CN117154102A - 复合集流体及其制备方法和应用 - Google Patents
复合集流体及其制备方法和应用 Download PDFInfo
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- CN117154102A CN117154102A CN202311091465.8A CN202311091465A CN117154102A CN 117154102 A CN117154102 A CN 117154102A CN 202311091465 A CN202311091465 A CN 202311091465A CN 117154102 A CN117154102 A CN 117154102A
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- layer
- conductive layer
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Classifications
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Abstract
本发明涉及集流体技术领域,公开了一种复合集流体及其制备方法和应用。所述复合集流体按顺序包括:保护层I、导电层I、粘结层I、基材、粘结层II、导电层II和保护层II。所述方法包括:在基材的上表面上制备粘结层I,在基材的和下表面上制备粘结层II,在所述粘结层I上制备导电层I,在所述粘结层II上制备导电层II,在所述导电层I上制备保护层I,在所述导电层II上制备保护层II,得到复合集流体。利用本发明中的复合集流体制备得到锂离子电池具有高稳定性、高安全性及更长的使用寿命。
Description
技术领域
本发明涉及集流体技术领域,具体涉及一种复合集流体及其制备方法和应用。
背景技术
与传统的纯铜/铝不同,复合集流体是基膜和铜/铝的复合材料。以PET铜箔为例,其结构为4.5μm PET基膜+两侧1μm铜层,其优点是:1)PET层和磁控溅射形成的阻燃结构,降低了电池燃烧、着火、爆炸的可能性;2)PET材料重量轻,降低了电池的整体质量,从而提高了能量密度;3)减少了铜箔/铝箔的用量,成本低。
与传统的箔制造工艺不同,传统的铝箔和铜箔主要采用轧制或电解工艺生产。复合铝/铜箔是在塑料薄膜表面通过磁控溅射和真空蒸发制成的金属层,然后通过水电镀将金属层加厚,制成复合金属箔,以替代传统集流体。而采用水电镀的方式,有如下缺陷:1)电镀材料单一,不导电的基材表面需要导电处理;2)镀膜容易产生色差,没有真空镀膜色泽稳定;3)电镀层的致密度差;4)存在废水、废气等环保问题,对环境不友好。
但是,现有的复合集流体中,一般是在柔性聚合物基材上真空沉积金属,来获得导电层+聚合物层+导电层这种“三明治”结构,而真空沉积这一块,由于基材存在“热损伤”的问题,需要在柔性基材反复成膜20次以上,通过这种方式得到的复合集流体,刚性过强,复合集流体薄膜脆性大,断裂伸长率非常低,同时基材与导电层之间的连接强度不足,导致导电层容易从基材上脱落,而在导电层上方,没有做任何的保护措施。
因此,亟待提供一种高效成膜而不出现“热损伤”等产品问题的、具有高结合力、高机械强度和高导电性的复合集流体产品。
发明内容
本发明的目的是为了克服现有技术存在的复合集流体机械强度低、导电性低、基材存在热损伤及基材与导电层之间连接强度低的问题,提供一种复合集流体及其制备方法和应用。
为了实现上述目的,本发明的第一方面提供了一种复合集流体,所述复合集流体按顺序包括:保护层I、导电层I、粘结层I、基材、粘结层II、导电层II和保护层II;
