CN117343670A - 一种水性锂离子电池负极用胶黏剂及其制备方法和应用 - Google Patents
一种水性锂离子电池负极用胶黏剂及其制备方法和应用 Download PDFInfo
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- CN117343670A CN117343670A CN202311483098.6A CN202311483098A CN117343670A CN 117343670 A CN117343670 A CN 117343670A CN 202311483098 A CN202311483098 A CN 202311483098A CN 117343670 A CN117343670 A CN 117343670A
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- negative electrode
- adhesive
- ion battery
- lithium ion
- water
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- 239000000463 material Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种水性锂离子电池负极用胶黏剂及其制备方法和应用，该水性锂离子电池负极用胶黏剂的原料组成包括有机盐类单体、水溶性单体、油溶性单体、分散剂、引发剂和去离子水；分散剂选自纤维素醚；以有机盐类单体、水溶性单体和油溶性单体的单体总质量计，分散剂的加入量为0.05～0.50wt％。本发明公开的水性锂离子电池负极用胶黏剂，在已有原料体系的基础上，只需要加入特定种类、特定含量的分散剂，即可显著降低水性胶黏剂的粘度同时提高其与负极极片间的粘结力，进而使得最终组装得到的锂离子电池的循环稳定性也得到了一定提升。
Description
技术领域
本发明涉及锂离子电池的技术领域，尤其涉及一种水性锂离子电池负极用胶黏剂及其制备方法和应用。
背景技术
锂电池作为新型可充电电池，具有重量轻、储能大、功率高、无污染、寿命长、自动放电系数小等优点。随着市场对锂离子电池能量密度要求的提高，对锂离子电池电极材料的要求也在不断提高。在电极材料中，胶粘剂主要起到将正、负极活性物质粘接附着在集流体上的作用，其作为一种活性材料，在电池生产和使用过程中起到维持极片的机械结构和电化学性能稳定的作用。
目前，锂离子电池采用的胶粘剂种类主要分为油性胶粘剂和水性胶粘剂，油性胶粘剂在电池的生产制备过程中存在有机溶剂挥发以及易燃易爆易中毒的问题；相较于油性胶粘剂，水性胶粘剂具备环保安全和易于加工等特性，正在逐步成为锂离子电池胶粘剂领域的研究热点。
水性锂电池聚丙烯酸胶黏剂是目前商业化锂离子电池常用的负极胶粘剂，如公开号为CN 1328104 A的中国专利文献中公开了一种锂离子电池水性粘合剂制备方法，先将亲水性单体、助剂溶于水中配制成水溶液，再加入亲油性单体，加热至30～80℃，加入引发剂引发聚合，反应结束后去除挥发性单体即制得锂离子电池水性粘合剂；助剂为双封端聚醚。该技术方案为目前常规的水性锂电池聚丙烯酸胶黏剂的制备工艺，但一方面合成过程中随着反应的进行，单体粒径不断增大，单体直接碰撞几率不断增大，在反应器内容易结块团聚；另一方面，制备得到的水性胶黏剂的粘度过大，与负极极片间的粘剂强度不高。
发明内容
针对现有技术中存在的上述问题，本发明公开了一种水性锂离子电池负极用胶黏剂，在已有原料体系的基础上，只需要加入特定种类、特定含量的分散剂，即可显著降低水性胶黏剂的粘度同时提高其与负极极片间的粘结力，进而使得最终组装得到的锂离子电池的循环稳定性也得到了一定提升。
具体技术方案如下：
一种水性锂离子电池负极用胶黏剂，原料组成包括有机盐类单体、水溶性单体、油溶性单体、分散剂、引发剂和去离子水；
所述分散剂选自纤维素醚；
以有机盐类单体、水溶性单体和油溶性单体的单体总质量计，分散剂的加入量为0.05～0.50wt％。
