 二次电池用导电材料及包含该导电材料的锂二次电池用电极 - Google Patents
二次电池用导电材料及包含该导电材料的锂二次电池用电极 Download PDFInfo
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- 239000004020 conductor Substances 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
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Abstract
本发明涉及包括涂敷沥青(pitch)的石墨烯片的二次电池用导电材料和包含该导电材料的二次电池用负极及锂二次电池。
Description
技术领域
本发明涉及二次电池用导电材料及包含该导电材料的锂二次电池用电极。
背景技术
随着电子产品、电子设备、通信设备的小型化、轻量化及高性能化的急速发展,很大程度上需要改善用作这些产品的电源的锂二次电池的性能。
上述锂二次电池包括:正极及负极,包含电极活性物质、粘合剂及导电材料作为主要成分;隔膜,介于上述正极和负极之间;以及电解液。
此时,在上述负极的情况下,由于作为活性物质的碳类物质本身的传导度高,可以一并发挥作为导电材料的作用。但随着充放电的进行,负极活性物质与锂离子发生反应,存在使电子传导通路变得不稳定的情况,因此,为了对此进行补充,还需要包含额外的导电材料。
像这样,锂二次电池的基本性能大大取决于电极活性物质及导电材料等材料的特性。
尤其,导电材料发挥着改善电极活性物质之间或活性物质和集电体之间的导电性的作用,若这种导电材料的量不充分或无法正常执行其作用,就会增加电极活性物质中无法反应的部分,电池容量会降低。并且,对高速充放电特性、高速率充放电效率及初期充放电效率也会产生坏影响。
以往,使用了乙炔黑或碳黑等点型导电材料等作为这种导电材料,但因高速率放电特性和初期充放电效率等低而具有发生电极活性物质的损耗(loss)等的缺点。
因此,正急需研发能够改善充放电效率等的二次电池用导电材料。
发明内容
发明要解决的技术问题
本发明用于解决如上所述的问题,提供一种传导性改善效果卓越的锂二次电池用导电材料及其制备方法。
本发明提供包含上述导电材料的二次电池用电极。
并且,本发明还提供通过包含上述二次电池用电极来提高循环寿命特性的锂二次电池。
解决技术问题的手段
具体地,本发明提供一种包括涂敷沥青(pitch)的石墨烯片的二次电池用导电材料。
并且,本发明提供二次电池用导电材料的制备方法,包括:制备纯的石墨烯片的步骤;
将石墨烯片和煤系沥青相混合的步骤;以及
对上述混合物进行高温煅烧,来制备涂敷沥青的石墨烯片的步骤。
并且,本发明还提供二次电池用电极,包括集电体及涂敷于上述集电体上的电极活性物质层,上述电极活性物质层包含电极活性物质、上述本发明的二次电池用导电材料及粘合剂。
并且,本发明提供一种包含正极、负极、介于正极和负极之间的隔膜及电解液的锂二次电池,其中,包含本发明的负极作为上述负极的锂二次电池。
发明的效果
在本发明中,提供包括涂敷沥青的石墨烯片的电极作为导电材料,能够提供循环安全性及寿命特性得到改善的二次电池。
附图说明
本说明书所附的以下附图用于例示本发明的优选实施例,起到与上述的发明内容一同使本发明的技术思想更好地得到理解的作用,因此,本发明不应仅限于这些附图所记载的事项来解释。
图1为对本发明的二次电池用电极的制备方法进行说明的图。
图2为表示在本发明的实施例及比较例中制备的二次电池的基于循环数的容量测定结果的图表。
具体实施方式
以下,为了助于对本发明的理解,对本发明进行更详细的说明。此时,使用于本说明书及发明要求保护范围的术语或单词不应限定为通常的或词典上的意义来解释,而是应立足于发明人员为了以最佳的方法说明自己的发明而能够适当地定义术语的概念的原则,以符合本发明的技术思想的意义和概念来解释。
最近,为了改善制造锂二次电池时的活性物质之间或活性物质和集电体之间的导电性,进行着试图使用作为导电材料能表达自我容量,且因与活性物质及集电体之间的接触面大而电子的移动路径(path)大的石墨烯的研究。但石墨烯与以往所使用的碳黑之类的点型导电材料相比,不仅传导性的改善效果不佳,而且由于露出很多面,因而与电解液之间的反应性也不高,具有降低二次电池的寿命特性的缺点。
