CN116333593A - 一种电解铜箔的环保型防氧化液及其防氧化工艺 - Google Patents
一种电解铜箔的环保型防氧化液及其防氧化工艺 Download PDFInfo
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 11
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 235000011006 sodium potassium tartrate Nutrition 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
本发明属于电解铜箔防氧化技术领域。本发明提供了一种电解铜箔的环保型防氧化液,包含如下质量浓度的组分:酒石酸钾钠35~45g/L,乙二胺四乙酸二钠3~7g/L,添加剂6~12g/L,羧酸及其衍生物1~8g/L,苯并三氮唑0.5~2g/L,硅烷偶联剂0.2~1g/L。本发明还提供了一种电解铜箔的环保型防氧化工艺。本发明的防氧化液中不含有对人体致癌的铬元素和降低电池性能的锌单质,能形成均匀的聚合物薄膜,提高锂离子电池用电解铜箔的常温高温抗氧化性能,润湿性和导电性。防氧化液能够很好的浸润铜表面防止铜被氧化,与铜的螯合能力强。
Description
技术领域
本发明涉及电解铜箔防氧化技术领域,尤其涉及一种电解铜箔的环保型防氧化液及其防氧化工艺。
背景技术
在锂离子电池用电解铜箔生产过程中,铜箔防氧化是一个非常重要的工艺,如果铜箔表面发生氧化变色,不仅影响铜箔的外观,更重要的是导致铜箔附着力下降,涂布出现露箔点,进而影响电池的性能,例如增大内阻,影响导电性;容量降低,循环寿命缩短。随着锂电铜箔客户对高端电池产品质量要求的提高,锂电铜箔具有耐高温氧化性能、良好的润湿性能成为发展趋势。
传统防氧化方法是在后处理机中进行防氧化,由于铜箔很薄,容易出现折皱、压坑、螺旋纹等质量问题,成品率非常低。近年来采用的防氧化液一般为酸性铬酸盐,金属与铬酸盐钝化剂接触后,表面发生部分溶解并以金属-铬氧化物的形式再沉淀。此生产过程距离长,在生产超薄电解铜箔时,易出现折皱、水点、色差等外观问题。而且,所用的防氧化液中常采用六价铬,并添加锌盐、镍盐等配制成防氧化液,这样防氧化液中添加了重金属,导致最后产生的废水中重金属种类多,污水处理比较困难,增加了生产成本,同时在电解铜箔工艺过程中,要求的温度较高,并且需要进行电镀,浪费能量。而且,现有的防氧化工艺得到的电解铜箔的高温抗氧化性、导电性和润湿性往往不能够同时满足高性能锂离子电池的要求。
因此,研究得到一种电解铜箔的环保型防氧化工艺,同时提高较薄电解铜箔的常温高温抗氧化性、导电性、润湿性、力学性能,具有重要的价值。
发明内容
本发明的目的是针对现有技术的不足提供一种电解铜箔的环保型防氧化液及其防氧化工艺。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种电解铜箔的环保型防氧化液,包含如下质量浓度的组分:
酒石酸钾钠35~45g/L,乙二胺四乙酸二钠3~7g/L,添加剂6~12g/L,羧酸及其衍生物1~8g/L,苯并三氮唑0.5~2g/L,硅烷偶联剂0.2~1g/L。
作为优选,所述添加剂为钨酸钠、次亚磷酸钠和α-烯基磺酸钠中的一种或几种。
作为优选,所述羧酸及其衍生物为羧乙基硫代丁二酸、柠檬酸、均三苯甲酸和酒石酸中的一种或几种。
作为优选,所述硅烷偶联剂为3-氨丙基三乙氧基硅烷、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷或γ-巯丙基三甲氧基硅烷。
作为优选,环保型防氧化液的溶剂为水,环保型防氧化液的pH值为2~5。
本发明还提供了一种电解铜箔的环保型防氧化工艺,包含如下步骤:
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔放入所述的环保型防氧化液中浸泡,然后顺次经挤压辊挤干、干燥、收卷、分切,得到成品电解铜箔。
作为优选,所述浸泡的温度为30~40℃。
作为优选,所述浸泡的时间为3~8s。
本发明的有益效果包括以下几点:
1)本发明的防氧化液中不含有对人体致癌的铬元素和降低电池性能的锌单质,能在电解铜箔表面形成均匀的聚合物薄膜,聚合物薄膜在多种溶剂中稳定不易溶解,具有很好的抗腐蚀保护作用,提高锂离子电池用电解铜箔的常温高温抗氧化性能,润湿性和导电性。防氧化液能够很好的浸润铜表面防止铜被氧化,与铜的螯合能力强,还可以改善铜表面的粗糙度,抗剥离强度较好。
2)本发明的防氧化液能够提高铜箔的外观质量,避免在使用一段时间后出现防氧化液变色以及导电辊和挤压辊产生结垢,造成铜箔表面出现黄色条纹色差、压印、打折、小黑点等外观问题。