在本领域技术人员的常规观念中，纤维素醚类由于较高的分子量、较多的-OH从而形成较强的氢键作用，以及其较大的空间结构都使得其具有增大溶液粘度(增稠)的作用，而在本发明中，发明人意外发现在水性锂离子电池负极用胶黏剂的体系中，加入特定含量的纤维素醚类作为分散剂不仅不会提高体系的粘度，反而会大幅降低体系的粘度，并提高其与负极极片间的粘结力，进而使得最终组装得到的锂离子电池的循环稳定性也得到了一定提升；基于该发现从而提出了本发明。
经试验发现，若将所述分散剂替换为本领域的其它常见种类，如其它合成高分子类分散剂(聚乙烯醇、聚丙烯酸钠等)，如其它天然高分子类分散剂(明胶)，再如无机分散剂(碳酸镁、碳酸钙、碳酸钡等)，不仅不会降低水性锂离子电池负极用胶黏剂的粘度，反而还会导致其升高，同时影响负极极片的粘结力。
经试验进一步发现，即使采用上述特殊种类的分散剂，但若加入的量不合适，也会导致水性锂离子电池负极用胶黏剂的粘度增加，降低负极极片的粘结力。
优选的，所述分散剂选自甲基纤维素、羟乙基甲基纤维素、羧甲基纤维素、乙基纤维素、苄基纤维素、羟乙基纤维素、羟丙基甲基纤维素、氰乙基纤维素、苄基氰乙基纤维素、羧甲基羟乙基纤维素、苯基纤维素、羧甲基纤维素钠、羧甲基纤维素锂中的一种或多种；
优选的：
分散剂占单体总质量的0.20～0.50wt％；进一步优选为0.20wt％。
经试验发现，所述分散剂的粘度对于制备的水性锂离子电池负极用胶黏剂的粘度以及对负极极片的粘结力也产生显著影响。
优选的：
所述分散剂的粘度为1000～8000mPa·s；进一步优选为2000～5000mPa·s；更优选为2000～3000mPa·s。
本发明中分散剂的粘度均是采用1wt％的分散剂水溶液在25℃条件下进行测试。
本发明中采用的原料单体包括有机盐类单体、水溶性单体和油溶性单体，均为本领域的常规原料种类；本发明中原料单体的质量即指上述三种单体的总质量。
所述有机盐类单体选自丙烯酸钠、丙烯酸锂、甲基丙烯酸钠、甲基丙烯酸锂、苯乙烯磺酸钠、苯乙烯磺酸锂、乙烯基磺酸钠、乙烯基磺酸锂、衣康酸钠、衣康酸锂、衣康酸钠单丁酯、衣康酸锂单丁酯、富马酸钠、富马酸锂、马来酸钠、马来酸锂中的一种或多种；
所述水溶性单体选自丙烯酸、甲基丙烯酸、苯乙烯磺酸、乙烯基磺酸、衣康酸、衣康酸单丁酯、富马酸、马来酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、乙氧基乙氧基乙基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基丙烯酰胺中的一种或多种；
所述油溶性单体选自丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸异冰片酯、醋酸乙烯酯、丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-溴丙烯腈、α-乙基丙烯腈、苯乙烯中的一种或多种；
优选的：
所述有机盐类单体选自丙烯酸钠、丙烯酸锂、甲基丙烯酸钠、甲基丙烯酸锂中的一种或多种；
所述水溶性单体选自丙烯酸、甲基丙烯酸、衣康酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基丙烯酰胺中的一种或多种；
所述油溶性单体选自丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-溴丙烯腈、α-乙基丙烯腈中的一种或多种。
优选的：
有机盐类单体、水溶性单体与油溶性单体的质量比为(1～40):
(10～70):(30～70)；
进一步优选：
有机盐类单体、水溶性单体与油溶性单体的质量比为(5～10):
(40～50):(45～55)。
本发明中采用的引发剂为本领域常规的原料种类，如过硫酸盐类引发剂、偶氮类引发剂、有机过氧化物类引发剂、氧化还原体系引发剂等等。
所述过硫酸盐类引发剂选自过硫酸钾，过硫酸铵，过硫酸钠等；
所述偶氮类引发剂选自ABIN、ABVN等；