其中,当导电层I和导电层II为铝时,所述保护层I和保护层II的材料分别独自地选自镍、铬、导电聚吡咯和导电聚苯胺中的一种或多种;当导电层I和导电层II为铜时,所述保护层I和保护层II的材料分别独自地选自镍、铬和改性苯并三氮唑中的一种或多种;
所述粘结层I和粘结层II的材料分别独自地选自镍、铜、铬、镍铬合金、镍铜合金、氧化钴、氧化铬、氧化镍和铝氧化物中的一种或多种。
本发明的第二方面提供了一种复合集流体的制备方法,所述方法包括以下步骤:
(1)在基材的上表面上制备粘结层I,在基材的下表面上制备粘结层II,得到第一中间体;
(2)在所述粘结层I上制备导电层I,在所述粘结层II上制备导电层II,得到第二中间体;
(3)在所述导电层I上制备保护层I,在所述导电层II上制备保护层II,得到复合集流体。
本发明的第三方面提供了一种本发明第一方面所述的复合集流体或利用本发明第二方面所述的制备方法制得的复合集流体在锂离子电池中的应用。
通过上述技术方案,本发明所取得的有益技术效果如下:
在本发明中,通过在复合集流体中设置粘结层,可以明显改善导电层与基材之间的连接强度,避免导电层在使用过程中出现的脱落。本发明中的复合集流体还具有机械强度高、导电性高、基材不存在热损伤的优点。利用本发明中的复合集流体制备得到锂离子电池具有高稳定性、高安全性及更长的使用寿命。
附图说明
图1是本发明所述的复合集流体的结构示意图。
附图标记说明
1-基材;2-粘结层I;3-粘结层II;4-导电层I;5-导电层II;6-保护层I;7-保护层II。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明的第一方面提供了一种复合集流体,如图1所示,所述复合集流体按顺序包括:保护层I 6、导电层I 4、粘结层I 2、基材1、粘结层II 3、导电层II 5和保护层II 7;其中,当导电层I 4和导电层II 5为铝时,所述保护层I 6和保护层II 7的材料分别独自地选自镍、铬、导电聚吡咯和导电聚苯胺中的一种或多种;当导电层I 4和导电层II 5为铜时,所述保护层I 6和保护层II 7的材料分别独自地选自镍、铬和改性苯并三氮唑中的一种或多种;
所述粘结层I 2和粘结层II 3的材料分别独自地选自镍、铜、铬、镍铬合金、镍铜合金、氧化钴、氧化铬、氧化镍和铝氧化物中的一种或多种。
所述粘结层用于增强基材和导电层之间的结合力。
其中,本发明中复合集流体的结构自上而下依次为保护层I-导电层I-粘结层I-基材-粘结层II-导电层II-保护层II。
在一个优选的实施方式中,所述基材1选自聚乙烯(PE)、聚苯乙烯(PS)、聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚丙烯(PP)、双向拉伸聚丙烯(BOPP)、聚丙乙烯(PPE)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PEN)、聚对苯二甲酰对苯二胺(PPA)、聚酰胺(PA)、聚酰亚胺(PI)、聚对苯醚(PPO)、聚对苯硫醚(PPS)、聚碳酸酯(PC)、聚醚醚酮(PEEK)、聚甲醛(POM)、环氧树脂、酚醛树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS)中的一种或多种,优选为聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)和聚酰亚胺(PI)中的一种或多种。
本发明中所述的双向拉伸聚丙烯薄膜(BOPP)是由聚丙烯颗粒经共挤形成片材后,再经纵横两个方向(双向)的拉伸而制得。本领域中现有的双向拉伸聚丙烯薄膜均可用于本发明。
