CN112940643A - 一种双聚合物凝胶材料及其制备方法和应用 - Google Patents
一种双聚合物凝胶材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种双聚合物凝胶材料,由导电聚合物凝胶网络和粘结聚合物凝胶网络相互穿插交错而成。本发明还公开了上述双聚合物凝胶材料的制备方法及其作为导电粘结剂在制备锂电池负极材料方面的应用。本发明制得的双聚合物凝胶材料能够作为电化学储能上的导电粘结剂,相比于单一的导电聚合物凝胶,通过往导电聚合物凝胶中加入柔性的粘结聚合物凝胶,大大增加了聚合物凝胶材料的弹性,同时,由导电聚合物凝胶网络和粘结聚合物凝胶网络相互穿插交错而成的聚合物凝胶材料彼此通过氢键、共价键合或离子键合连接,不仅提高了聚合物凝胶网络之间的相互作用力,还增强了聚合物凝胶网络与活性材料之间的相互作用力,进而增强了硅@复合凝胶材料的结构稳定性;并且两个凝胶网络同时生成,不仅能提高双聚合物凝胶网络的分布均匀性,也能够进一步增大彼此的相互作用力。
Description
技术领域
本发明涉及一种双聚合物凝胶材料,还涉及上述双聚合物凝胶材料的制备方法及其作为导电粘结剂在制备锂电池负极材料方面的应用。
背景技术
在电化学储能中,活性材料需要与导电剂和粘结剂一起分散到溶剂中形成浆料、再进一步涂覆到集流体上。在传统工艺中,导电剂一般采用具有高电导率的碳纳米材料,如零维碳黑颗粒、一维碳纳米管和二维石墨烯材料,这些碳导电剂在电极中是相互游离的,不能提供持续的电子传输通道且在持续的充放电过程中易与活性材料失去电接触,这会导致电极材料比容量、循环寿命和倍率性能的下降。
凝胶材料是一种具有互连网络结构的新型多孔材料,其中,导电聚合物凝胶可以提供三维电子/离子混合传输通道,因而有望取代传统碳导电剂用于电化学能量存储领域。但是,单一的导电聚合物凝胶的机械性能较差,而且其与活性材料之间的相互作用普遍较弱,这在一定程度上制约了其在电化学储能领域的商业化应用。
发明内容
发明目的:本发明针对现有技术中单一导电聚合物凝胶存在的机械性能差,与活性材料之间的相互作用弱的问题,提供一种双聚合物凝胶材料,本发明还提供上述双聚合物凝胶材料的制备方法及其作为导电粘结剂在制备锂电池负极材料方面的应用。
技术方案:本发明所述的双聚合物凝胶材料,由导电聚合物凝胶网络和粘结聚合物凝胶网络相互穿插交错而成。
其中,所述导电聚合物凝胶网络由横向排布的导电聚合物凝胶和纵向排布的导电聚合物凝胶相互穿插形成三维网络框架结构;所述粘结聚合物凝胶网络由横向排布的粘结聚合物凝胶和纵向排布的粘结聚合物凝胶相互穿插形成三维网络框架结构。
其中,所述导电聚合物凝胶网络由吡咯或苯胺单体经氧化聚合而成;所述粘结聚合物凝胶网络由含羧基、羟基或胺基的粘结聚合物与交联剂经共价缩合而成。
其中,在制备导电聚合物凝胶网络时,还加入有掺杂剂,掺杂剂通过静电作用引入到导电聚合物中来提升导电聚合物凝胶网络的电导率。
上述双聚合物凝胶材料的制备方法,具体包括如下步骤:
(1)将单体材料、掺杂剂和含羧基、羟基或胺基的粘结聚合物溶解到水中,形成混合溶液;
(2)将交联剂和氧化剂一起加入步骤(1)的混合溶液中,静置或搅拌至体系呈凝胶状态,得到双聚合物凝胶材料;其中,单体材料的氧化聚合反应与粘结聚合物的共价缩合反应是同时进行的;
其中,步骤(1)中,所述单体材料为吡咯或苯胺,所述掺杂剂为酞菁铜四磺酸四钠盐或植酸,所述粘结聚合物为聚乙烯醇、壳聚糖或聚丙烯酸中的一种,所述交联剂为戊二醛、硼砂或三羟甲基三聚氰胺中的一种,所述氧化剂为过硫酸铵或铁氰化钾。
其中,步骤(1)中,所述单体材料和掺杂剂的加入摩尔比为1:1~1000:1;所述单体材料与粘结聚合物的加入质量比为1:5~5:1。