所述有机过氧化物类引发剂选自LPO、IPP、EHP、BPO等；
所述氧化还原体系引发剂选自过氧化氢-亚铁盐体系，过硫酸盐-亚硫酸盐体系等。
优选的，引发剂占单体总质量的0.05～0.5wt％。
本发明还公开了所述的水性锂离子电池负极用胶黏剂的制备方法，包括：
步骤一：将有机盐类单体、油溶性单体、水溶性单体、分散剂和去离子水混合均匀，升温至40～85℃并通入惰性气体进行保护，再加入引发剂，经聚合反应后制备得到聚合物悬浮液；
步骤二：在聚合物悬浮液中加入无机碱中和，直至调节pH为6.0～9.0，再加入去离子水稀释得到固含量为2.5～25.0wt的水性锂离子电池负极用胶黏剂。
所述无机碱选自氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠、碳酸锂、碳酸氢锂、磷酸钠、磷酸二氢钠、磷酸氢二钠、磷酸锂、磷酸二氢锂、磷酸氢二锂中的一种或多种。
本发明还公开了以上述的水性锂离子电池负极用胶黏剂制备的锂离子电池用负极片，以及以该负极片组装得到的锂离子电池。
与现有技术相比，本发明具有如下优点：
本发明公开了一种水性锂离子电池负极用胶黏剂，在原有原料体系的基础上，仅添加了特殊添加量的纤维素醚为分散剂，就意外获得了显著降低产物水性锂离子电池负极用胶黏剂的粘度，显著提高其与负极极片的粘结力的技术效果。
将本发明制备的水性锂离子电池负极用胶黏剂用于制备负极片时，由于胶黏剂的粘度低，可以提高负极浆料的固含量，改善加工性能；以该负极片组装得到的锂离子电池，具有更高的循环稳定性，在25℃下，循环1000圈的容量保持率最高可达98.5％；在45℃下，循环1000圈的容量保持率最高可达90.7％。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明进行具体描述，但本发明并不限于这些实施例，该领域技术人员在本发明核心指导思想下做出的非本质改进和调整，仍然属于本发明的保护范围。
实施例1
将5重量份丙烯酸钠、40重量份甲基丙烯酸、5重量份N-羟甲基丙烯酰胺、40重量份丙烯腈、10重量份丙烯酸丁酯混合，加入0.2重量份的羧甲基纤维素钠(1wt％水溶液粘度：3000mPa·s)和100重量份水混合均匀后倒入反应釜中，设置搅拌速率为250rpm，升温至50℃并通入氮气进行保护，待温度稳定后加入0.2重量份过硫酸铵和0.1重量份的亚硫酸氢钠，聚合10h后得到聚合物悬浮液。在聚合物悬浮液中，加入氢氧化钠调节至pH值为8.0，加入去离子水稀释后得到固含量为5wt％水性锂离子电池负极用胶黏剂。
将本实施例制备的水性锂离子电池负极用胶黏剂在25℃下进行测试，测试的粘度数据列于下表1中。
对比例1
制备工艺与实施例1基本相同，区别仅在于未加入分散剂。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
对比例2
制备工艺与实施例1基本相同，区别仅在于将加入的分散剂替换为等重量份的明胶。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
对比例3
制备工艺与实施例1基本相同，区别仅在于将加入的分散剂替换为等重量份的聚乙烯醇(1wt％水溶液粘度：2000mPa·s)。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
对比例4
制备工艺与实施例1基本相同，区别仅在于将加入的分散剂替换为等重量份的聚丙烯酸钠(1wt％水溶液粘度：3000mPa·s)。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
对比例5
制备工艺与实施例1基本相同，区别仅在于将加入的分散剂替换为等重量份的碳酸镁。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例2
制备工艺与实施例1基本相同，区别仅在于将加入的羧甲基纤维素钠替换为0.05重量份。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例3