3)本发明的防氧化工艺可操作性强,无需通电,无需水洗,不会产生废水,对环境无污染,降低后处理成本,具有绿色、安全和环保的优点。
具体实施方式
本发明提供了一种电解铜箔的环保型防氧化液,包含如下质量浓度的组分:
酒石酸钾钠35~45g/L,乙二胺四乙酸二钠3~7g/L,添加剂6~12g/L,羧酸及其衍生物1~8g/L,苯并三氮唑0.5~2g/L,硅烷偶联剂0.2~1g/L。
本发明的环保型防氧化液包含35~45g/L酒石酸钾钠,优选为37~42g/L,进一步优选为39~41g/L,更优选为40g/L。
本发明的环保型防氧化液包含3~7g/L乙二胺四乙酸二钠,优选为4~6g/L,进一步优选为5g/L。
乙二胺四乙酸二钠是良好的配合剂,含有六个配位原子,几乎能与所有的金属原子形成稳定的螯合物。
本发明的环保型防氧化液包含6~12g/L添加剂,优选为7~11g/L,进一步优选为8~10g/L。
本发明中,所述添加剂优选为钨酸钠、次亚磷酸钠和α-烯基磺酸钠中的一种或几种。
本发明的环保型防氧化液包含1~8g/L羧酸及其衍生物,优选为2~7g/L,进一步优选为3~6g/L,更优选为4~5g/L。
本发明中,所述羧酸及其衍生物优选为羧乙基硫代丁二酸、柠檬酸、均三苯甲酸和酒石酸中的一种或几种。
羧酸及其衍生物的主要作用是:①除垢作用,导电辊通电、挤压辊长时间通电运行后会产生结垢,添加羧酸及其衍生物有效减少结垢的产生;②调节防氧化液的pH值,使防氧化液在合适的pH条件下发挥防氧化钝化作用。
本发明的环保型防氧化液包含0.5~2g/L苯并三氮唑,优选为0.8~1.8g/L,进一步优选为1~1.5g/L,更优选为1.2~1.3g/L。
本发明的环保型防氧化液包含0.2~1g/L硅烷偶联剂,优选为0.3~0.8g/L,进一步优选为0.4~0.7g/L,更优选为0.5~0.6g/L。
本发明中,所述硅烷偶联剂优选为3-氨丙基三乙氧基硅烷、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷或γ-巯丙基三甲氧基硅烷。
本发明中,环保型防氧化液的溶剂优选为水,进一步优选为去离子水;环保型防氧化液的pH值优选为2~5,进一步优选为3~4。
本发明中,各组分相互配合,所形成的防氧化膜均匀一致,抗氧化效果好,提高了电解铜箔的浸润性和导电性,不影响锂离子电容量、使用寿命等基本性能。添加剂能够改善铜箔的表面粗糙度,使其在防氧化处理过程中形成均匀的钝化膜。羧酸及其衍生物的鳌合能力强,耐高温,将铜包裹在羧酸内部,增强铜的稳定性,从而阻止了铜的进一步氧化。
本发明还提供了一种电解铜箔的环保型防氧化工艺,包含如下步骤:
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔放入所述的环保型防氧化液中浸泡,然后顺次经挤压辊挤干、干燥、收卷、分切,得到成品电解铜箔。
本发明中,所述浸泡的温度优选为30~40℃,进一步优选为32~38℃,更优选为34~36℃。
本发明中,所述浸泡的时间优选为3~8s,进一步优选为4~7s,更优选为5~6s。
下面结合实施例对本发明提供的技术方案进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
环保型防氧化液由酒石酸钾钠、乙二胺四乙酸二钠、次亚磷酸钠、羧乙基硫代丁二酸、苯并三氮唑、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷和去离子水组成,各组分的质量浓度为酒石酸钾钠37g/L、乙二胺四乙酸二钠4g/L、次亚磷酸钠7g/L、羧乙基硫代丁二酸2g/L、苯并三氮唑0.7g/L、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷0.3g/L。
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔完全浸没于环保型防氧化液中浸泡,浸泡的温度为32℃,时间为8s;然后将原箔顺次经挤压辊挤干、130℃热风吹干、收卷、分切,得到成品电解铜箔。
实施例2
环保型防氧化液由酒石酸钾钠、乙二胺四乙酸二钠、钨酸钠、均三苯甲酸、苯并三氮唑、3-氨丙基三乙氧基硅烷和去离子水组成,各组分的质量浓度为酒石酸钾钠43g/L、乙二胺四乙酸二钠7g/L、钨酸钠11g/L、均三苯甲酸7.8g/L、苯并三氮唑1.8g/L、3-氨丙基三乙氧基硅烷0.9g/L。
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔完全浸没于环保型防氧化液中浸泡,浸泡的温度为40℃,时间为3s;然后将原箔顺次经挤压辊挤干、140℃热风吹干、收卷、分切,得到成品电解铜箔。
实施例3
