CN106981665A - 一种负极集流体、其制备方法及其应用 - Google Patents

一种负极集流体、其制备方法及其应用 Download PDF

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CN106981665A
CN106981665A CN201710243658.9A CN201710243658A CN106981665A CN 106981665 A CN106981665 A CN 106981665A CN 201710243658 A CN201710243658 A CN 201710243658A CN 106981665 A CN106981665 A CN 106981665A
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current collector
negative current
coating
copper
film
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邱洪礼
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Shenzhen Xin Chi Technology Co Ltd
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Shenzhen Xin Chi Technology Co Ltd
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Priority to CN201710243658.9A priority Critical patent/CN106981665A/zh
Publication of CN106981665A publication Critical patent/CN106981665A/zh
Priority to CN201710619524.2A priority patent/CN107369810B/zh
Priority to US15/723,208 priority patent/US20180301709A1/en
Priority to EP17196591.6A priority patent/EP3389122A1/en
Priority to KR1020170134685A priority patent/KR20180116096A/ko
Priority to JP2017208420A priority patent/JP2018181823A/ja
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Abstract

本发明公开了一种负极集流体、其制备方法及其应用，负极集流体具有多层结构，包括塑料薄膜，在所述塑料薄膜的上、下表面依次镀有粘接力增强层、铜金属镀层和防氧化层。制备方法包括依次利用磁控溅射镀膜工艺在塑料薄膜上镀粘接力增强层，利用蒸发镀膜工艺镀铜，利用电子束蒸发或磁控溅射镀膜工艺镀防氧化层；该负极集流体的应用主要是在锂离子电池中的应用。本发明的负极集流体既能实现电池的轻量化，提高能量密度，降低成本，又能使镀铜层不容易脱落、不容易氧化。