制备工艺与实施例1基本相同，区别仅在于将加入的羧甲基纤维素钠替换为0.5重量份。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
对比例6
制备工艺与实施例1基本相同，区别仅在于将加入的羧甲基纤维素钠替换为0.02重量份。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
对比例7
制备工艺与实施例1基本相同，区别仅在于将加入的羧甲基纤维素钠替换为1重量份。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例4
制备工艺与实施例1基本相同，区别仅在于将加入的羧甲基纤维素钠替换为等重量份的羟乙基甲基纤维素(1wt％水溶液粘度：3000mPa·s)。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例5
制备工艺与实施例1基本相同，区别仅在于加入的羧甲基纤维素钠的粘度为2000mPa·s(1wt％水溶液粘度)。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例6
制备工艺与实施例1基本相同，区别仅在于加入的羧甲基纤维素钠的粘度为5000mPa·s(1wt％水溶液粘度)。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例7
制备工艺与实施例1基本相同，区别仅在于加入的羧甲基纤维素钠的粘度为1000mPa·s(1wt％水溶液粘度)。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例8
制备工艺与实施例1基本相同，区别仅在于加入的羧甲基纤维素钠的粘度为8000mPa·s(1wt％水溶液粘度)。
本对比例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例9
制备工艺与实施例1基本相同，区别在于将加入的引发剂替换为0.3重量份的过硫酸钾，聚合反应温度替换为60℃。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
实施例10
制备工艺与实施例1基本相同，区别仅在于将加入的单体组成替换为10重量份甲基丙烯酸钠、30重量份衣康酸、10重量份丙烯酸羟乙酯、40重量份丙烯腈、10重量份丙烯酸异辛酯。
本实施例制备的负极用胶黏剂的粘度数据列于下表1中。
性能测试：
一、将各实施例和对比例分别制备的负极用胶黏剂配制成检测浆料，具体步骤如下：
将负极用胶黏剂、石墨、导电炭黑、丁苯橡胶(SBR)、羧甲基纤维素钠(CMC)与去离子水按质量比为1.5:96.5:1.0:0.5:0.5充分搅拌均匀后得到浆料，并均匀涂布在10μm的铜箔上，80℃烘干后，进行剥离强度测试，所得极片粘接力数据列于下表1中。
表1
二、以制备的负极用胶黏剂制备负极片并组装得到锂离子电池，具体步骤如下：
负极片的制备：将本发明制备的负极用胶粘剂1.5wt％，增稠剂羧甲基纤维素钠0.5wt％，丁苯橡胶0.5wt％，导电剂Super.P Li 1.0wt％，石墨96.5wt％和去离子水进行混合，制备得到固含量为54wt％负极浆料，而后将负极浆料涂覆在铜箔表面，干燥和辊压后得到负极片，测试此时的极片粘接力，并将实验结果列于下表2中；
正极片的制备：将磷酸铁锂材料96.5wt％，导电剂Super.P Li
1.5wt％，粘接剂聚偏氟乙烯2wt％和N-甲基吡咯烷酮进行混合，制备得到固含量为60wt％的正极浆料，而后将正极浆料涂覆在铝箔表面，干燥和辊压之后的得到正极片；
锂离子电池的制备：将正极片、负极片和电解液(新宙邦LBC338B86)进行组装，得到容量为3Ah的软包电池。测试其电芯循环性能。循环性能测试条件为：在25℃或45℃条件下，1C倍率的电流充电至3.65V，并以3.65V恒压，然后采用1C倍率电流放电到截止电压2.5V，重复该流程。实验结果如下表2。
