CN116715999A - 一种耐腐蚀涂层及其制备方法和应用 - Google Patents
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Abstract
本发明提供一种耐腐蚀涂层及其制备方法和应用,该耐腐蚀涂层,适用于铝塑复合膜的尼龙层外表面,按照重量份数计,包括90~110份的氟碳树脂,10~20份异氰酸酯固化剂,1~4份有机硅微粉,20~40份稀释剂。制备步骤为:(1)将有机硅微粉、异氰酸酯固化剂加入稀释剂中,充分搅拌,分散均匀,制得稀释液A;(2)将氟碳树脂加入所述稀释液A中,充分搅拌均匀,得到耐腐蚀涂料。将所述耐腐蚀涂料辊涂于铝塑复合膜的尼龙外表层上,烘干,于室温熟化6‑18h,再于50℃‑60℃温度下熟化6‑24h,在尼龙层外表面形成耐腐蚀涂层。该耐腐蚀涂层具有优异的耐电解液性能,适用于铝塑复合膜的尼龙层外表面,避免了软包电池注液过程中由于电解液飞溅在尼龙外表面上造成的外观不良问题。
Description
技术领域
本发明涉及软包锂电池技术领域,尤其涉及一种耐腐蚀涂层及其制备方法和应用。
背景技术
软包锂电池具有能量密度高、安全性强、布局灵活、轻量化好、循环寿命长等优点,被应用到多种场合。软包锂电池是电池的一种封装形式,在结构上采用铝塑膜(也称铝塑复合膜)包装,是起到保护内部电芯材料的作用。铝塑复合膜一般包括铝箔及位于该铝箔两侧的保护层及热封层,保护层一般为尼龙,热封层一般为聚丙烯膜。在软包锂电池的制备过程中,当电解液进行注液过程中,经常会发生电解液滴落铝塑复合膜表面,从而污染尼龙膜外表面的情况。为了解决该难题,行业内通常做法是在铝塑膜尼龙外表面再贴附一层PET薄膜,但有一定的缺点:1.PET薄膜偏硬,对铝塑膜的冲深有一定的影响;2.在PET薄膜的复合过程中会影响良品率。
此外,中国专利104466039A公开了一种表层做疏油处理的锂电池封装用铝塑膜及其制备工艺,具体公开了在尼龙层外设置一层疏油防护层,疏油防护层包括氟元素改性的涂层、硅元素改性的涂层或氟硅共改性的涂层,但是其采用光固化工艺,固化条件常规铝塑膜生产过程中难以达到,因此应用范围受到限制。
发明内容
鉴于目前的难题,本发明的目的在于提供一种耐腐蚀涂层,具有优异的耐电解液性能,适用于铝塑复合膜的尼龙层外表面,避免了软包电池注液过程中由于电解液飞溅在尼龙外表面上造成的外观不良问题。
为实现上述目的,本发明提供一种耐腐蚀涂层,适用于铝塑复合膜的尼龙层外表面,按照重量份数计,包括90~110份的氟碳树脂,10~20份异氰酸酯固化剂,1~4份有机硅微粉,20~40份稀释剂。
在一些实施例中,所述氟碳树脂的数均分子量为15000-20000,但不以此为限。
在一些实施例中,氟碳树脂为氟乙烯-乙烯基醚共聚物,优选地,氟碳树脂为三氟氯乙烯与乙烯基酯的共聚物,在一个优秀的实施例中,氟碳树脂采用氟含量为20-25%的三氟氯乙烯与乙烯基酯的树脂,氟含量合适,既保证了耐化学性的同时也保证了其对于尼龙薄膜表面的附着力。
在一些实施例中,所述异氰酸酯固化剂为脂肪族异氰酸酯固化剂或者芳香族异氰酸酯固化剂。作为示例地,异氰酸酯固化剂为脂肪族异氰酸酯固化剂。
在一些实施例中,所述有机硅微粉的粒径为3~5um,有机硅微粉的加入赋予涂层较低的摩擦,提高爽滑性,在一定程度上可以省略后续的涂粉工艺,缩短了工序。
在一些实施例中,所述稀释剂选自乙酸乙酯、乙酸丁酯、丙酮或丁酮中的至少一种,作为示例地,稀释剂为丁酮或乙酸乙酯。
相应地,本发明还提供一种上述耐腐蚀涂层的制备方法,包括步骤:
(1)将有机硅微粉、异氰酸酯固化剂加入稀释剂中,充分搅拌,分散均匀,制得稀释液A;
(2)将氟碳树脂加入所述稀释液A中,充分搅拌均匀,得到耐腐蚀涂料。
相应地,本发明还提供一种耐腐蚀涂层及耐腐蚀涂层的制备方法制得的耐腐蚀涂料在铝塑复合膜中的应用。
在一些实施例中,将所述耐腐蚀涂料辊涂于铝塑复合膜的尼龙外表层上,烘干,然后收卷,室温熟化6-18h,再于50℃-60℃温度下熟化6-24h,在尼龙层外表面形成耐腐蚀涂层。本发明的耐腐性涂料可以在低温下进行熟化,若不进行第二次熟化,则会出现整卷粘连现象。
在一些实施例中,烘干的温度为150℃-200℃。
本发明的有益效果有:
(1)本发明的耐腐蚀涂层包含氟碳树脂、异氰酸酯固化剂、有机硅微粉和稀释剂,相较于当前通用的PET外层,具有一定柔软性,故有利于后续铝塑膜的冲压;
(2)耐腐蚀涂层中氟碳树脂以C-F为骨架,具备良好的耐电解液性能,尤其是采用20-25%的三氟氯乙烯与乙烯基酯的树脂,氟含量合适,既保证了耐化学性的同时也保证了其对于尼龙薄膜表面的附着力;
(3)耐腐蚀涂层中还包含有机硅微粉,有机硅微粉呈球状结构,能在涂层表面形成凹凸的微结构,有利于降低涂层的动摩擦系数,增加爽滑性,在一定程度上可以省略后续的涂粉工艺,缩短了工序。
具体实施方式
以下所述是本发明实施例的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明实施例原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明实施例的保护范围。
实施例1
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将20份异氰酸酯固化剂(科思创BL3370MPA固化剂)、4份有机硅微粉(粒径为3-5um)加入至20份丁酮中,充分搅拌,分散均匀,制得稀释液A;
(2)将100份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后在室温熟化12h后,再放入熟化室于55℃熟化12h,即在尼龙外表面形成耐腐蚀涂层。
实施例2
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将15份异氰酸酯固化剂(科思创BL3370MPA固化剂)、3份有机硅微粉(粒径为3-5um)加入至20份乙酸丁酯中,充分搅拌,分散均匀,制得稀释液A;
(2)将90份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后在室温熟化12h后,再放入熟化室于55℃熟化12h,即在尼龙外表面形成耐腐蚀涂层。
实施例3
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将10份异氰酸酯固化剂(科思创BL3370MPA固化剂)、2份有机硅微粉(粒径为3-5um)加入至15份丁酮中,充分搅拌,分散均匀,制得稀释液A;
(2)将110份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后在室温熟化12h后,再放入熟化室于55℃熟化24h,即在尼龙外表面形成耐腐蚀涂层。
对比例1
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将20份异氰酸酯固化剂(科思创BL3370MPA固化剂)加入至20份丁酮中,不加入有机硅微粉,充分搅拌,分散均匀,制得稀释液A;
(2)将100份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后在室温熟化12h后,再放入熟化室于55℃熟化12h,即在尼龙外表面形成耐腐蚀涂层。
对比例2
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将20份异氰酸酯固化剂(科思创BL3370MPA固化剂)、4份有机硅微粉(粒径为3-5um)加入至20份丁酮中,充分搅拌,分散均匀,制得稀释液A;
(2)将80份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后在室温熟化12h后,再放入熟化室于55℃熟化12h,即在尼龙外表面形成耐腐蚀涂层。
对比例3
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将20份异氰酸酯固化剂(科思创BL3370MPA固化剂)、4份有机硅微粉(粒径为3-5um)加入至20份丁酮中,充分搅拌,分散均匀,制得稀释液A;
(2)将120份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后在室温熟化12h后,再放入熟化室于55℃熟化12h,即在尼龙外表面形成耐腐蚀涂层。
对比例4
一种耐腐蚀涂层的制备方法,包括步骤:
(1)在室温下,将20份异氰酸酯固化剂(科思创BL3370MPA固化剂)、4份有机硅微粉(粒径为3-5um)加入至20份丁酮中,充分搅拌,分散均匀,制得稀释液A;