在一个优选的实施方式中,所述粘结层I 2和粘结层II 3的材料中,所述镍铬合金中镍的质量分数为70-90%,例如70%、75%、80%、85%、90%,以及上述任意两个数值组成的范围内的任意值;铬的质量分数为10-30%,例如10%、15%、20%、25%、30%,以及上述任意两个数值组成的范围内的任意值。
在本发明中,通过在复合集流体中设置粘结层,可以明显改善导电层I与基材,以及基材与导电层II之间的连接强度,避免导电层I和导电层II在使用过程中出现的脱落,显著提高利用本发明中的复合集流体制备得到锂离子电池的稳定性和安全性。
在一个优选的实施方式中,所述导电层I 4和导电层II 5的材料相同,选自铝或铜。其中,在本发明中,当导电层I 4和导电层II 5的材料为铝时,复合集流体为正极集流体;当导电层I 4和导电层II 5的材料为铜时,复合集流体为负极集流体。
在一个优选的实施方式中,所述导电层I 4和导电层II 5为铝,所述保护层I 6和保护层II 7的材料分别独自地选自镍、铬、导电聚吡咯和导电聚苯胺中的一种或多种。
在本发明中,镍或铬在空气条件下生成氧化镍或氧化铬,可以作为保护层。
在本发明中,导电聚吡咯和导电聚苯胺可通过掺杂方式来获得。聚苯胺的掺杂可以用质子酸。聚吡咯的掺杂一般分为化学掺杂(氧化剂为三价铁、过硫酸铵或金属有机物偶联)和电化学掺杂(电场)。
在本发明中,在导电层上制备保护层,其作用在于导电、防腐蚀,金属镍、铬本身具有导电性,其在自然状态下会生成致密耐蚀的氧化膜,可以起到防腐蚀的作用;掺杂后的聚吡咯/聚苯胺具有高导电性,质轻,单体成本低,易加工成膜。
在一个优选的实施方式中,所述导电层I 4和导电层II 5为铜,所述保护层I 6和保护层II 7的材料分别独自地选自镍和/或改性苯并三氮唑(改性BTA)。
在本发明中,金属镍会在自然条件下生成氧化镍,防止铜层氧化变色。
在一个优选的实施方式中,所述改性苯并三氮唑为苯并三氮唑(BTA)和2-巯基苯并噻唑(MBT)的混合物。在制备保护层时,导电层经BTA处理后,在铜表面可形成一层由BTA和一价铜离子生成的络合物(Cu2BTA)保护膜,能阻碍铜的进一步腐蚀。2-巯基苯并噻唑(MBT)分子巯基上的氢原子能在水中离解,硫原子和铜之间的化学吸附形成十分牢固的络合物(Cu-MBT)保护膜来抑制铜的腐蚀。
所述改性苯并三氮唑的制备方法可选择:配制0.5mmol/L BTA和0.5mmol/L MBT复配溶液,磁力搅拌至完全溶解,涂布机涂布于铜集流体基膜上,在50-80℃的干燥箱中干燥30min,取出。
其中,在本发明中,利用镍和/或改性BTA制备的保护层I和保护层II可以防止铜被氧化,防止电解液对导电层的腐蚀。
也即,在本发明中,通过在复合集流体中设置保护层I和保护层II,可以降低集流体与活性物之间的界面电阻,进而降低利用本发明中的复合集流体制备得到锂离子电池的内阻,改善锂离子电池的倍率性能和循环性能。
在一个优选的实施方式中,所述基材1的厚度为2-12μm,例如2μm、3μm、5μm、8μm、10μm、12μm,以及上述任意两个数值组成的范围内的任意值。所述粘结层I 2和粘结层II 3的厚度分别独自地选自0.01-0.1μm,例如0.01μm、0.03μm、0.05μm、0.08μm、0.1μm,以及上述任意两个数值组成的范围内的任意值。所述导电层I 4和导电层II 5的厚度分别独自地选自0.1-1.5μm,例如0.1μm、0.3μm、0.5μm、1μm、1.2μm、1.5μm,以及上述任意两个数值组成的范围内的任意值。所述保护层I 6和保护层II 7的厚度分别独自地选自0.01-1μm,例如0.01μm、0.05μm、0.1μm、0.3μm、0.5μm、0.8μm、1μm,以及上述任意两个数值组成的范围内的任意值。
