CN105670550B - 一种导热胶及含有该导热胶的二次电池 - Google Patents

一种导热胶及含有该导热胶的二次电池 Download PDF

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CN105670550B
CN105670550B CN201610207240.8A CN201610207240A CN105670550B CN 105670550 B CN105670550 B CN 105670550B CN 201610207240 A CN201610207240 A CN 201610207240A CN 105670550 B CN105670550 B CN 105670550B
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heat
conducting glue
secondary cell
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battery core
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CN105670550A (zh
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明帮生
高伟
赵德强
贾士强
赵丰刚
耿继斌
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Dongguan Amperex Technology Ltd
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Abstract

本申请涉及锂离子电池领域，具体讲，涉及一种导热胶及含有该导热胶的锂离子电池。本申请通过在热熔胶体系中添加导热填料制备得到导热胶，该导热胶具有良好的导热性能及粘接性能，可以将保护器件与电芯粘接牢固，同时通过导热胶把电芯热量快速传递给保护器件使其快速断开改善过充安全，保护电芯；本申请导热胶的初粘力较强，依靠其强的粘接性使保护器件与电芯保持良好接触，避免导热胶在电芯发生胀气或变形等情况下脱离电芯。

Description

一种导热胶及含有该导热胶的二次电池
技术领域
本申请涉及锂离子电池领域，具体讲，涉及一种导热胶及含有该导热胶的二次电池。
背景技术
锂离子电池具有能量密度高、循环寿命长、环境友好及可再生产等诸多优点，目前己被广泛应用于各类消费电子产品中。但是，由于锂离子的化学体系不尽相同，以过度充电(overcharge)为代表的滥用安全性能是锂离子电池面临的重要困难。目前常用的提高锂离子电池在滥用时的安全性的措施是通过外接保护装置，这种措施可以在很大程度上提高锂离子电池在滥用时的安全性。
目前，商用锂离子电池一般在电池外部焊接温度保险丝、断路器、PTC等作为安全保护装置，当电池由于滥用导致产热并温度上升时，电池主体的热量传导给温度保险丝，当温度高于温度保险丝的触发温度时，保险丝便会断开，切断电路，保证电池的安全性。
目前市场上主要采用双面胶进行粘接，其具有导热性差、粘接性不足的缺陷。针对现有技术中存在的缺陷和不足，特提出本申请。
发明内容
本申请的首要发明目的在于提出一种导热胶。
本申请的第二发明目的在于提出该导热胶的应用。
本申请的第三发明目的在于提出含有该导热胶的锂离子电池。
本申请的第四发明目的在于提出该锂离子电池的制备方法。
为了完成本申请的发明目的，采用的技术方案为：
本申请涉及一种导热胶，所述导热胶中含有热熔胶和导热填料。
优选的，所述热熔胶选自EVA热熔胶、聚酰胺热熔胶、聚氨酯热熔胶、聚酯热熔胶、聚乙烯热熔胶、聚酯酰胺热熔胶、苯乙烯系热塑性弹性体的至少一种；优选的，所述聚氨酯热熔胶选自异氰酸酯聚氨酯预聚体；优选的，所述苯乙烯系热塑性弹性体选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物。
