CN106159241A - 一种正极极片及含有该正极片的无定形碳锂电池 - Google Patents

一种正极极片及含有该正极片的无定形碳锂电池 Download PDF

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CN106159241A
CN106159241A CN201610774118.9A CN201610774118A CN106159241A CN 106159241 A CN106159241 A CN 106159241A CN 201610774118 A CN201610774118 A CN 201610774118A CN 106159241 A CN106159241 A CN 106159241A
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龚本利
范未峰
张健
钱军
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Abstract

本发明涉及锂电池技术领域,具体涉及一种正极极片及含有该正极片的无定形碳锂电池,正极极片包括正极集流体和附着于正极集流体表面的正极材料层,所述正极材料层包含钒酸锂,钒酸锂具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为1‑3V。本发明无定形碳锂电池在正极极片的正极材料层中加入钒酸锂,在充电时,钒酸锂脱出的锂用于负极活性物质表面SEI膜(固体电解质界面膜)的形成,放电时,锂离子不会回到脱锂态的钒酸锂中,从而避免正极活性物质中锂的不可逆消耗,提高电池的首次充放电池效率和电池容量;而且本发明正极极片和无定型碳锂电池结构简单,制备成本低廉,可以提高锂电池的首次效率及容量,对促进锂电池的应用发展具有重要意义。

