CN111063891B - 水性导电粘结剂的制备方法 - Google Patents
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Abstract
一种水性导电粘结剂,其特征在于该粘结剂采用海洋生物多糖与高弹体聚合物通过交联反应,然后将反应溶液蒸发提高浓度后制得,前述的交联反应采用了引发剂,所述的海洋生物多糖为含有氨基或羟基的极性基团生物多糖或其衍生物;所述的高弹体聚合物为结晶性硬链段和非结晶性软链段组成的嵌段共聚物。本发明还公开了水性导电粘结剂的制备方法。本发明的粘结剂机械强度大,具良好的粘结力和弹性,利于提高锂离子电池的性能。
Description
技术领域
本发明涉及一种应用于锂离子电池的粘结剂,本发明还涉及该粘结剂的制备方法。
背景技术
锂离子电池因其具有能量密度高、循环性能好、自放电率低、环保无污染等优点成为当今世界应用和研究最广泛的二次电池之一。目前,锂离子电池不但大规模应用于手机、笔记本电脑等便携式电子设备,也逐步向汽车动力以及储能系统等领域发展。新的应用对锂离子电池的比容量、倍率特性、循环寿命等性能提出了更高的要求。
锂离子电池的性能很大程度上取决于组成电池的正负极材料,而石墨是目前商业化锂离子电池最常用的负极材料。传统石墨负极材料的实际比容量已经接近其理论比容量372mAh/g,进一步改性提升的空间已经非常有限,难以满足市场对高容量负极日益增长的需求。故此以高比容量著称的硅基复合负极材料,因其具有数倍于石墨负极的理论比容量,成为当今世界的研究热点。
硅碳负极材料比较传统石墨负极的优势在于比容量大幅度提高,但是目前依旧存在循环性能不理想的问题。在进行电化学反应的同时,伴随着多个锂离子的脱嵌,自身产生了巨大的体积变化,容易粉化、剥落、刺穿隔膜,使得电池结构遭到严重破坏,进而导致循环比容量的迅速下降。
针对这一缺陷,有不少研究者通过石墨包覆硅纳米粒子等方法对硅碳负极材料自身进行修饰改性,如专利号为CN201510545414.7的中国发明专利《一种掺杂石墨烯的中空多孔的碳/硅纳米纤维锂电池负极材料及其制备方法》,它是由硅纳米粒子和石墨烯均匀地分散在碳纳米纤维基质中构成。具体制备方法为:以聚丙烯腈/聚甲基丙烯酸甲酯/正硅酸乙酯/氧化石墨烯的混合溶液作为壳层溶液,以聚甲基丙烯酸甲酯溶液作为芯层溶液,利用同轴静电纺丝技术得到掺杂氧化石墨烯的聚丙烯腈/聚甲基丙烯酸甲酯/二氧化硅纳米纤维,将得到的纳米纤维在200-300℃条件下预氧化,然后在500-1000℃条件下进行高温碳化,最后利用镁粉热还原得到掺杂石墨烯的中空多孔的碳/硅纳米纤维锂电池负极材料。该方法提高了电极材料的导电性,改善了锂电池负极材料的循环稳定性,但容易带来容量下降等问题。如专利申请公开号CN 104332632 A也报道了对硅碳负极材料自身进行修饰改性的一些方法,但是也存在容易带来容量下降等问题。
发明内容
本发明所要解决的第一个技术问题是针对上述的技术现状而提供一种能提高电池性能的水性导电粘结剂。
本发明所要解决的第二个技术问题是提供一种能提高电池性能的水性导电粘结剂的制备方法。
本发明解决上述第一技术问题所采用的技术方案为:一种水性导电粘结剂,其特征在于该粘结剂采用海洋生物多糖与高弹体聚合物通过交联反应,然后将反应溶液蒸发提高浓度后制得,前述的交联反应采用了交联剂,所述的海洋生物多糖为含有氨基或羟基的极性基团生物多糖或其衍生物;所述的高弹体聚合物为结晶性硬链段和非结晶性软链段组成的嵌段共聚物;所述的高弹体聚合物与海洋生物多糖的重量比为3:1~1:3;所述引发剂浓度为海洋生物多糖重量分数的0.2%~0.5%。
作为优选,所述的海洋生物多糖为羧甲基壳聚糖、海藻酸钠、褐藻胶中的至少一种。
作为优选,所述的高弹体聚合物为改性天然橡胶、苯乙烯-丁二烯嵌段共聚物(SBS)、苯乙烯-异戊二烯嵌段共聚物(SIS)、聚己内酰胺-聚乙二醇嵌段共聚物(TPAE)中的至少一种。
作为优选,所述的引发剂过硫酸铵、过硫酸钠或过硫酸钾中的至少一种。
本发明解决上述第二技术问题所采用的技术方案为:一种水性导电粘结剂的制备方法,其特征在于包括如下步骤:
①在反应容器中将海洋生物多糖溶于去离子水,得到重量百分比为1%~4%的溶液;
②在上述溶液中加入高弹体聚合和交联剂,维持恒温45℃~65℃,并搅拌12~36小时;
③上述反应完成后,将反应液在开放环境中加热至70~90℃(最佳为80℃)加速蒸发8~10小时,待体系固含量上升至25%后,即得到水性导电粘结剂。