在一个优选的实施方式中,所述导电层I 4与基材1之间和所述导电层II 5与基材1之间的结合力分别独自地为0.5-20N/15mm,例如0.5N/15mm、1N/15mm、2N/15mm、4N/15mm、5N/15mm、7N/15mm、8N/15mm、10N/15mm、11N/15mm、13N/15mm、15N/15mm、18N/15mm、20N/15mm,以及上述任意两个数值组成的范围内的任意值,优选为2-15N/15mm。
在一个优选的实施方式中,所述复合集流体的方阻为3-5000mΩ/□,优选为10-500mΩ/□。
在一个优选的实施方式中,所述复合集流体的电阻率为1×10-8-8×10-8Ω·m,优选为1.5×10-8-5×10-8Ω·m。
在一个优选的实施方式中,所述导电层I 4和导电层II 5的晶粒尺寸为10nm-2000nm,例如10nm、100nm、300nm、500nm、1000nm、1500nm、2000nm,以及上述任意两个数值组成的范围内的任意值。在本发明中,所述晶粒尺寸是指导电层I 4和导电层II 5中金属粒子的尺寸。
在一个优选的实施方式中,所述复合集流体的厚度为0.1-13μm,例如0.1μm、1μm、3μm、5μm、8μm、10μm、13μm,以及上述任意两个数值组成的范围内的任意值,优选为2-12μm。
在一个优选的实施方式中,所述复合集流体能够获得优异的抗拉强度、断裂伸长率、弹性模量、方阻、电阻率。
在一个优选的实施方式中,所述复合集流体可以获得以下性能:
抗拉强度为100-400MPa,断裂伸长率≥20%,结合力≥0.5N/15mm,方阻为3-5000mΩ/□,电阻率为1×10-8-8×10-8Ω·m。
其中,本发明中提供的复合集流体,保护层(保护层I和保护层II)、导电层(导电层I和导电层II)、粘结层(粘结层I和粘结层II)与基材之间相互作用,可以减少铝铜的用量,减小集流体的厚度,减轻集流体的重量,增大集流体的机械性能,可降低集流体的生产成本,提升锂离子电池的能量密度和使用寿命。
在本发明中,通过在复合集流体中设置粘结层,可以明显改善导电层与基材之间的连接强度,避免导电层在使用过程中出现的脱落。本发明中的复合集流体还具有机械强度高、导电性高、基材不存在热损伤的优点。利用本发明中的复合集流体制备得到锂离子电池具有高稳定性、高安全性及更长的使用寿命。
本发明的第二方面提供了一种本发明第一方面所述的复合集流体的制备方法,所述方法包括以下步骤:
(1)在基材的上表面上制备粘结层I,在基材的下表面上制备粘结层II,得到第一中间体;
(2)在所述粘结层I上制备导电层I,在所述粘结层II上制备导电层II,得到第二中间体;
(3)在所述导电层I上制备保护层I,在所述导电层II上制备保护层II,得到复合集流体。
在一个优选的实施方式中,所述粘结层I和粘结层II的材料分别独自地选自镍和/或镍铬合金,粘结层I和粘结层II的制备方法为溅射或蒸镀。
在一个优选的实施方式中,所述粘结层I和粘结层II的材料为铝氧化物,粘结层I和粘结层II的制备方法为原位反应。
在一个优选的实施方式中,所述导电层I和导电层II的制备方法为蒸镀,优选为阻蒸或电子枪蒸镀。
在本发明中,阻蒸是指电阻加热蒸发法。
其中,在本发明中,通过采用阻蒸或电子枪蒸镀制备导电层I和导电层II,可以得到高致密度的导电层,因此缺陷少,电阻率相对低,所得到的复合集流体更满足电池的需求。
在一个优选的实施方式中,所述保护层I和保护层II的材料为镍,所述保护层I和保护层II的制备方法为溅射。
在一个优选的实施方式中,所述导电层I和导电层II为铝,所述保护层I和保护层II的材料为导电聚吡咯,所述保护层I和保护层II的制备方法包括:先在所述导电层I和导电层II的表面依次涂覆硅烷偶联剂、吡咯单体溶液和FeCl3溶液进行聚合,然后进行清洗和干燥。
