CN103872396B - 抑制钛酸锂电池产气的电解液 - Google Patents

抑制钛酸锂电池产气的电解液 Download PDF

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CN103872396B
CN103872396B CN201410119778.4A CN201410119778A CN103872396B CN 103872396 B CN103872396 B CN 103872396B CN 201410119778 A CN201410119778 A CN 201410119778A CN 103872396 B CN103872396 B CN 103872396B
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electrolytic solution
potassium
sylvite
lithium titanate
titanate battery
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CN103872396A (zh
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杨光
廖红英
孟蓉
李冰川
付呈琳
赵季飞
王磊
王倩
牛嵩林
李洪雨
王纲
强京林
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Beijing Chemical Reagents Research Institute LLC
Hebei Zhonglan Huateng New Energy Materials Co ltd
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BEIJING INST OF CHEMICAL REAGENT
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

本发明公开了一种抑制钛酸锂电池产气的电解液,属于钛酸锂电池领域,该电解液中含有钾盐,所述钾盐在该电解液中的质量百分比为0.001%~30%。通过在电解液中加入特定用量的钾盐,通过钾盐对钛酸锂负极的电化学稳定作用,使电解液在钛酸锂负极表面保持稳定,不易分解,从而抑制钛酸锂电池产气。

Description

抑制钛酸锂电池产气的电解液
技术领域
本发明涉及钛酸锂电池领域,尤其涉及一种抑制钛酸锂电池产气的电解液。
背景技术
钛酸锂(Li4Ti5O12)具有尖晶石结构,是一种“零应变”电极材料,放电电压平稳,嵌锂电位高(vs.1.55V),不易引起金属锂析出,材料来源广,清洁环保。采用钛酸锂作为负极的电池,具有优异的循环性能,有望在电动车、储能电池中得到应用。但是在循环过程中,尤其在高温下,电池会在一定程度上产气,引起电池膨胀,影响外观及使用。
发明内容
本发明要解决的技术问题是提供一种抑制钛酸锂电池产气的电解液,能使钛酸锂负极表面保持稳定,不易引起电解液分解,从而抑制钛酸锂电池产气,从而解决现有钛酸锂电池产气引起电池膨胀,影响外观及使用的问题。
为解决上述技术问题,本发明提供一种抑制钛酸锂电池产气的电解液,该电解液中含有钾盐,所述钾盐在该电解液中的质量百分比为0.001%~30%。
上述电解液中,所述钾盐为六氟磷酸钾、四氟硼酸钾、双草酸硼酸钾、三氟甲基磺酸钾、双(三氟甲基磺酰)亚胺钾、六氟砷酸钾、碳酸钾、高氯酸钾、硝酸钾、硫酸钾、氯化钾、碘化钾、溴化钾中的一种或几种。
上述电解液中,所述电解液中的有机溶剂为碳酸乙烯酯、碳酸二乙酯和碳酸甲乙酯的混合物,其中碳酸乙烯酯、碳酸二乙酯与碳酸甲乙酯的质量比为1:1:1。
所述电解液中的电解质为六氟磷酸锂,其用量为1升有机溶剂中加入1摩尔六氟磷酸锂。
本发明的有益效果为:通过在电解液中加入特定用量的钾盐,通过钾盐对钛酸锂负极的电化学稳定作用,使电解液在钛酸锂负极表面保持稳定,不易分解,从而抑制钛酸锂电池产气。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。
本发明实施例提供一种抑制钛酸锂电池产气的电解液,该电解液中含有钾盐,所述钾盐在电解液中的质量百分比为0.001%~30%。
上述电解液中,钾盐为六氟磷酸钾、四氟硼酸钾、双草酸硼酸钾、三氟甲基磺酸钾、双(三氟甲基磺酰)亚胺钾、六氟砷酸钾、碳酸钾、高氯酸钾、硝酸钾、硫酸钾、氯化钾、碘化钾、溴化钾中的一种或几种。
上述电解液中的有机溶剂为碳酸乙烯酯、碳酸二乙酯和碳酸甲乙酯的混合物,其中碳酸乙烯酯、碳酸二乙酯与碳酸甲乙酯的质量比为1:1:1;
该电解液中的电解质为六氟磷酸锂,其用量为1升有机溶剂中加入1摩尔六氟磷酸锂。
下面结合具体实施例对本发明的电解液作进一步说明。
实施例一
本实施例提供一种抑制钛酸锂电池产气的电解液,该电解液的有机溶剂中含有钾盐,钾盐为六氟磷酸钾,钾盐在电解液中的质量百分比为0.1%。电解液中的有机溶剂为碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)的混合物,其中EC、DEC、EMC的质量比为1:1:1,电解质为1mol/L的LiPF6(六氟磷酸锂)。
实施例二
本实施例提供一种抑制钛酸锂电池产气的电解液,该电解液的有机溶剂中含有钾盐,钾盐为六氟磷酸钾,钾盐在电解液中的质量百分比为0.5%。电解液中的有机溶剂为碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)的混合物,其中EC、DEC、EMC的质量比为1:1:1,电解质为1mol/L的LiPF6(六氟磷酸锂)。
实施例三
本实施例提供一种抑制钛酸锂电池产气的电解液,该电解液的有机溶剂中含有钾盐,钾盐为六氟磷酸钾,钾盐在电解液中的质量百分比为1%。电解液中的有机溶剂为碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)的混合物,其中EC、DEC、EMC的质量比为1:1:1,电解质为1mol/L的LiPF6(六氟磷酸锂)。
可以知道,上述各实施例中电解液所采用的有机溶剂仅为举例说明,只要是能构成用在酸锂电池中的电解液的有机溶剂,加入本发明限定用量的钾盐,均可以实现抑制电解液产气的目的,而并不限于上述各实施例中有机溶剂构成的几种电解液。
比较实施例一
电解液中的有机溶剂为碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)的混合物,其中EC、DEC、EMC的质量比为1:1:1,电解质为1mol/L的LiPF6
将上述实施例及比较例中的电解液注入到钛酸锂电池中。该电池正极为锰酸锂,负极为钛酸锂,铝塑膜封装,额定容量为1Ah。在55℃下循环2000周,膨胀率及容量保持率见表1。
表1
膨胀率 容量保持率
实施例1 1.6% 99.8%
实施例2 1.2% 99.9%
实施例3 1.4% 99.7%
比较实施例例1 2.5% 99.7%
由上表可见,添加钾盐(如六氟磷酸钾)可有效抑制电池产气,降低膨胀率,且不影响电池的循环性能。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。