优选的，所述导热填料选自金属、金属氧化物、碳材料、氮化物、碳化物、硅材料中的至少一种；所述金属优选银、铜或锡中的至少一种；所述金属氧化物优选氧化铝、氧化镁、氧化锌、氧化钛、SnOy中的至少一种；所述碳材料优选硬碳、软碳、中间相炭微球、碳纳米管、石墨、石墨烯中的至少一种；所述氮化物优选氮化硅、氮化铝、氮化硼、氮化钛中的至少一种；所述碳化物优选碳化硅、碳化钨中的至少一种；所述硅材料优选Si，SiOx中的至少一种；其中，0＜x≤2，0＜y≤2。
优选的，所述导热填料的导热系数为1W/mK～10000W/mK，优选20～6000W/mK。
优选的，所述导热填料的粒径为1nm～100μm，或所述导热填料中含有粒径大于等于1nm且小于1μm的导热填料颗粒与粒径大于等于1μm且小于等于50μm的导热填料颗粒。
优选的，所述导热填料占所述导热胶的质量百分比1％～99％，优选为20～75％。
优选的，所述导热胶的熔融粘度为1000～1×106CPs，初粘性为0.5～100N，剥离强度为0.1～20N/3mm，融化温度为120～190℃，导热系数为0.1～10000W/mK；优选的，所述导热胶的熔融粘度为1000～20000CPs，初粘性为0.5～60N，剥离强度为0.5～10N/3mm，融化温度为160～180℃，导热系数为0.1～100W/mK。
本申请还涉及该导热胶在二次电池中的应用。
本申请还涉及一种二次电池，包含电芯、固定在电芯上的安全部件以及位于电芯和安全部件之间的导热胶，所述导热胶为本申请的导热胶；
优选的，所述导热胶的面积为1mm2～500mm2，所述导热胶的厚度为0.01～10mm。
本申请还涉及该电池的制备方法，具体步骤为：在所述安全部件上施加所述导热胶，或在电芯上施加所述导热胶，施加0.1～100N的压力使安全部件与电芯粘接牢固。
本申请所能达到的有益技术效果为：
1、本申请通过在热熔胶体系中添加导热填料制备得到导热胶，该导热胶具有良好的导热性能，优选的，导热胶的导热系数为0.1～100W/mK范围内，从而把电芯热量快速传递给保护器件使其温度能够与电芯内保持同步并快速断开从而保护电芯，改善过充安全性能；
2、本申请的导热胶的初粘力较强，依靠其强的粘接性使保护器件与电芯保持良好接触，避免了电芯在滥用条件下发生胀气或变形时导热胶脱离电芯表面；
3、本申请的导热胶可采用喷涂工艺将其喷到电芯放置保护器件位置来把保护器件与电池良好的粘接起来，实现定量定位布胶，并且本申请的导热胶初粘力强提高了生产效率，量产工艺连贯可靠满足量产工艺要求。
附图说明
图1为热熔胶凝固与粘接时的机理图；
图2为实施例1在过充时温度、电压、电流随时间温度的变化曲线；
图3为对比例2在过充时温度、电压、电流随时间温度的变化曲线。
具体实施方式
下面结合具体实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
本申请涉及一种导热胶，该导热胶中含有热熔胶和导热填料。
作为本申请导热胶的一种改进，导热填料选自金属、金属氧化物、碳材料、氮化物、碳化物、硅材料中的至少一种；
优选的，金属为金属粉末，并选自银、铜或锡中的至少一种，并优选银；
优选的，金属氧化物选自氧化铝、氧化镁、氧化锌、氧化钛、SnOy中的至少一种，0＜y≤2；
优选的，碳材料选自硬碳、软碳、中间相炭微球、碳纳米管、石墨、石墨烯中的至少一种；
优选的，氮化物选自氮化硅、氮化铝、氮化硼、氮化钛中的至少一种；
优选的，碳化物选自碳化硅、碳化钨中的至少一种；
优选的，硅材料选自Si、SiOx中的至少一种；0＜x≤2。
本申请中的导热填料还可以为含有上述化合物的天然矿物。
作为本申请导热胶的一种改进，导热填料的粒径1nm～100μm，本申请中的粒径指填料的中值粒径。如果粒径过大会导热填料填充度不够，导热率不高，粒径过小加工性能偏差。