为此,本发明提供通过改善上述石墨烯的缺点来提高传导性的二次电池用导电材料。
具体地,本发明一实施例提供包括涂敷沥青的石墨烯片的二次电池用导电材料。
此时,上述沥青油煤系沥青组成,以二次电池用导电材料的总重量为基准,包含约6至15重量百分比。在上述二次电池用导电材料中的沥青的含量为6%以下的情况下,石墨烯片的表面的边缘(edge)部分一部分露出,从而难以获得传导性的改善效果,在沥青的含量为15%以上的情况下,过量包含非晶质碳层,从而发生电极活性物质容量的降低加深的问题。具体地,以二次电池用导电材料的总重量为基准,可包含约10重量百分比的上述煤系沥青。
并且,优选地,在本发明的二次电池用导电材料中,上述石墨烯片为通过执行化学剥离过程从石墨中分离的单层的石墨烯片形态。
并且,上述煤系沥青可以为涂敷于石墨烯片的整个表面或一部分的形态。
并且,本发明一实施例提供二次电池用导电材料的制备方法,包括:
制备纯的石墨烯片的步骤;
将上述石墨烯片与煤系沥青相混合的步骤;
对上述混合物进行高温煅烧,来制备沥青涂敷的石墨烯片的步骤。
此时,在上述方法中,纯的石墨烯片利用以下常规方法来形成:由石墨中形成氧化石墨烯,并对石墨烯片进行剥离之后,使用还原剂来实现还原(参照J.Am.Chem.Soc.1958,80(6),1339及Carbon 2007,45,1558)。其中,普通的氧化石墨烯片因本身的氧含量高而传导性低,因此,可包括在Ar/H2的混合气体气氛下对这种从石墨中分离出的单层的石墨烯片实施热处理来除去石墨烯片所包含的氧的步骤。此时,上述热处理温度优选为约1100℃,但也能在低于1100℃的温度下实施。
在本发明的方法中,上述沥青涂敷层可以为涂敷于石墨烯片的整个表面或一部分的形态。
并且,上述高温煅烧的步骤可通过以下步骤来实施:在将石墨烯片和沥青相混合之后,在空气气氛下,在作为接近沥青的软化点的250℃温度下维持3小时,并且在氮气气氛下以2℃/分钟的速度使温度上升至1150℃之后,在1150℃温度下煅烧5小时来实现碳化。
另一方面,在上述石墨烯片的涂敷步骤中,除了沥青涂敷之外,可利用不会与电解液引起副反应的,在涂敷于活性物质的表面时通常所使用的涂敷材料、重油(heavy oil)等非晶质碳物质。
像这样,本发明在单层的石墨烯片上涂敷石油系沥青来使用为导电材料,从而减少以往所使用的石墨烯片的露出面积,由此,不仅能够防止与电解液之间的副反应,而且通过增加每面积的能量密度,从而能够提高传导性。尤其,在沥青涂敷的石墨烯片的情况下,由于能够一同执行导电材料兼活性物质的作用,因此,能够增加二次电池的能量密度,改善寿命特性。
并且,本发明优选的一实施例提供二次电池用电极,包括集电体及涂敷于上述集电体上的电极活性物质层,上述电极活性物质层包含电极活性物质11、本发明的导电材料13及粘合剂(未图示)(参照图1)。
此时,本发明的电极可以为正极或负极。
具体地,在本发明的二次电池用电极中,上述集电体只要是不会在该上述电池中引发化学变化,又具有导电性的,就不受特殊限制,例如,可使用铜、不锈钢、铝、镍、钛、焙烧炭、在铜或不锈钢的表面利用碳、镍、钛及银等进行表面处理的物质以铝-镉合金等。并且,可使用表面形成有细微的凹凸的膜、薄片、箔、网、多孔质体及无纺布等多种形态。
并且,上述电极活性物质可以为能够吸藏及释放锂离子的含锂的钛复合氧化物(LTO)、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,包含选自由Al、Si、Sn、Ag、Bi、Mg、Zn、In、Ge、Pb、Pd、Pt及Ti等金属及包含这种元素的金属(Me)氧化物(MeOx)组成的组中的单一物或两种以上的混合物的负极活性物质。更具体地,上述电极活性物质可以为球形化的天然石墨,例如,被非晶质涂敷的球形化的天然石墨。
并且,上述粘合剂作为有助于活性物质和导电材料的结合以及对集电体的结合的成分,通常以电极活性物质总重量为基准,包含1至20重量百分比的上述粘合剂。作为这种粘合剂树脂的例,可以举出聚偏氟乙烯(PVDF)、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、三元乙丙橡胶(EPDM)、磺化-三元乙丙橡胶、丁苯橡胶、氟橡胶及它们的多种共聚物等。