在一个优选的实施方式中,所述硅烷偶联剂为KH550。
在一个优选的实施方式中,所述吡咯单体溶液为吡咯单体的乙醇溶液。例如,经提纯的吡咯单体与无水乙醇配制成一定浓度的吡咯单体溶液。
在一个优选的实施方式中,所述FeCl3溶液为FeCl3的水溶液。
其中,在本发明中,在导电层I和导电层II的表面先涂覆硅烷偶联剂,然后再涂覆吡咯单体溶液,接着再涂覆FeCl3溶液,硅烷偶联剂、吡咯单体和FeCl3室温下接触可发生聚合反应,生成导电聚吡咯。聚合反应结束后可分别用清水和乙醇进行清洗,以除去多余的FeCl3溶液,之后再进行干燥,可得到聚吡咯薄膜。
在一个优选的实施方式中,所述导电层I和导电层II为铝,所述保护层I和保护层II的材料为导电聚苯胺,所述保护层I和保护层II的制备方法包括:先将苯胺、对甲苯磺酸溶液(作为质子酸)和重铬酸钾混合均匀,得到混合涂料;然后将所述混合涂料涂覆在所述导电层I和导电层II的表面上,在真空、80-90℃下反应20-30h。
在一个优选的实施方式中,所述真空条件的真空度为100-150Pa,优选为133Pa。
其中,在本发明中,当导电层I和导电层II为铝时,苯胺、对甲苯磺酸和重铬酸钾在导电层I和导电层II的表面上发生聚合反应,可以生成导电聚苯胺,得到聚苯胺薄膜。
在一个优选的实施方式中,所述导电层I和导电层II为铜,所述保护层I和保护层II的材料为改性苯并三氮唑。
在一个优选的实施方式中,所述溅射为磁控溅射。优选地,所述磁控溅射的操作条件包括:真空度高于10-3Pa;主辊温度为-25℃至+35℃,例如-25℃、-15℃、-5℃、0℃、10℃、20℃、25℃、30℃、35℃,或前述数值之间的任意值;主辊走速为20m/min以下,例如5m/min、10m/min、15m/min、20m/min,或前述数值之间的任意值;溅射功率为20kW以下,例如5kW、15kW、20kW,或前述数值之间的任意值。
关于真空度的说明如下:真空状态下气体的稀薄程度,数值越小,表示气体越稀薄,真空度越高。
在一个优选的实施方式中,所述蒸镀为真空蒸镀。优选地,所述真空蒸镀的操作条件包括:真空度高于10-3Pa;冷辊温度为-25℃至+35℃,例如-25℃、-15℃、-5℃、0℃、10℃、20℃、25℃、30℃、35℃,或前述数值之间的任意值;ES距离≥50mm,例如50mm、55mm、60mm、70mm、80mm、100mm、120mm,或前述数值之间的任意值;蒸发温度为≥800℃,例如800℃、850℃、900℃、1000℃、1100℃、1200℃、1500℃,或前述数值之间的任意值。
在本发明中,ES距离是指蒸发源与基材的距离。
蒸发源是指在真空蒸镀腔室内加热蒸发并使之气化的导电金属材料。基材是指预蒸镀的膜材。
本发明的第三方面提供了一种本发明第一方面所述的复合集流体或利用本发明第二方面所述制备方法制备得到的复合集流体在锂离子电池中的应用。
在本发明中,相关参数的测试方法如下:
厚度/粗糙度:中华人民共和国国家标准GB/T 11378-2005(金属覆盖层覆盖层厚度测量轮廓仪法)。
面密度:中华人民共和国国家标准GB/T 22638.10-2016(铝箔试验方法第10部分:涂层表面密度的测定)。
方阻/电阻率:美国的ASTM F390(用共线四探针法测定金属薄膜的薄膜电阻的标准试验方法)。
结合力:中华人民共和国国家标准GB/T 2792-2014(胶粘带剥离强度的试验方法)。
机械性能:中国的HG/T 2580-2008(橡胶或塑料涂覆织物拉伸强度和拉断伸长率的测定)。
润湿张力:中华人民共和国国家标准GB/T 22638.4-2016(铝箔试验方法第4部分:表面润湿张力的测定)。
以下通过实施例对本发明进行详细说明,但本发明的保护范围并不限于下述说明。