表2
以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，以上应用了具体实例对本发明进行阐述，只是用于帮助理解本发明，并不用以限制本发明。本发明所属技术领域的技术人员依据本发明的构思，还可以做出若干简单推演、变形、替换或结合。这些推演、变形、替换或结合方案也落入本发明的权利要求范围内。
Claims (10)
1.一种水性锂离子电池负极用胶黏剂，其特征在于，原料组成包括有机盐类单体、水溶性单体、油溶性单体、分散剂、引发剂和去离子水；
所述分散剂选自纤维素醚；
以有机盐类单体、水溶性单体和油溶性单体的单体总质量计，分散剂的加入量为0.05～0.50wt％。
2.根据权利要求1所述的水性锂离子电池负极用胶黏剂，其特征在于：
所述有机盐类单体选自丙烯酸钠、丙烯酸锂、甲基丙烯酸钠、甲基丙烯酸锂、苯乙烯磺酸钠、苯乙烯磺酸锂、乙烯基磺酸钠、乙烯基磺酸锂、衣康酸钠、衣康酸锂、衣康酸钠单丁酯、衣康酸锂单丁酯、富马酸钠、富马酸锂、马来酸钠、马来酸锂中的一种或多种；
所述水溶性单体选自丙烯酸、甲基丙烯酸、苯乙烯磺酸、乙烯基磺酸、衣康酸、衣康酸单丁酯、富马酸、马来酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、乙氧基乙氧基乙基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基丙烯酰胺中的一种或多种；
所述油溶性单体选自丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸异冰片酯、醋酸乙烯酯、丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-溴丙烯腈、α-乙基丙烯腈、苯乙烯中的一种或多种；
所述引发剂选自过硫酸盐类引发剂、偶氮类引发剂、有机过氧化物类引发剂、氧化还原体系引发剂。
3.根据权利要求1所述的水性锂离子电池负极用胶黏剂，其特征在于：
有机盐类单体、水溶性单体与油溶性单体的质量比为(1～40):
(10～70):(30～70)；
引发剂占单体总质量的0.05～0.5wt％。
4.根据权利要求1所述的水性锂离子电池负极用胶黏剂，其特征在于：
所述分散剂选自甲基纤维素、羟乙基甲基纤维素、羧甲基纤维素、乙基纤维素、苄基纤维素、羟乙基纤维素、羟丙基甲基纤维素、氰乙基纤维素、苄基氰乙基纤维素、羧甲基羟乙基纤维素、苯基纤维素、羧甲基纤维素钠、羧甲基纤维素锂中的一种或多种；
分散剂占单体总质量的0.20～0.50wt％。
5.根据权利要求4所述的水性锂离子电池负极用胶黏剂，其特征在于：
所述分散剂的粘度为1000～8000mPa·s。
6.根据权利要求5所述的水性锂离子电池负极用胶黏剂，其特征在于：
所述分散剂的粘度为2000～5000mPa·s。
7.一种根据权利要求1～6任一项所述的水性锂离子电池负极用胶黏剂的制备方法，其特征在于，包括：
步骤一：将有机盐类单体、油溶性单体、水溶性单体、分散剂和去离子水混合均匀，升温至40～85℃并通入惰性气体进行保护，再加入引发剂，经聚合反应后制备得到聚合物悬浮液；
步骤二：在聚合物悬浮液中加入无机碱中和，直至调节pH为6.0～9.0，再加入去离子水稀释得到固含量为2.5～25.0wt％的水性锂离子电池负极用胶黏剂。
8.根据权利要求7所述的水性锂离子电池负极用胶黏剂的制备方法，其特征在于，步骤二中：所述无机碱选自氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠、碳酸锂、碳酸氢锂、磷酸钠、磷酸二氢钠、磷酸氢二钠、磷酸锂、磷酸二氢锂、磷酸氢二锂中的一种或多种。
9.一种锂离子电池用负极片，其特征在于，采用根据权利要求1～6任一项所述的水性锂离子电池负极用胶黏剂。
10.一种锂离子电池，其特征在于，包括如权利要求9所述的锂离子电池用负极片。
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