环保型防氧化液由酒石酸钾钠、乙二胺四乙酸二钠、钨酸钠、柠檬酸、苯并三氮唑、γ-巯丙基三甲氧基硅烷和去离子水组成,各组分的质量浓度为酒石酸钾钠40g/L、乙二胺四乙酸二钠5g/L、钨酸钠9g/L、柠檬酸5g/L、苯并三氮唑1.2g/L、γ-巯丙基三甲氧基硅烷0.6g/L。
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔完全浸没于环保型防氧化液中浸泡,浸泡的温度为35℃,时间为5s;然后将原箔顺次经挤压辊挤干、132℃热风吹干、收卷、分切,得到成品电解铜箔。
实施例4
环保型防氧化液由酒石酸钾钠、乙二胺四乙酸二钠、α-烯基磺酸钠、酒石酸、苯并三氮唑、3-氨丙基三乙氧基硅烷和去离子水组成,各组分的质量浓度为酒石酸钾钠38g/L、乙二胺四乙酸二钠5.5g/L、α-烯基磺酸钠8g/L、酒石酸4g/L、苯并三氮唑1g/L、3-氨丙基三乙氧基硅烷0.5g/L。
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔完全浸没于环保型防氧化液中浸泡,浸泡的温度为36℃,时间为6s;然后将原箔顺次经挤压辊挤干、137℃热风吹干、收卷、分切,得到成品电解铜箔。
对比例1
将实施例3的钨酸钠省去,酒石酸钾钠的质量浓度改为25g/L,苯并三氮唑的质量浓度改为3g/L,原箔浸泡的时间改为15s,其他条件和实施例3相同。
对比例2
将实施例3的乙二胺四乙酸二钠和γ-巯丙基三甲氧基硅烷省去,柠檬酸的质量浓度改为0.5g/L,原箔浸泡的温度改为20℃,其他条件和实施例3相同。
对实施例1~4和对比例1~2得到的电解铜箔的常温高温抗氧化性、抗剥离强度、润湿性进行测试。将150mm×150mm的电解铜箔在温度30℃,相对湿度80%下测试常温抗氧化性;将150mm×150mm的电解铜箔在240℃的恒温下测试高温抗氧化性;用达因笔测试润湿性能。
实施例1的电解铜箔的厚度为6.2μm,常温下72h无氧化现象,高温下40min无氧化现象,达因值为36,抗剥离强度为2.2N/mm。
实施例2的电解铜箔的厚度为6.0μm,常温下72h无氧化现象,高温下40min无氧化现象,达因值为38,抗剥离强度为2.4N/mm。
实施例3的电解铜箔的厚度为5.7μm,常温下72h无氧化现象,高温下40min无氧化现象,达因值为42,抗剥离强度为2.6N/mm。
实施例4的电解铜箔的厚度为5.6μm,常温下72h无氧化现象,高温下40min无氧化现象,达因值为40,抗剥离强度为2.4N/mm。
对比例1的电解铜箔常温下28h出现氧化现象,高温下20min出现氧化现象,达因值为32,抗剥离强度为1.8N/mm。
对比例2的电解铜箔常温下24h出现氧化现象,高温下15min出现氧化现象,达因值为30,抗剥离强度为1.5N/mm。
以上所述仅是本发明的优选实施方式,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,这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种电解铜箔的环保型防氧化液,其特征在于,包含如下质量浓度的组分:
酒石酸钾钠35~45g/L,乙二胺四乙酸二钠3~7g/L,添加剂6~12g/L,羧酸及其衍生物1~8g/L,苯并三氮唑0.5~2g/L,硅烷偶联剂0.2~1g/L。
2.根据权利要求1所述的环保型防氧化液,其特征在于,所述添加剂为钨酸钠、次亚磷酸钠和α-烯基磺酸钠中的一种或几种。
3.根据权利要求1或2所述的环保型防氧化液,其特征在于,所述羧酸及其衍生物为羧乙基硫代丁二酸、柠檬酸、均三苯甲酸和酒石酸中的一种或几种。
4.根据权利要求3所述的环保型防氧化液,其特征在于,所述硅烷偶联剂为3-氨丙基三乙氧基硅烷、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷或γ-巯丙基三甲氧基硅烷。
5.根据权利要求4所述的环保型防氧化液,其特征在于,环保型防氧化液的溶剂为水,环保型防氧化液的pH值为2~5。
6.一种电解铜箔的环保型防氧化工艺,其特征在于,包含如下步骤:
将电解铜箔原箔经剥离轴从阴极辊上剥离,由导辊将原箔放入权利要求1~5任一项所述的环保型防氧化液中浸泡,然后顺次经挤压辊挤干、干燥、收卷、分切,得到成品电解铜箔。
7.根据权利要求6所述的环保型防氧化工艺,其特征在于,所述浸泡的温度为30~40℃。
8.根据权利要求6或7所述的环保型防氧化工艺,其特征在于,所述浸泡的时间为3~8s。
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CN106544709A (zh) * | 2016-11-03 | 2017-03-29 | 山东金宝电子股份有限公司 | 一种提高电解铜箔高温防氧化性能的表面处理工艺 |
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