或所述导热填料中含有粒径大于等于1nm且小于1μm的导热填料颗粒与粒径大于等于1μm且小于等于50μm的导热填料颗粒，选用多种粒径大小颗粒可提高填充量提升导热效果。
作为粒径均一的导热填料，其粒径优选为20nm～10μm之间。
作为本申请导热胶的一种改进，导热填料占导热胶的质量百分比1％～99％，优选20～75％。如果添加的量过大会导致粘接性能偏差，如果添加的量过小不能显著提升导热效果。
作为本申请导热胶的一种改进，导热填料为导热系数为1W/mK～10000W/mK(25℃)，优选为20～6000W/mK(25℃)，更优选为20～5000W/mK(25℃)。
如采用导热系数为25W/mK～500W/mK的导热填料，导热填料在导热胶中所占质量百分比优选为20～70％；
如采用导热系数为1000W/mK～5000W/mK的导热填料，导热填料在导热胶中所占质量百分比优选为1～10％。
本申请中的热熔胶为可塑性粘合剂，在一定温度范围内其物理状态随温度改变而改变，而化学特性不变。
作为本申请导热胶的一种改进，热熔胶选自EVA(乙烯-醋酸乙烯共聚物)热熔胶、聚酰胺热熔胶、聚氨酯热熔胶、聚酯热熔胶、聚乙烯热熔胶、聚酯酰胺热熔胶、苯乙烯系热塑性弹性体的至少一种。
作为本申请导热胶的一种改进，本申请中的乙烯-醋酸乙烯共聚物(也称为乙烯-乙酸乙烯共聚物)是由乙烯(E)和乙酸乙烯(VA)共聚而制得，简称为EVA。本申请为了保证导热胶的粘贴性能及其他性能，优选采用乙酸乙烯(VA)含量为30％的乙烯-醋酸乙烯共聚物。
本申请中的聚酰胺(PA)为大分子主链重复单元中含有酰胺基团的高聚物。聚酰胺可由内酸胺开环聚合制得，也可由二元胺与二元酸缩聚等得到的。PA具有良好的综合性能，包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性，PA可选自PA6、PA66、PA11、PA12、PA46、PA610、PA612、PA1010等。为了适应本申请导热胶的粘贴性能或其他，优选PA12。
本申请中的聚氨酯全称为聚氨基甲酸酯，为主链上含有重复氨基甲酸酯基团的大分子化合物，是由有机二异氰酸酯或多异氰酸酯与二羟基或多羟基化合物加聚而成。
本申请中的聚乙烯(PE)热熔胶，包括高密度聚乙烯(HDPE)热熔胶和低密度聚乙烯(LDPE)热熔胶。HDPE粉末热熔胶是一种结晶度高、非极性的热塑性树脂，LDPE粉末热熔胶融化温度低，熔融后流动性好。
本申请中的聚酯酰胺为分子链上含有酯键和酰胺键的聚合物，其综合了聚酯和聚酰胺的优点，包括线型聚酯酰胺和交联聚酯酰胺。作为本申请的热熔胶，优选为交联聚酯酰胺。
作为本申请热熔胶使用的聚酯，是由二元酸与二元醇酯化而得的热塑性产物。通常由对苯二甲醇二甲酯、间苯二甲酸、乙二醇和丁二醇等为原料。聚酯热熔胶与聚酰胺热熔胶一样，具有较高的耐热性，良好的耐候、耐水性和弹性。
作为本申请导热胶的一种改进，聚氨酯热熔胶优选异氰酸酯基聚氨酯预聚体；其聚合的反应式为：
异氰酸酯基聚氨酯预聚体中含异氰酸酯基的化合物可选自：甲苯二异氰酸酯、多亚甲基多苯基异氰酸酯、1,6-己二异氰酸酯、二苯基甲烷4，4’-二异氰酸酯、甲苯二异氰酸酯等；异氰酸酯基聚氨酯预聚体中含羟基的化合物可选自：聚氧化丙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸一缩二乙二醇酯二醇、聚己二酸乙二醇-丙二醇酯二醇、聚己二酸乙二醇酯二醇。
异氰酸酯基聚氨酯预聚体在粘贴过程中，固态胶体被加热熔融成流体涂抹在基材表面，热熔胶中的活泼端基-NCO基团与基材表面吸附水、吸收空气中的水以及表面存在的羟基等活泼氢发生化学反应，生成聚脲结构。聚氨酯胶粘剂表现出高度的活性与极性，与含有活泼氢的基材，如泡沫、塑料、木材、皮革、织物、纸张、陶瓷等多孔材料，以及金属、玻璃、橡胶、塑料等表面光洁的材料都有优良的化学粘接力。这使得该体系导热胶将保护器件和电池良好粘接牢固。
热熔胶凝固与粘接时的机理图如图1所示；异氰酸酯基聚氨酯预聚体凝固与粘接时发生的化学反应为：
1、导热胶自身交联的化学反应