Claims (1)

1.一种抑制钛酸锂电池产气的电解液,其特征在于,该电解液中含有钾盐,所述钾盐在该电解液中的质量百分比为0.001%~30%;
所述钾盐为六氟磷酸钾、四氟硼酸钾、三氟甲基磺酸钾、双(三氟甲基磺酰)亚胺钾、六氟砷酸钾、高氯酸钾、硝酸钾、硫酸钾、氯化钾、碘化钾、溴化钾中的一种或几种;
所述电解液中的有机溶剂为碳酸乙烯酯、碳酸二乙酯和碳酸甲乙酯的混合物,其中碳酸乙烯酯、碳酸二乙酯与碳酸甲乙酯的质量比为1:1:1;
所述电解液中的电解质为六氟磷酸锂,其用量为1升有机溶剂中加入1摩尔六氟磷酸锂。
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CN104891517A (zh) * 2015-06-09 2015-09-09 天津金牛电源材料有限责任公司 一种利用六氟磷酸锂回收混合酸生产氟硼酸钾的方法
CN106570959A (zh) * 2016-11-01 2017-04-19 通化师范学院 基于gsm模块的智能防盗电控门锁系统
CN109449485B (zh) * 2018-10-15 2021-07-20 苏州大学 一种耐超低温锂电池电解液

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