Description

一种正极极片及含有该正极片的无定形碳锂电池
技术领域
本发明涉及锂电池技术领域,具体涉及一种正极极片及含有该正极片的无定形碳锂电池。
背景技术
自从 1991 年,碳材料创造性的运用于锂离子电池领域,并带来该领域革命性的变化,即高效而安全的进行多次充放电后,其便被广泛的运用于移动电话、摄像机、笔记本电脑以及其他便携式电器上。与传统的铅酸、Ni-Cd、MH-Ni 电池相比,锂离子电池具有更高的比体积能量密度、比重量能量密度、更好的环境友好性、更小的自放电以及更长的循环寿命等,是二十一世纪理想的移动电器电源、电动汽车电源以及储电站用储电器。
目前商品化的负极材料主要是天然石墨、人造石墨、中间相炭微球等石墨类碳材料。石墨类碳材料,虽然具有导电性好、结晶程度高,具有良好的充放电平台等优点,但由于石墨为层状结构,与有机溶剂相溶性较差,在锂离子电池充电过程中,其溶剂分子很容易随锂离子共嵌入石墨片层内而破坏石墨层状结构,致使石墨层状结构发生剥离、石墨颗粒发生崩裂或粉化,进而导致锂离子电池循 环性劣化和容量的降低;且由于石墨自身结构的特殊性,其大功率充放电性能也相对较差, 因此,一定程度上限制了石墨类碳材料在大功率锂离子电池上的应用,这也给非石墨类碳 材料留下了更为广阔的发展空间。
无定形性碳是一种非石墨类材料,主要包括硬碳、软碳等,它们的热处理温度低,石墨化过程不完全;但无定形碳层间距d002比石墨大,同时石墨微晶大小La和Lc都比石墨小,脱嵌锂电位比石墨高,因此有很好的倍率充电性能,低温性能和安全性能,非常适合于动力电池。但硬碳、软碳的首次效率比较低,在与LiCoO2、镍钴锰酸锂、镍钴铝酸锂、LiFePO4、LiMn2O4等组成电池时,首次充电SEI膜形成消耗正极的锂,造成全电池首次效率低,电池容量低等问题。
因此,本发明提供一种可以提高无定形碳锂电池的首次效率及容量的正极极片及含有该正极片的无定形碳锂电池。
发明内容
本发明的目的在于解决以上技术问题,提供一种正极极片及含有该正极片的无定形碳锂电池,本发明正极极片和无定型碳锂电池结构简单,制备成本低廉,可以提高锂电池的首次效率及容量,对促进锂电池的应用发展具有重要意义。
为解决上述问题,本发明采用以下技术方案:
一种正极极片,包括正极集流体和附着于正极集流体表面的正极材料层,所述正极材料层包含钒酸锂,钒酸锂具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为1-3V。
进一步地,所述钒酸锂为LiVO2、LiV2O4、LiV2O5、Li4V3O8中的至少一种。
进一步地,所述正极材料层还包含活性物质、导电剂和粘结剂。
进一步地,所述正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为80-98: 0.5-10:0.5-5:1-5。
更进一步地,所述活性物质为LiCoO2、镍钴锰酸锂、镍钴铝酸锂、LiFePO4、LiFeMnPO4、Li3V2(PO4)2、LiMn2O4中至少一种。
一种无定型碳锂电池,包括正极极片和负极极片,所述正极极片为上述的正极极片。
进一步地,所述负极极片的材料为硬碳或软碳。
本发明的无定型碳锂电池在首次充电时,钒酸锂由于脱锂电位低于正极活性物质,因此先于活性物质脱锂,脱出的锂离子用于负极SEI膜(固体电解质界面膜)的形成;随着充电进行,正极电位提高,正极活性物质发生脱锂反应,脱出的锂则主要用于负极活性物质的可逆嵌锂。当电池首次放电时,由于钒酸锂电位低,锂离子不进入到其结构中,这样钒酸锂中的锂离子可以脱出但不能回嵌,补充了负极SEI膜形成时消耗的不可逆锂,从而提高电池的首次充放电池效率和电池容量。
本发明一种正极极片及含有该正极片的无定形碳锂电池,与现有技术相比,其突出的特点和优异的效果在于:
1.本发明无定形碳锂电池在正极极片的正极材料层中加入钒酸锂,在充电时,钒酸锂脱出的锂用于负极活性物质表面SEI膜(固体电解质界面膜)的形成,放电时,锂离子不会回到脱锂态的钒酸锂中,从而避免正极活性物质中锂的不可逆消耗,提高电池的首次充放电池效率和电池容量。
2.本发明正极极片和无定型碳锂电池结构简单,制备成本低廉,可以提高锂电池的首次效率及容量,对促进锂电池的应用发展具有重要意义。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明,但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
一种正极极片,所述正极极片包括正极集流体和附着于正极集流体表面的正极材料层,正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为80: 5:5:10,所述钒酸锂为LiVO2,具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为2.5-3.0V,活性物质为LiFePO4
实施例2
一种无定形碳锂电池,包括正极极片和负极极片,所述正极极片包括正极集流体和附着于正极集流体表面的正极材料层,正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为98: 0.5: 0.5: 0.5,所述钒酸锂为LiV2O4和Li4V3O8的混合物,具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为2.5-3V,活性物质为LiCoO2,负极极片的材料为硬碳。
实施例3
一种无定形碳锂电池,包括正极极片和负极极片,所述正极极片包括正极集流体和附着于正极集流体表面的正极材料层,正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为88: 7:3:2,所述钒酸锂为LiV2O5和Li4V3O8的混合物,具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为2.5-3V,活性物质为镍钴铝酸锂和LiMn2O4的混合物,负极极片的材料为软碳。
实施例4
一种无定形碳锂电池,包括正极极片和负极极片,所述正极极片包括正极集流体和附着于正极集流体表面的正极材料层,正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为90: 4:3:3,所述钒酸锂为LiV3O8,具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为2.5-3.0V,活性物质为镍钴铝酸锂,负极极片的材料为硬碳。
实施例5
一种无定形碳锂电池,包括正极极片和负极极片,所述正极极片包括正极集流体和附着于正极集流体表面的正极材料层,正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为92: 2:4:2,所述钒酸锂为LiV2O4,具有电化学脱锂活性,脱锂电位(VS. Li+/Li)为2.5-3.0V,活性物质为Li3V2(PO4)2,负极极片的材料为软碳。

Claims (7)

1.一种正极极片,包括正极集流体和附着于正极集流体表面的正极材料层,其特征在于,所述正极材料层包含钒酸锂,钒酸锂具有电化学脱锂活性,脱锂电位为1-3V。
2.根据权利要求1所述的一种正极极片,其特征在于,所述钒酸锂为LiVO2、LiV2O4、LiV2O5、Li4V3O8中的至少一种。
3.根据权利要求1所述的一种正极极片,其特征在于,所述正极材料层还包含活性物质、导电剂和粘结剂。
4.根据权利要求3所述的一种正极极片,其特征在于,所述正极材料层中活性物质:钒酸锂:导电剂:粘结剂的质量比为80-98: 0.5-10:0.5-5:1-5。
5.根据权利要求3或4所述的一种正极极片,其特征在于,所述活性物质为LiCoO2、镍钴锰酸锂、镍钴铝酸锂、LiFePO4、LiFeMnPO4、Li3V2(PO4)2、LiMn2O4中至少一种。
6.一种无定型碳锂电池,包括正极极片和负极极片,其特征在于,所述正极极片为权利要求1-6任意一项所述的正极极片。
7.根据权利要求6所述的一种无定型碳锂电池,其特征在于,所述负极极片的材料为硬碳或软碳。
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