2、导热胶与基材之间的化学反应
其中，苯乙烯系热塑性弹性体选自苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)。
作为本申请导热胶的一种改进，导热胶中还可以添加增粘剂、抗氧剂、催化剂、粘度调节剂中的至少一种，对导热胶的性能进行调节。
作为本申请导热胶的一种改进，所述导热胶的熔融粘度为1000～1×106CPs(175℃)，初粘性为0.5～100N，剥离强度为0.1～20N/3mm，融化温度为120～190℃，导热系数为0.1～10000W/mK(25℃)；优选的，导热胶的熔融粘度为1000～20000CPs(175℃)，初粘性为0.5～60N，剥离强度为0.5～10N/3mm，融化温度为160～180℃，导热系数为0.1～100W/mK(25℃)。
更优选的，本申请导热胶的导热系数为0.2～50W/mK(25℃)。
本申请导热胶的制备方法为：在无水份惰性气体保护环境，将原料加热后，添加导热填料，搅拌分散均匀，然后密封。
本申请还涉及该导热胶的用途，本申请的导热胶可用于二次电池中，适用于二次电池中任何需要粘结的位置，并优选安装于电芯和安全部件之间。其中，安全部件包含断路器、PTC(Positive Temperature Coefficient)和保险丝。
本申请还涉及一种二次电池，包含电芯、固定在电芯上的安全部件以及位于电芯和安全部件之间的导热胶，其中，导热胶为本申请的导热胶。
作为本申请二次电池的一种改进，导热胶的面积为1mm2～500mm2，导热胶的厚度为0.05～5mm。
本申请还涉及该二次电池的制备方法，在安全部件上施加导热胶，或在电芯上施加导热胶，施加0.1～100N的压力使安全部件与电芯粘接牢固。优选的，导热胶加热融化后进行操作的温度为150～200℃。
本申请中导热胶的施加方式可为涂覆、粘贴、放置等；涂覆方法可采用打点、涂线、喷涂等方式。
本申请实施例中使用的异氰酸酯基聚氨酯预聚体购于广州雅威公司；
本申请实施例中使用的乙烯-醋酸乙烯共聚物(EVA)、聚酰胺(PA)、低密度聚乙烯(LDPE)、聚酯酰胺(PEA)购自华工百川公司；
本申请实施例中使用的双面胶纸3M467、导热双面胶3M8805购自3M公司；
本申请实施例中使用的高密度聚乙烯(HDPE)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)购自深圳市塑源实业有限公司。
实施例1～9
按照表1所示的热熔胶与导热填料制备导热胶，并将制备得到的导热胶涂覆于电芯和安全部件之间，并对电芯的性能进行检测。
导热胶制备方法：在无水份惰性气体保护环境，将原料加热后添加导热填料，搅拌分散均匀，然后密封。
电池的制备方法：在安全部件上施加导热胶，或在电芯上施加导热胶，施加0.1～100N的压力使安全部件与电芯粘接牢固；导热胶的操作温度为150～200℃。
表1：
检测方法为：
(一)初粘力测试方法：以0.03mg/mm滴胶量制样品，切3mm×20mm样品，滴胶后粘结TCO，完成制样2分钟内在常温环境下测试拉力。
(二)剥离强度测试方法：以0.06mg/mm的滴胶量制作粘接样品，切3mm宽样品，滴胶后粘结TCO，然后180℃剥离检测得到电池的性能。
(三)过充测试方法：1C恒流充电到10V，CV 10V持续2h或电芯温度降低到40℃以下停止测试。其中，实施例1与对比例2过充时不同温度和时间下温度、电压、电流的变化曲线分别如图2和图3所示。
实施例1～9的导热胶以及对比例1～3的性能如表2和表3所示：
表2：
表3：
实施例2
按照表4所示的热熔胶与导热填料制备导热胶，并将制备得到的导热胶涂覆于电芯和安全部件之间，并对电芯的性能进行检测。制备方法同实施例1。
表4：
实施例10～26的导热胶和采用导热胶制备得到的电池的性能如表5和表6所示：
表5：
表6：
对比例4～12
按照表7所示的热熔胶与导热填料制备导热胶，并将制备得到的导热胶涂覆于电芯和安全部件之间，并对电芯的性能进行检测。制备方法同实施例1。
