CN112864393A - 一种低温高倍率锂离子电池 - Google Patents
一种低温高倍率锂离子电池 Download PDFInfo
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Abstract
本发明公开了一种低温高倍率锂离子电池，其包括：正极片、负极片、隔膜、电解液；所述正极活性物质一次颗粒为纳米级包覆磷酸铁锂，负极活性物质为小颗粒无定型固相软碳或硬碳包覆石墨，既保证电池高容量的发挥，又提升低温倍率性能；低温导电低粘度电解液可有效改善电池低温下极化加剧现象；高透气度、高离子电导率湿法陶瓷隔膜，有利于提升电池在高倍率下电解液的保持率。本发明的低温高倍率锂离子电池具有优异的低温倍率性能，通过优选材料，使电池在‑40℃下能达到3C的放电能力和0.2C充电能力，20℃能达到10C放电能力和10C充电能力，解决了现有技术中存在的问题。
Description
技术领域
本发明涉及电池技术领域，是一种低温高倍率锂离子电池。
背景技术
锂离子电池具有能量密度高、循环寿命长及充放电效率高等优点，随着行业的发展，对锂离子电池高低温充放电性能提出了更高的的需求。高倍率锂离子电池具有充放电性能优异、爆发力足，内阻小等特点，广泛用于航拍无人机，农业植保无人机，应急启动电源、航模、电动工具等一些轻型设备上，低温型锂电池在高寒、高海拔地区以及航空航天、国防装备等需求潜力巨大。
常规的倍率型锂离子电池多采用锰酸锂、钴酸锂、三元材料及磷酸铁锂作为正极材料。锰酸锂以成本低，安全性好而被广泛使用，但循环性能及电化学稳定性较差；钴酸锂尽管在目前商业化正极材料中低温和倍率性能是最优秀的，但也存在电池成本高、循环寿命短、安全性能差等问题；三元材料多应用于高能量密度动力电池，安全性能同样广受诟病；磷酸铁锂具有成本低、安全稳定、循环寿命优越的性能，但电池大多在常温下使用，低温下易出现放电能量低或不能放电的问题，直接影响电池的正常的使用。
因此，从锂离子电池成本、安全及电性能等方面考虑，以小颗粒磷酸铁锂和石墨作为正负极材料，对锂离子电池的材料进行合理选用，制备一种在低温-40℃下可高倍率放电并能持续充电，同时具备在常温下可高倍率充放电的锂离子电池。
发明内容
本发明的目的是提供一种低温高倍率锂离子电池，使电池能够在低温下和常温下具有优异的充放电倍率性能。
为实现上述目的，本发明提供了一种低温高倍率锂离子电池，其包括：正极片、负极片、隔膜、电解液；所述正极片包含正极活性物质与涂碳铝箔，负极片包含负极活性物质与铜箔。
上述的低温高倍率锂离子电池，其中，所述正极活性物质为磷酸铁锂，负极活性物质为石墨。
上述的低温高倍率锂离子电池，其中，所述磷酸铁锂为碳包覆型产品，采用磷酸铁工艺制备，二次颗粒粒径D50在2-5μm左右，由大量的一次颗粒团聚而成，一次颗粒粒径为纳米级（50-200nm），形状规则，类似球形。
上述的低温高倍率锂离子电池，其中，所述石墨为无定型软碳或硬碳包覆型产品，采用固相包覆工艺，粒径D50为5-10μm，材料内部结构致密、表面光滑。
上述的低温高倍率锂离子电池，其中，所述铝箔为双面涂炭型，厚度为15-20μm，单面涂炭层为1-2μm。
上述的低温高倍率锂离子电池，其中，所述铜箔厚度为8-15μm。
上述的低温高倍率锂离子电池，其中，所述电解液包括：溶剂、添加剂和锂盐等。溶剂为环状和线性酯类，具有低温导电、低粘度特征；添加剂为含硫添加剂，具有抗氧化性能；锂盐为六氟磷酸锂、四氟硼酸锂和双草酸硼酸锂的一种或多种，锂盐浓度为0.8-1.5mol/L。
上述的低温高倍率锂离子电池，其中，所述隔膜为湿法隔膜，包括聚烯烃基膜和涂敷在基膜上的纳米陶瓷层，基膜厚度为12-16μm，纳米陶瓷层厚度为2-4μm，隔膜透气度为200-300s/100ml。
与现有技术相比，本发明具有以下有益效果：
碳包覆型磷酸铁锂一次颗粒为纳米级，可以有效提高锂离子扩散系数，放电平台电压较一般材料有优势，有利于锂离子电池低温倍率性能。小颗粒石墨可缩短锂离子扩散距离、增加电解液浸润面积，无定形碳包覆可以避免溶剂与石墨直接接触，减少电化学反应活性位点，降低副反应的发生；另一方面，无定形碳的层间距比石墨的层间距大，有利于锂离子的快速扩散，提高电池倍率性能。铝箔为双面涂碳层，可增加导电及黏附性以进一步降低极片内阻。低温导电、低粘度电解液可以提高电导率并改善电池在低温环境工作时由于粘度较高导致放电平台电压低的问题；而含硫添加剂具有良好的低温性能，低温下可以在石墨表面形成一层致密的SEI膜，有利于电池的低温循环性能。选择的隔膜为湿法聚烯烃基膜，具有高透气度、高离子电导率特征，其单面涂敷陶瓷，可增加保液量，进一步提升电池倍率放电及循环性能。
附图说明
图1为本发明实施案例1中提供的低温高倍率锂离子电池在-40℃下3C放电曲线图。
图2为本发明实施案例1中提供的低温高倍率锂离子电池在-40℃下0.2C充电曲线图。