以下实施例和对比例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购途径获得的常规产品。
铝复合集流体实施例
实施例1
以6μm PET为基材,采用电阻蒸发沉积的方式,成膜时腔室真空度10-4Pa,蒸发舟经过润舟、预熔及稳定送丝后,打开shutter挡板,同时在PET基材附近通一定量的氧气,热蒸发的Al原子与O2在PET基膜的一个表面发生反应生成AlOx,当反应生成AlOx的厚度为10nm时,停止通O2,Al丝的热蒸发送丝速度保持不变,直至在AlOx表面生成1μm的金属Al膜。用同样的方法制备另一面的原位AlOx+Al结构。
将苯胺、对甲苯磺酸溶液和重铬酸钾混合均匀,得到混合涂料;然后用涂布机将所述混合涂料均匀涂覆在Al的上下表面之上,在真空、80-90℃下反应20-30h;得到上下共九层结构的铝复合集流体。
对铝复合集流体的材料性能进行测试,测试材料的力学性能、方阻/电阻率、粗糙度、润湿张力、结合力和面密度。测试标准如前所述。结果如表1所示。
实施例2
按照实施例1的制备方法,不同的是,保护层的制备材料和方法:在导Al的上下表面先涂覆硅烷偶联剂,然后再涂覆吡咯单体溶液,接着再涂覆FeCl3溶液,硅烷偶联剂、吡咯单体和FeCl3室温下接触可发生聚合反应,生成导电聚吡咯。聚合反应结束后可分别用清水和乙醇进行清洗,以除去多余的FeCl3溶液,之后再进行干燥,得到聚吡咯薄膜。
对实施例2的铝复合集流体的材料性能进行测试,测试材料的力学性能,方阻/电阻率,粗糙度,润湿张力,结合力,面密度。测试标准如前所述。结果如表1所示。
实施例3
按照实施例1的制备方法,不同的是,原位10nmAlOx层改为原位30nm AlOx粘结层。结果如表1所示。
实施例4
按照实施例2的制备方法,不同的是,原位10nmAlOx层改为原位30nm AlOx粘结层。结果如表1所示。
实施例5
按照实施例1的制备方法,不同的是,原位AlOx层改为磁控溅射10nm NiCr粘结层。结果如表1所示。
实施例6
按照实施例2的制备方法,不同的是,原位AlOx层改为磁控溅射10nm NiCr粘结层。结果如表1所示。
实施例7
按照实施例1的制备方法,不同的是,原位AlOx层改为磁控溅射30nm NiCr粘结层。结果如表1所示。
实施例8
按照实施例2的制备方法,不同的是,原位AlOx层改为磁控溅射30nm NiCr粘结层。结果如表1所示。
对比例1
按照实施例1的制备方法,不同的是,不做AlOx粘结层和保护层,只得到PET+Al双面结构,共3层,Al的厚度不变。结果如表1所示。
对比例2
按照实施例1的制备方法,不同的是,不做保护层,只得到PET+10nm AlOx+Al双面结构,共5层。结果如表1所示。对比例3
按照实施例4的制备方法,不同的是,不做保护层,只得到PET+30nm AlOx+Al双面结构,共5层。结果如表1所示。
对比例4
按照实施例5的制备方法,不同的是,不做保护层,只得到PET+10nm NiCr+Al双面结构,共5层。结果如表1所示。
对比例5
按照实施例7的制备方法,不同的是,不做保护层,只得到PET+30nm NiCr+Al双面结构,共5层。结果如表1所示。
对比例6
按照实施例1的制备方法,不同的是,不做原位反应的粘结层,只得到PET+Al+聚苯胺保护层双面结构,共5层。结果如表1所示。
对比例7
按照实施例2的制备方法,不同的是,不做原位反应的粘结层,只得到PET+Al+聚吡咯保护层双面结构,共5层。结果如表1所示。
表1
通过表1的结果可以看出,采用本发明实施例1-8可以得到更优力学性能,导电性,结合力及表面能的铝复合集流体。
铜复合集流体实施例
实施例9