并且,本发明以电极活性物质总重量为基准,可添加1至15重量百分比的导电材料,用于提高活性物质的导电性。在本发明的导电材料的含量为1重量百分比以下的情况下,在长期的循环期间存在寿命特性劣化的隐患,在本发明的导电材料的含量大于15重量百分比的情况下,由于在制备浆料时需要更多的粘合剂等,因此,相对减少活性物质的含量,从而具有容量减少的缺点。
并且,本发明的一实施例包含正极、负极、介于上述正极和负极之间的隔膜及电解液,上述正极及负极中的一个提供包含本发明的二次电池用电极的锂二次电池。
以下,通过实施例及比较例对本发明进行更加详细的说明。但实施例仅用于例示本发明,本发明的范围并不局限于这些实施例。
实施例
(制备例:涂敷沥青的石墨烯的制备)
在将从石墨中分离的纯的石墨烯片(90重量百分比)和煤系沥青(10重量百分比)相混合之后,在空气气氛下,在作为接近沥青的软化点的250℃温度下维持3小时,并在氮气氛下,以2℃/分钟的速度使温度上升至1150℃之后,在1150℃温度下煅烧5小时来实现碳化,从而制成了沥青涂敷的石墨烯片。
(实施例1)
以91重量百分比、6重量百分比及3重量百分比的比例混合LiCoO2、作为导电剂的石墨及作为粘合剂的PVdF,并分散于N-甲基吡咯烷酮(NMP)来制成了正极用浆料。将上述浆料涂敷于作为正极集电体的铝箔的一侧面,并在进行干燥之后,利用辊压机进行压缩成形,制成了正极。
然后,将95%的球形化的天然石墨、4%的作为粘合剂的羧甲基纤维素+丁苯橡胶及1%的作为导电材料的上述制备例1的沥青涂敷的石墨烯片分散于H2O,制成了负极用浆料。并且,在将上述浆料涂敷于作为负极集电体的铜(Cu)箔的一侧面之后,利用辊压机进行压缩成形,制成了负极。
然后,使聚烯烃系列的分离膜介于所制备的上述正极和负极之间,从而制成了电池组装体。在以1:1的体积比混合上述电池组装体和碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的溶剂中注入溶解有1M的LiPF6的电解质来制备了硬币型全电池。
*(比较例1)
除了使用常规的石墨烯片作为上述负极导电材料之外,以与上述实施例1相同的方法制备了负极、正极及硬币型全电池。
(比较例2)
除了上述碳黑作为上述负极导电材料之外,以与上述实施例1相同的方法制备了负极、正极及硬币型全电池。
(实验例1)
在将上述实施例1比较例1及比较例2所制备的硬币型全电池以0.1C充电/0.1C放电的方式进行3循环之后,以1C/1C方式进行了97循环的充放电。此时,充电以CC-CV模式(0.005C切断(cut off)),放电以CC模式进行。充放电电压(voltage)区间为2.5至4.2V。将基于循环数的标准容量,即,容量寿命特性的结果示于图2。
观察图2,当进行最初的充放电时,使用普通的石墨烯作为导电材料的比较例1的电池性能最优良,但在进行长期循环的期间内,使用本发明的沥青涂敷的石墨烯片的实施例1的电池呈现出最优良的寿命特性。
Claims (4)
1.一种二次电池用电极,包括集电体及涂敷于所述集电体上的电极活性物质层,所述二次电池用电极的特征在于,
所述电极活性物质层包含电极活性物质、导电材料及粘合剂,
其中所述电极活性物质是球形化的天然石墨,且
其中所述导电材料包含涂敷沥青的石墨烯片,且其中以二次电池用导电材料的总重量为基准,包含6至15重量百分比的所述沥青,且
其中所述沥青为煤系沥青,且其中所述煤系沥青为涂敷于石墨烯片的整个表面的形态。
2.根据权利要求1所述的二次电池用电极,其特征在于,所述电极活性物质为非晶质涂敷的球形化的天然石墨。
3.根据权利要求1所述的二次电池用电极,其特征在于,以电极活性物质总重量为基准,包含1至15重量百分比的所述导电材料。
4.一种锂二次电池,包含正极、负极、介于所述正极和负极之间的隔膜及电解液,所述锂二次电池的特征在于,
所述正极及负极中的一个包含如权利要求1所述的二次电池用电极。
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