与现有技术相比,本发明的优点在于:采用来源广泛、成本低廉的海洋生物多糖作为改性原料,在提高粘结剂机械强度的同时降低了生产成本;同时,海洋生物多糖与高弹体聚合物交联后形成的大量连接点确保Si负极活性颗粒在充放电循环中反复伸缩后仍能连接在集流体上,并遏制活性材料颗粒发生不可逆滑移,提升了锂离子电池的循环性能。所得粘结剂具良好的粘结力和弹性。
附图说明
图1为实施例1中壳聚糖粘结剂、与SBS嵌段共聚物交联后的壳聚糖粘结剂、和较为常见的聚丙烯酸粘结剂三种不同粘结剂制备的扣式电池,在相同测试条件下的循环容量衰减对比图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1:该制备方法包括以下步骤;
(1)在反应容器中将8g羧甲基壳聚糖溶于392g去离子水,得到2%的溶液。
(2)在上述溶液中加入高弹体聚合物——苯乙烯-丁二烯嵌段共聚物SBS 20g(高弹体聚合物与海洋生物多糖的质量比为2.5:1),和交联剂过硫酸铵0.0032g,维持恒温50℃,并搅拌24小时。
(3)上述反应完成后,将反应液在开放环境中加热至80℃加速蒸发8小时,待体系固含量上升至25%后,即得到目标粘结剂。
(4)将得到的粘结剂按照质量比硅基负极材料:导电剂:粘结剂=70:15:15搅拌均匀,将此负极浆料涂覆在导电铜箔集流体表面,加热烘干、辊压膜切后,得到成品极片,测得剥离强度为27N/m,高于同一测试流程下,常规锂离子电池水性负极粘结剂丁苯橡胶乳液与羧甲基纤维素混合物(SBR+CMC)的15N/m左右。
(5)上述极片样品组装为扣式锂离子电池,并以自交联壳聚糖粘结剂和聚丙烯酸粘结剂在相同环境及步骤下制备的扣式电池为对照。由附图1可见,使用与SBS嵌段共聚物交联壳聚糖粘结剂制备的扣式电池,在循环容量衰减上较另外两者有明显优势。
从图1中可见,与SBS嵌段共聚物交联后的壳聚糖粘结剂,其循环容量衰减幅度远优于聚丙烯酸粘结剂,也好于未处理的壳聚糖粘结剂。这对提高Si负极的使用寿命有益。
实施例2:该制备方法包括以下步骤;
(1)在反应容器中将1g海藻酸钠溶于399g去离子水,得到1%的溶液。
(2)在上述溶液中加入高弹体聚合物——环氧化天然橡胶3g(高弹体聚合物与海洋生物多糖的质量比为3:1),和交联剂过硫酸钠0.0032g,维持恒温45℃,并搅拌36小时。
(3)上述反应完成后,将反应液在开放环境中加热至80℃加速蒸发10小时,待体系固含量上升至25%后,即得到目标粘结剂。
(4)将得到的粘结剂按照质量比硅基负极材料:导电剂:粘结剂=60:30:10搅拌均匀,将此负极浆料涂覆在导电铜箔集流体表面,加热烘干、辊压膜切后,得到成品极片,测得剥离强度为19N/m,高于同一测试流程下,常规锂离子电池水性负极粘结剂丁苯橡胶乳液与羧甲基纤维素混合物(SBR+CMC)的12N/m左右。
实施例3:该制备方法包括以下步骤;
(1)在反应容器中将16g褐藻胶溶于384g去离子水,得到4%的溶液。
(2)在上述溶液中加入高弹体聚合物——聚己内酰胺-聚乙二醇嵌段共聚物TPAE5.3g(高弹体聚合物与海洋生物多糖的质量比为1:3),和交联剂过硫酸钾0.08g,维持恒温65℃,并搅拌12小时。
(3)上述反应完成后,将反应液在开放环境中加热至80℃加速蒸发8小时,待体系固含量上升至25%后,即得到目标粘结剂。
(4)将得到的粘结剂按照质量比硅基负极材料:导电剂:粘结剂=75:10:15搅拌均匀,将此负极浆料涂覆在导电铜箔集流体表面,加热烘干、辊压膜切后,得到成品极片,测得剥离强度为22N/m,高于同一测试流程下,常规锂离子电池水性负极粘结剂丁苯橡胶乳液与羧甲基纤维素混合物(SBR+CMC)的13N/m左右。
Claims (2)
1.一种水性导电粘结剂的制备方法,其特征在于包括如下步骤:
①在反应容器中将1g海藻酸钠溶于399g去离子水,得到1%的溶液;
②在上述溶液中加入环氧化天然橡胶3g和交联剂过硫酸钠0.0032g,维持恒温45℃,并搅拌36小时;
③上述反应完成后,将反应液在开放环境中加热至80℃加速蒸发10小时,待体系固含量上升至25%后,即得到目标粘结剂。
2.一种水性导电粘结剂的制备方法,其特征在于包括如下步骤:
①在反应容器中将16g褐藻胶溶于384g去离子水,得到4%的溶液;
②在上述溶液中加入聚己内酰胺-聚乙二醇嵌段共聚物TPAE 5.3g和交联剂过硫酸钾0.08g,维持恒温65℃,并搅拌12小时;
③上述反应完成后,将反应液在开放环境中加热至80℃加速蒸发8小时,待体系固含量上升至25%后,即得到目标粘结剂。
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