(1)以4.5μm PET为基材,采用磁控溅射方式,分别在PET上下表面沉积10nm NiCr,形成粘结层I和粘结层II;然后采用电阻蒸发沉积的方式,成膜时腔室真空度10-4Pa,镀铜蒸发舟经过润舟,预熔及稳定送丝后,打开shutter挡板,分别在10nm NiCr表面沉积1μm金属Cu,形成导电层I和导电层II;
(2)配制0.5mmol/L的BTA和0.5mmol/L的MBT复配溶液,磁力搅拌至完全溶解,用涂布机分别涂布在导电层I和导电层II的表面,形成保护层I和保护层II;在50-80℃的干燥箱内干燥30min,取出,得到铜复合集流体。
对铜复合集流体的性能进行测试,测试其力学性能、方阻/电阻率、粗糙度、润湿张力和结合力,以及高温富氧环境是否发生变色(150℃,30min),测试结果如表2所示。
实施例10
以4.5μm PET为基材,采用磁控溅射方式,分别在PET上下表面沉积10nmNiCr,形成粘结层I和粘结层II;然后采用电阻蒸发沉积的方式,成膜时腔室真空度10-4Pa,镀铜蒸发舟经过润舟,预熔及稳定送丝后,打开shutter挡板,分别在10nm NiCr表面沉积1μm金属Cu,形成导电层I和导电层II;然后在导电层I和导电层II上分别磁控溅射10nm Ni保护层,得到铜复合集流体。
对铜复合集流体的性能进行测试,测试其力学性能、方阻/电阻率、粗糙度、润湿张力和结合力,以及高温富氧环境是否发生变色(150℃,30min),测试结果如表2所示。
实施例11
按照实施例9的制备方法,不同的是,磁控溅射30nm的NiCr粘结层。测试结果如表2所示。
实施例12
按照实施例10的制备方法,不同的是,磁控溅射30nm的NiCr粘结层。测试结果如表2所示。
对比例8
以4.5μm PET为基材,采用电阻蒸发沉积的方式,成膜时腔室真空度10-4Pa,镀铜蒸发舟经过润舟,预熔及稳定送丝后,打开shutter挡板,分别在PET上下表面沉积1μm金属Cu,形成导电层I和导电层II;在50-80℃的干燥箱内干燥30min,取出,得到铜复合集流体。测试结果如表2所示。
对比例9
以4.5μm PET为基材,采用磁控溅射方式,分别在PET上下表面沉积10nm NiCr,形成粘结层I和粘结层II;然后采用电阻蒸发沉积的方式,成膜时腔室真空度10-4Pa,镀铜蒸发舟经过润舟,预熔及稳定送丝后,打开shutter挡板,分别在10nm NiCr表面沉积1μm金属Cu,形成导电层I和导电层II;在50-80℃的干燥箱内干燥30min,取出,得到铜复合集流体。测试结果如表2所示。
对比例10
以4.5μm PET为基材,采用磁控溅射方式,分别在PET上下表面沉积30nm NiCr,形成粘结层I和粘结层II;然后采用电阻蒸发沉积的方式,成膜时腔室真空度10-4Pa,镀铜蒸发舟经过润舟,预熔及稳定送丝后,打开shutter挡板,分别在10nm NiCr表面沉积1μm金属Cu,形成导电层I和导电层II;在50-80℃的干燥箱内干燥30min,取出,得到铜复合集流体。测试结果如表2所示。
表2
通过表2的结果可以看出,采用本发明实施例9-12可以得到更有力学性能,导电性,结合力及表面防氧化效果的铜复合集流体。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (10)
1.一种复合集流体,其特征在于,所述复合集流体按顺序包括:保护层I、导电层I、粘结层I、基材、粘结层II、导电层II和保护层II;
其中,当导电层I和导电层II为铝时,所述保护层I和保护层II的材料分别独自地选自镍、铬、导电聚吡咯和导电聚苯胺中的一种或多种;当导电层I和导电层II为铜时,所述保护层I和保护层II的材料分别独自地选自镍、铬和改性苯并三氮唑中的一种或多种;