(2)将100份的氟碳树脂(CF-803树脂,购自上海德予得贸易公司)加入稀释液A中,充分搅拌均匀,得到耐腐蚀涂料;
(3)将耐腐蚀涂料加入料盘中,以辊涂方式通过70目辊涂布在铝塑膜用BOPA薄膜(双向拉伸尼龙薄膜)表面涂布耐腐蚀涂料,涂布量为8g/m2,通过烘箱烘干,烘箱温度为160℃,时间为6s,然后直接放入熟化室于55℃熟化12h,即在尼龙外表面形成耐腐蚀涂层。
对比例5
在铝塑膜BOPA薄膜(双向拉伸尼龙薄膜)表面,使用双组分聚氨酯胶黏剂贴合一层6um的PET。
将实施例与对比例制得的产品制成铝塑复合膜,并进行相关性能测试,测试结果见表1:
测试项目和方法如下:
1.动摩擦测试:根据GB/T 22895-2008对涂层表面动摩擦进行测试;
2.耐电解液能力测试:冲壳后在模壳四角滴电解液,静置并观察其表面是否开裂,持续观察72h;
3.冲深测试:用18350模具对铝塑膜进行冲壳,测试铝塑膜冲不破的稳定冲深;
4.厚度测试:利用GB/T450进行采样,利用膜厚仪进行测量。
其中,对比例4因直接采用55℃熟化12h,其产品制得的铝塑复合膜整卷相互粘黏,属于不良品,不进行相关测试。
表1性能测试结果
从表1的数据可知,本发明实施例1-3制得的耐腐蚀涂层具有较低的摩擦系数,免除了后续爽滑剂涂布过程(现有技术为获得摩擦系数较低,均会采用爽滑剂涂布在尼龙层外表面),及具有良好的耐电解液性能,能够避免软包电池注液过程中由于电解液飞溅在尼龙上造成的外观不良问题。
从实施例1与对比例1的数据可知,对比例1不加入有机硅微粉,动摩擦系数增加较大,冲深时模具模头与铝塑膜之间的摩擦力较大,会导致冲壳破损,降低冲型良品率。实施例1与对比例2-3的数据可知,当氟碳树脂含量较小时,耐电解液性能不佳,这主要是因为作为耐电解液腐蚀的主体树脂含量较小,在尼龙膜上尚未形成一定厚度和强度的耐腐蚀膜,从而无法抵挡抵挡电解液的侵蚀;而当氟碳树脂含量较大时,耐电解液性能不佳,这主要是因为氟碳树脂上的羟基没有与多官的异氰酸酯交联固化完全,没有形成高强度的网状结构,电解液渗透进膜内部腐蚀整个体系。
从对比例5的数据可知,相对于本发明的耐腐蚀涂层,PET层也具有较好的耐电解液腐蚀性能,但是由于PET的刚性结构,对铝塑膜的冲深有一定的负面影响。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,但是也并不仅限于实施例中所列,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种耐腐蚀涂层,适用于铝塑复合膜的尼龙层外表面,其特征在于,按照重量份数计,包括90~110份的氟碳树脂,10~20份异氰酸酯固化剂,1~4份有机硅微粉,20~40份稀释剂。
2.根据权利要求1所述的耐腐蚀涂层,其特征在于,所述氟碳树脂的数均分子量为15000-20000。
3.根据权利要求1所述的耐腐蚀涂层,其特征在于,所述氟碳树脂采用氟含量为20-25%的三氟氯乙烯与乙烯基酯的树脂。
4.根据权利要求1所述的耐腐蚀涂层,其特征在于,所述有机硅微粉的粒径为3~5um。
5.根据权利要求1所述的耐腐蚀涂层,其特征在于,所述异氰酸酯固化剂为脂肪族异氰酸酯固化剂或者芳香族异氰酸酯固化剂。
6.根据权利要求1所述的耐腐蚀涂层,其特征在于,所述稀释剂选自乙酸乙酯、乙酸丁酯、丙酮或丁酮中的至少一种。
7.根据权利要求1-6任意一项所述的耐腐蚀涂层的制备方法,其特征在于,包括步骤:
(1)将有机硅微粉、异氰酸酯固化剂加入稀释剂中,充分搅拌,分散均匀,制得稀释液A;
(2)将氟碳树脂加入所述稀释液A中,充分搅拌均匀,得到耐腐蚀涂料。
8.根据权利要求1-7任意一项所述的耐腐蚀涂层及权利要求7所述的耐腐蚀涂层的制备方法制得的耐腐蚀涂料在铝塑复合膜中的应用。
9.根据权利要求8所述的应用,其特征在于,将所述耐腐蚀涂料辊涂于铝塑复合膜的尼龙外表层上,烘干,于室温熟化6-18h,再于50℃-60℃温度下熟化6-24h,在尼龙层外表面形成耐腐蚀涂层。
10.根据权利要求9所述的应用,其特征在于,烘干的温度为150℃-200℃。
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