Description

一种负极集流体、其制备方法及其应用
技术领域
本发明涉及一种负极集流体、其制备方法及其应用。
背景技术
传统锂离子电池负极集流体是铜箔。随着锂电技术的发展，锂离子电池的高能量密度、轻量化和柔性化成为人们的追求。减薄铜箔，可实现锂离子电池的轻量化，提高能量密度，降低成本。但由于制备技术的局限，铜箔的厚度很难再降低(目前铜箔可量产到6μm)；另外铜箔变薄之后，机械强度降低，致使加工性能降低，因此需要新的“减薄技术”。
现有技术中有将铜镀在塑料(例如PET)上作为集流体来提高电池能量密度、降低成本、让电池轻量化。但其镀铜的最厚厚度达1.5μm(需要一定的厚度来达到令人满意的导电性)，这相对于传统包装材料镀铜膜镀层厚度来说要厚很多，而镀层越厚，镀铜层越容易从塑料上脱落。
另外，铜箔的表面需要进行防氧化处理，因为铜箔直接与负极材料接触，时间长后，会被电解液腐蚀，从而降低锂离子电池的使用寿命。我们发现在塑料上直接镀铜后，再采用传统的防氧化方法容易致使铜镀层的脱落。
发明内容
有鉴于此，为克服上述技术问题，本发明的目的一方面在于提供一种既能实现电池的轻量化，提高能量密度，降低成本，又能使镀铜层不容易脱落、不容易氧化的负极集流体。
本发明的另一方面在于，提供一种负极集流体的制备方法。
本发明的第三方面在于，提供负极集流体的应用。
本发明提供的一种负极集流体，其具有多层结构，包括塑料薄膜，在所述塑料薄膜的上、下表面依次镀有粘接力增强层、铜金属镀层和防氧化层。
进一步地，所述塑料薄膜为OPP、PI、PET、CPP或PVC。
进一步地，所述塑料薄膜的厚度为2-12μm。
进一步地，所述粘接力增强层为金属镀膜或非金属镀膜，当为金属镀膜时，所述金属为Ni；当为非金属镀膜时，所述非金属为SiC、Si3N4或Al2O3。
进一步地，所述粘接力增强层的厚度为10-100nm。
进一步地，所述铜金属镀层的厚度为100-1000nm。
进一步地，所述防氧化层是致密的金属层或非金属层，当为金属层时，所述金属为Ni；当为非金属层时，所述非金属为Al2O3、Si3N4或SiC。
进一步地，所述防氧化层的厚度为10-100nm。
本发明提供的一种负极集流体的制备方法，包括如下步骤：
S1.首先对需要镀膜的塑料薄膜表面进行电晕处理，然后将卷筒塑料薄膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上双面往返高效镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜上形成一层镀镍层，即粘接力增强层；
S2.将S1得到的镀镍膜置入双面往返蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到5×10-3-8×10-3Pa，采用蒸发的方式将纯度≥99.9％的铜进行加热，调整好放卷速度、收卷速度和蒸发量，铜在蒸发机构中持续熔化、蒸发，在移动的薄膜表面形成一层镀铜层，即铜金属镀层；
S3.将S2得到的镀铜膜置入双面往返电子束蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，采用电子枪加速电子轰击碰撞蒸镀原料Al2O3，调整好放卷速度、收卷速度和蒸发量，Al2O3吸热气化，在移动的薄膜表面形成一层Al2O3镀层，即防氧化层；
或者S3.将S2得到的镀铜膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜表面形成一层镀镍层，即防氧化层。
本发明提供的负极集流体的应用主要是在电池中的应用，尤其是在锂离子电池中的应用。
本发明的有益效果在于，
(1)通过塑料薄膜层实现减重，其中镀铜膜集流体较传统铜箔集流体可实现减重70％，显著提高电池能量密度。
(2)塑料薄膜作为基底具有更强的拉伸强度，使得制备工序中的张力，压力等窗口会更大，从而备料段可采用更高的压力实现更大压实密度，提高过程制造能力；
(3)镀上一层粘接力增强层，可减少铜金属镀层的脱落，可有效防止铜金属镀层容易脱落导致集流体的性能丧失；
(4)用这种新的镀铜塑料膜集流体替代原有锂电池中的铜箔集流体，由传统的6μm的纯铜箔减少到不到1μm的镀铜层，铜的用量大大减少，集流体成本可下降50％以上。
(5)采用镀膜的方式得到的防氧化层，可解决塑料上铜镀层脱落的问题，同时达到防氧化的目的。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明的负极集流体的多层结构示意图。
具体实施方式
下面将结合本发明实施例中的附图，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优选的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
参见图1所示，一种负极集流体，其具有多层结构，包括塑料薄膜1，在所述塑料薄膜1的上、下表面依次镀有粘接力增强层2、铜金属镀层3和防氧化层4。
通过塑料薄膜层实现减重，其中镀铜膜集流体较传统铜箔集流体可实现减重70％，显著提高电池能量密度。塑料薄膜优选为OPP、PI、PET、CPP或PVC。其中OPP为定向拉伸聚丙烯塑料；PI为聚酰亚胺塑料；PET为聚对苯二甲酸乙二醇酯塑料、CPP为流延聚丙烯塑料、PVC为聚氯乙烯塑料。进一步优选PET、PI、CPP；塑料薄膜的厚度优选为2-12μm，进一步优选为4-8μm。塑料薄膜的耐温性120-300℃。
镀上一层粘接力增强层，可减少铜金属镀层的脱落，可有效防止铜金属镀层容易脱落导致集流体的性能丧失。该粘接力增强层优选为金属镀膜或非金属镀膜，当为金属镀膜时，所述金属为Ni；当为非金属镀膜时，所述非金属为SiC、Si3N4或Al2O3,进一步优选为Al2O3。Ni或Al2O3与塑料薄膜层和铜金属镀层的粘接性能较好，这样镀铜层更不易脱落。粘接力增强层的厚度优选为10-100nm，进一步优选为10-50nm。
铜金属镀层的厚度可为100-1000nm，进一步优选为200-600nm；通过此镀铜塑料膜集流体替代原有锂电池中的铜箔集流体，由传统的6μm的纯铜箔减少到不到1μm的镀铜层，铜的用量大大减少，集流体成本可降低50％以上。
防氧化层的作用或目的是为了防止铜金属镀层被氧化。防氧化层可以是致密的金属层或非金属层，当为金属层时，所述金属为Ni；当为非金属层时，所述非金属为Al2O3、Si3N4或SiC，进一步优选为Al2O3。当采用镀膜的方式得到的防氧化层，可解决塑料上铜镀层脱落的问题，同时达到防氧化的目的。防氧化层的厚度可为10-100nm，可进一步优选为10-50nm。
下面通过具体实施例来进一步说明。
实施例1
一种负极集流体的制备方法，包括如下步骤：
S1.首先对需要镀膜的塑料薄膜表面进行电晕处理，然后将卷筒塑料薄膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上双面往返高效镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜上形成一层镀镍层，即粘接力增强层；
S2.将S1得到的镀镍膜置入双面往返蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到5×10-3-8×10-3Pa，采用蒸发的方式将纯度≥99.9％的铜进行加热，调整好放卷速度、收卷速度和蒸发量，铜在蒸发机构中持续熔化、蒸发，在移动的薄膜表面形成一层镀铜层，即铜金属镀层；
S3.将S2得到的镀铜膜置入双面往返电子束蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，采用电子枪加速电子轰击碰撞蒸镀原料Al2O3，调整好放卷速度、收卷速度和蒸发量，Al2O3吸热气化，在移动的薄膜表面形成一层Al2O3镀层，即防氧化层；
从而得到具有多层结构的负极集流体。
实施例2
一种负极集流体的制备方法，包括如下步骤：
S1.首先对需要镀膜的塑料薄膜表面进行电晕处理，然后将卷筒塑料薄膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上双面往返高效镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜上形成一层镀镍层，即粘接力增强层；
S2.将S1得到的镀镍膜置入双面往返蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到5×10-3-8×10-3Pa，采用蒸发的方式将纯度为≥99.9％的铜进行加热，调整好放卷速度、收卷速度和蒸发量，铜在蒸发机构中持续熔化、蒸发，在移动的薄膜表面形成一层镀铜层，即铜金属镀层；
S3.将S2得到的镀铜膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜表面形成一层镀镍层，即防氧化层。
从而得到具有多层结构的负极集流体。
将实施例1与实施例2得到的负极集流体用于锂离子电池中，其最基本的功能是汇集电流，同时作为载体来存放负极材料，即将负极材料(电池活性物质)产生的电流汇集起来以便形成较大的电流对外输出。
将实施例1与实施例2得到的负极集流体进行测试，测试结果可得到如下结论：
(1)通过塑料薄膜层实现减重，其中镀铜膜集流体较传统铜箔集流体可实现减重70％，显著提高能量密度；
(2)塑料薄膜作为基底具有更强的拉伸强度，使得制备工序中的张力，压力等窗口会更大，从而备料段可采用更高的压力实现更大压实密度，提高过程制造能力；
(3)镀上一层粘接力增强层，可减少铜金属镀层的脱落，可有效防止铜金属镀层容易脱落导致集流体的性能丧失；
(4)用这种新的铜集流体替代原有锂电池中的铜箔集流体，由传统的6μm的纯铜箔减少到不到1μm的镀铜层，铜的用量大大减少，集流体成本可降低50％以上。
(5)采用镀膜的方式得到的防氧化层，可解决塑料上铜镀层脱落的问题，同时达到防氧化的目的。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施例的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施例或变更均应包含在本发明的保护范围之内。