所述粘结层I和粘结层II的材料分别独自地选自镍、铜、铬、镍铬合金、镍铜合金、氧化钴、氧化铬、氧化镍和铝氧化物中的一种或多种。
2.根据权利要求1所述的复合集流体,其中,所述基材选自聚乙烯、聚苯乙烯、聚氯乙烯、聚偏氟乙烯、聚四氟乙烯、聚丙烯、双向拉伸聚丙烯、聚丙乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酰对苯二胺、聚酰胺、聚酰亚胺、聚对苯醚、聚对苯硫醚、聚碳酸酯、聚醚醚酮、聚甲醛、环氧树脂、酚醛树脂和丙烯腈-丁二烯-苯乙烯共聚物中的一种或多种。
3.根据权利要求1或2所述的复合集流体,其中,所述粘结层I和粘结层II的材料中,所述镍铬合金中镍的质量分数为70-90%,铬的质量分数为10-30%。
4.根据权利要求1-3中任意一项所述的复合集流体,其中,所述导电层I与基材之间和所述导电层II与基材之间的结合力分别独自地为0.5-20N/15mm,优选为2-15N/15mm;
优选地,所述复合集流体的方阻为3-5000mΩ/□,优选为10-500mΩ/□;电阻率为1×10-8-8×10-8Ω·m,优选为1.5×10-8-5×10-8Ω·m。
5.根据权利要求1-4中任意一项所述的复合集流体,其中,所述导电层I和导电层II的晶粒尺寸为10nm-2000nm;
优选地,所述复合集流体的厚度为0.1-13μm,优选为2-12μm。
6.一种复合集流体的制备方法,其特征在于,所述方法包括以下步骤:
(1)在基材的上表面上制备粘结层I,在基材的下表面上制备粘结层II,得到第一中间体;
(2)在所述粘结层I上制备导电层I,在所述粘结层II上制备导电层II,得到第二中间体;
(3)在所述导电层I上制备保护层I,在所述导电层II上制备保护层II,得到复合集流体。
7.根据权利要求6所述的制备方法,其中,步骤(1)中,所述粘结层I和粘结层II的材料分别独自地选自镍和/或镍铬合金,粘结层I和粘结层II的制备方法为溅射或蒸镀;
优选地,所述粘结层I和粘结层II的材料为铝氧化物,粘结层I和粘结层II的制备方法为原位反应;
优选地,步骤(2)中,所述导电层I和导电层II的制备方法为蒸镀,优选为阻蒸或电子枪蒸镀。
8.根据权利要求6或7所述的制备方法,其中,步骤(3)中,所述保护层I和保护层II的材料为镍,所述保护层I和保护层II的制备方法为溅射;
优选地,所述导电层I和导电层II为铝,所述保护层I和保护层II的材料为导电聚吡咯,所述保护层I和保护层II的制备方法包括:先在所述导电层I和导电层II的表面依次涂覆硅烷偶联剂、吡咯单体溶液和FeCl3溶液进行聚合,然后进行清洗和干燥;
优选地,所述导电层I和导电层II为铝,所述保护层I和保护层II的材料为导电聚苯胺,所述保护层I和保护层II的制备方法包括:先将苯胺、对甲苯磺酸溶液和重铬酸钾混合均匀,得到混合涂料;然后将所述混合涂料涂覆在所述导电层I和导电层II的表面上,在真空、80-90℃下反应20-30h;
优选地,所述导电层I和导电层II为铜,所述保护层I和保护层II的材料为改性苯并三氮唑。
9.根据权利要求6-8中任意一项所述的制备方法,其中,所述溅射为磁控溅射;
优选地,所述磁控溅射的操作条件包括:真空度高于10-3Pa;主辊温度为-25℃至+35℃;主辊走速为20m/min以下;溅射功率为20kW以下;
优选地,所述蒸镀为真空蒸镀;
优选地,所述真空蒸镀的操作条件包括:真空度高于10-3Pa;冷辊温度为-25℃至+35℃;ES距离≥50mm;蒸发温度≥800℃。
10.权利要求1-5中任意一项所述的复合集流体或利用权利要求6-9中任意一项所述的制备方法制得的复合集流体在锂离子电池中的应用。
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