图3为本发明实施案例1中提供的低温高倍率锂离子电池在常温下10C放电曲线图。
图4为本发明实施案例1中提供的低温高倍率锂离子电池在常温下10C充电曲线图。
具体实施方式
以下结合附图并通过具体实施案例对本发明作进一步的阐述，这些实施例仅用于说明本发明，并不是对本发明保护范围的限制。
本发明提供了一种低温高倍率锂离子电池，包括：正极耳、负极耳、正极片、负极片、隔膜、电解液、铝塑膜；所述正极片包含正极活性物质与涂炭铝箔，负极片包含负极活性物质与铜箔。负极片、隔膜与正极片通过Z字形叠片形成一个叠片体，正极耳与负极耳同侧焊接在叠片体对应的正极片与负极片集流体上，通过铝塑膜对叠片体进行封装，电解液注入铝塑膜内浸润叠片体，然后通过化成、分容，最终形成电芯。
优选的，正极活性物质为磷酸铁锂，负极活性物质为石墨。
优选的，所述磷酸铁锂为碳包覆型产品，采用磷酸铁工艺制备，二次颗粒粒径D50在2-5μm左右，由大量的一次颗粒团聚而成，一次颗粒粒径为纳米级（10-100nm），形状规则，类似球形。
优选的，所述石墨为无定型软碳或硬碳包覆型产品，采用固相包覆工艺，粒径D50为5-10μm，材料内部结构致密、表面光滑。
优选的，所述铝箔为双面涂炭型，厚度为15-20μm，单面涂炭层为1-2μm。
优选的，所述铜箔厚度为8-12μm。
优选的，所述电解液包括：溶剂、添加剂和锂盐等。溶剂为环状和线性酯类，具有低温导电、低粘度特征；添加剂为含硫添加剂，具有抗氧化性能；混合锂盐为六氟磷酸锂、四氟硼酸锂和双草酸硼酸锂的一种或多种，锂盐浓度为0.8-1.5mol/L；
优选的，所述隔膜为湿法隔膜，包括聚烯烃基膜和涂敷在基膜上的纳米陶瓷层，基膜厚度为12-16μm，纳米陶瓷层厚度为2-4μm，隔膜透气度为200-300 s/100ml。
实施例1
本实施例提供了一种标称容量为20Ah的低温高倍率锂离子电池。所用材料：正极活性物质磷酸铁锂，粒径D50为3μm，一次颗粒为50-200nm；负极活性物质石墨，粒径D50为7μm；涂碳铝箔厚度为（20+2）μm；铜箔厚度为12 μm；电解液锂盐为六氟膦酸锂和四氟硼酸锂，浓度为1.2mol/L；所用隔膜为湿法PE陶瓷隔膜，厚度为(12+4) μm。经过搅拌、涂布、辊压、模切、叠片、点焊、封装、烘烤、注液、化成、除气、baking、除气、分容、老化、二封等工序，最后制成成品电池。
按照上述选材及工序制作的20Ah低温高倍率锂离子电池，如图1、图2所示，在-40℃环境温度下3C倍率放电以及0.2C充电曲线，充电及放电容量保持率>90%。如图3、图4所示，在25℃环境温度下10C充电和放电曲线，放电容量保持率>90%，充电容量保持率>80%.
综上所述，常规的高倍率锂离子电池多采用锰酸锂、钴酸锂和三元材料作为正极材料，或存在安全性能差、成本高、循环寿命短等问题，而本发明采用磷酸铁锂作为正极材料，最大优势在于电池安全稳定、成本低、循环寿命好。根据低温高倍率锂离子电池充放电电流大、使用环境温度低等特征，本发明选用粒径小的正负极活性物质材料(正极一次颗粒纳米级，负极5-10μm)可以有效提高锂离子扩散系数及平台电压，无定形碳包覆石墨制备工艺可增加电解液保液量并降低副反应发生，有利于电池循环及低温放电性能。低温导电、低粘度、混合锂盐型电解液可进一步改善电池在低温环境下极化加剧现象。此外，本发明选用的湿法陶瓷隔膜除了具备干法膜的高透气度外，还具有高离子电导率、高保液量特征，有利于提升电池在高倍率下电解液的保持率。
最后说明的是，尽管本发明的内容通过优选实施例进行了详细说明，但对于不同优选实施的任意组合或在不脱离本发明的原理的情况下进行修改、替换，同样应当视为本发明所公开的内容。
Claims (5)
1.一种低温高倍率锂离子电池，其特征在于，包括：正极片、负极片、隔膜、电解液；所述正极片包含正极活性物质磷酸铁锂与铝箔，负极片包含负极活性物质石墨与铜箔。
2.根据权利要求1所述的低温高倍率锂离子电池，其特征在于，所述磷酸铁锂为碳包覆型产品，粒径D50为2-5μm，一次颗粒为纳米级（50-200nm）；所述石墨为固相无定型软碳或硬碳包覆型产品，粒径D50为5-10μm。
3.根据权利要求1所述的低温高倍率锂离子电池，其特征在于，所述铝箔为双面涂炭型，铝箔总厚度为15-20μm，单面涂炭层为1-2μm；铜箔厚度为8-15μm。
4.根据权利要求1所述的低温高倍率锂离子电池，其特征在于，所述电解液包括：溶剂、添加剂和锂盐等，溶剂为环状和线性酯类，添加剂为含硫添加剂，锂盐为六氟磷酸锂、四氟硼酸锂和双草酸硼酸锂一种或多种，锂盐浓度为0.8-1.5mol/L。
5.根据权利要求1所述的低温高倍率锂离子电池，其特征在于，所述隔膜为湿法陶瓷隔膜，基膜厚度为12-16μm，纳米陶瓷层厚度为2-4μm，透气度为200-300 s/100ml。
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