Claims (10)

1.一种负极集流体，其特征在于，其具有多层结构，包括塑料薄膜，在所述塑料薄膜的上、下表面依次镀有粘接力增强层、铜金属镀层和防氧化层。
2.根据权利要求1所述的负极集流体，其特征在于，所述塑料薄膜为OPP、PI、PET、CPP或PVC。
3.根据权利要求1所述的负极集流体，其特征在于，所述塑料薄膜的厚度为2-12μm。
4.根据权利要求1所述的负极集流体，其特征在于，所述粘接力增强层为金属镀膜或非金属镀膜，当为金属镀膜时，所述金属为Ni；当为非金属镀膜时，所述非金属为SiC、Si3N4或Al2O3。
5.根据权利要求1所述的负极集流体，其特征在于，所述粘接力增强层的厚度为10-100nm。
6.根据权利要求1所述的负极集流体，其特征在于，所述铜金属镀层的厚度为100-1000nm。
7.根据权利要求1所述的负极集流体，其特征在于，所述防氧化层是致密的金属层或非金属层，当为金属层时，所述金属为Ni；当为非金属层时，所述非金属为Al2O3、Si3N4或SiC。
8.根据权利要求1所述的负极集流体，其特征在于，所述防氧化层的厚度为10-100nm。
9.一种权利要求1所述的负极集流体的制备方法，其特征在于，包括如下步骤：
S1.首先对需要镀膜的塑料薄膜表面进行电晕处理，然后将卷筒塑料薄膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上双面往返高效镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜上形成一层镀镍层，即粘接力增强层；
S2.将S1得到的镀镍膜置入双面往返蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到5×10-3-8×10-3Pa，采用蒸发的方式对纯度≥99.9％的铜进行加热，调整好放卷速度、收卷速度和蒸发量，铜在蒸发机构中持续熔化、蒸发，在移动的薄膜表面形成一层镀铜层，即铜金属镀层；
S3.将S2得到的镀铜膜置入双面往返电子束蒸发镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，采用电子枪加速电子轰击碰撞蒸镀原料Al2O3，调整好放卷速度、收卷速度和蒸发量，Al2O3吸热气化，在移动的薄膜表面形成一层Al2O3镀层，即防氧化层；
或者S3.将S2得到的镀铜膜置入双面往返磁控溅射镀膜机真空室内，将真空室密封，逐级抽真空至真空度达到3×10-3-6×10-3Pa，利用磁控溅射在塑料薄膜上镀膜，靶材为镍，纯度≥99.9％，调整好放卷速度、收卷速度，溅射的镍原子在移动的薄膜表面形成一层镀镍层，即防氧化层。
10.权利要求1-8所述的负极集流体在电池中的应用。
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Application publication date: 20170725