其中，环氧树脂的结构式为：
式1；
式2。
表7：
对比例4～12的导热胶和采用导热胶制备得到的电池的性能如表8和表9所示：
表8：
表9：
对比例4的实验结果说明，如果导热填料的粒径过大，导热性能及粘接性能都会下降；
对比例5和6的实验结果说明，如果不添加导热填料，或者添加导热系数较低的填料，制备得到的导热胶的导热系数无法得到有效提升；
对比例7～9的实验结果说明，采用导热性能适中的导热填料，如果添加的量过低，其导热性能无法得到有效提升，如果添加量过大，导热胶的物理性能会收到影响，其粘结力较差，无法与电池和安全部件形成稳固的连接。
对比例10～12的实验结果说明，采用其他基材，导热胶初粘力较小，无法满足实际应用的需要，或者凝固时间过长，造成生产效率过低。
本申请虽然以较佳实施例公开如上，但并不是用来限定权利要求，任何本领域技术人员在不脱离本申请构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (17)

1.一种二次电池，包含电芯、固定在电芯上的安全部件以及位于电芯和安全部件之间的导热胶，其特征在于，所述导热胶中含有热熔胶和导热填料，所述热熔胶选自聚氨酯热熔胶，所述聚氨酯热熔胶的原料选自异氰酸酯聚氨酯预聚体。
2.根据权利要求1所述的二次电池，其特征在于，所述导热填料选自金属、金属氧化物、碳材料、氮化物、碳化物、硅材料中的至少一种。
3.根据权利要求2所述的二次电池，其特征在于，所述金属选自银、铜或锡中的至少一种。
4.根据权利要求2所述的二次电池，其特征在于，所述金属氧化物选自氧化铝、氧化镁、氧化锌、氧化钛、SnOy中的至少一种，其中，0＜y≤2。
5.根据权利要求2所述的二次电池，其特征在于，所述碳材料选自硬碳、软碳、中间相炭微球、碳纳米管、石墨、石墨烯中的至少一种。
6.根据权利要求2所述的二次电池，其特征在于，所述氮化物选自氮化硅、氮化铝、氮化硼、氮化钛中的至少一种。
7.根据权利要求2所述的二次电池，其特征在于，所述碳化物选自碳化硅、碳化钨中的至少一种。
8.根据权利要求2所述的二次电池，其特征在于，所述硅材料选自Si，SiOx中的至少一种；其中，0＜x≤2。
9.根据权利要求1所述的二次电池，其特征在于，所述导热填料的导热系数为1W/mK～10000W/mK。
10.根据权利要求9所述的二次电池，其特征在于，所述导热填料的导热系数为20W/mK～6000W/mK。
11.根据权利要求1所述的二次电池，其特征在于，所述导热填料的粒径为1nm～100μm，或所述导热填料中含有粒径大于等于1nm且小于1μm的导热填料颗粒与粒径大于等于1μm且小于等于50μm的导热填料颗粒。
12.根据权利要求1所述的二次电池，其特征在于，所述导热填料占所述导热胶的质量百分比1％～99％。
13.根据权利要求12所述的二次电池，其特征在于，所述导热填料占所述导热胶的质量百分比20～75％。
14.根据权利要求1～13任一权利要求所述的二次电池，其特征在于，所述导热胶的熔融粘度为1000～1×106CPs，初粘性为0.5～100N，剥离强度为0.1～20N/3mm，融化温度为120～190℃，导热系数为0.1～10000W/mK。
15.根据权利要求14所述的二次电池，其特征在于，所述导热胶的熔融粘度为1000～20000CPs，初粘性为0.5～60N，剥离强度为0.5～10N/3mm，融化温度为160～180℃，导热系数为0.1～100W/mK。
16.根据权利要求1所述的二次电池，所述导热胶的面积为1mm2～500mm2，所述导热胶的厚度为0.01～10mm。
17.一种如权利要求1～16任一权利要求所述二次电池的制备方法，其特征在于，在所述安全部件上施加所述导热胶，或在电芯上施加所述导热胶，施加0.1～100N的压力使安全部件与电芯粘接牢固。
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