其中,步骤(2)中,单体材料和氧化剂的加入摩尔比为1:1~1:5,粘结聚合物与交联剂的加入质量比为1:10~10:1。
上述双聚合物凝胶材料作为导电粘结剂在制备锂电池负极材料方面的应用。
有益效果:本发明制得的双聚合物凝胶材料能够作为电化学储能上的导电粘结剂,相比于单一的导电聚合物凝胶(呈脆性,因此容易破碎),通过往导电聚合物凝胶中加入柔性的粘结聚合物凝胶,大大增加了聚合物凝胶材料的弹性,同时,由导电聚合物凝胶网络和粘结聚合物凝胶网络相互穿插交错而成的聚合物凝胶材料彼此通过氢键、共价键合或离子键合连接,不仅提高了聚合物凝胶网络之间的相互作用力,还增强了聚合物凝胶网络与活性材料之间的相互作用力,进而增强了硅@复合凝胶材料的结构稳定性;并且两个凝胶网络同时生成,不仅能提高双聚合物凝胶网络的分布均匀性,也能够进一步增大彼此的相互作用力。
附图说明
图1为实施例1制得的双聚合物凝胶材料的透射电镜图(1μm);
图2为实施例1制得的双聚合物凝胶材料的结构示意图;
图3为实施例1制得的双聚合物凝胶材料的透射电镜图(200nm);
图4为实施例1制得的双聚合物凝胶材料的透射电镜图(10nm);
图5为实施例1制得的硅@双聚合物凝胶电极的扫描电镜图(5μm);
图6为实施例1制得的硅@双聚合物凝胶电极的透射电镜图(50nm);
图7为实施例1制得的硅@双聚合物凝胶电极的首次充放电曲线图(0.1A·g-1);
图8为实施例1制得的硅@双聚合物凝胶电极的循环性能图(2-100圈,0.5A·g-1);
图9为实施例1制得的硅@双聚合物凝胶电极的倍率性能图(2-50圈,0.5-5A·g-1)。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步说明。
实施例1
本发明双聚合物凝胶材料的制备方法,包括如下步骤:
步骤1,将吡咯、酞菁铜四磺酸四钠盐和聚乙烯醇溶解到水中,形成均匀的混合溶液,混合溶液中,吡咯和酞菁铜四磺酸四钠盐的加入摩尔比为719:1,吡咯与聚乙烯醇的加入质量比为1:1.4;
步骤2,将戊二醛和过硫酸铵加入步骤1的混合溶液中,混合溶液中,聚乙烯醇与戊二醛的加入质量比为1:1.3,吡咯和过硫酸铵的加入摩尔比为1:1.4,静置至体系呈凝胶状态,得到双聚合物凝胶材料。
由透射电镜图(图1)和结构示意图(图2)可见,实施例1得到的双聚合物凝胶材料是由导电聚合物凝胶网络与粘结聚合物凝胶网络在三维方向上相互交织而成的双聚合物凝胶材料,其中,导电聚合物聚吡咯凝胶网络由吡咯单体与过硫酸铵经氧化聚合形成,酞菁铜四磺酸四钠盐作为掺杂剂掺杂到聚吡咯中提升其电导率,而粘结聚合物凝胶网络由富含羟基的聚乙烯醇与戊二醛经共价缩合形成。由透射电镜图(图3和图4)可见,在双聚合物凝胶材料内部包含丰富的互连纳米孔洞,而且导电聚合物聚吡咯凝胶网络与粘结聚合物聚乙烯醇凝胶网络在纳米尺度上实现了高度均匀分布,这有利于最大程度发挥两者的功能及其协同效应。
实施例2
本发明双聚合物凝胶材料的制备方法,包括如下步骤:
步骤1,将吡咯、植酸和聚乙烯醇溶解到水中,形成均匀的混合溶液,混合溶液中,吡咯和植酸的加入摩尔比为1:1,吡咯与聚乙烯醇的加入质量比为1:5;
步骤2,将硼砂和过硫酸铵加入步骤1的混合溶液中,混合溶液中,聚乙烯醇与硼砂的加入质量比为10:1,吡咯和过硫酸铵的加入摩尔比为1:1,搅拌至体系呈凝胶状态,得到双聚合物凝胶材料。
实施例2所得的双聚合物凝胶材料也为由导电聚合物凝胶网络与粘结聚合物凝胶网络在三维方向上相互交织而成的双聚合物凝胶材料,与实施例1得到的材料结构相似。
实施例3
本发明双聚合物凝胶材料的制备方法,包括如下步骤:
步骤1,将吡咯、酞菁铜四磺酸四钠盐和聚乙烯醇溶解到水中,形成均匀的混合溶液,混合溶液中,吡咯和酞菁铜四磺酸四钠盐的加入摩尔比为200:1,吡咯与聚乙烯醇的加入质量比为5:1;
步骤2,将三羟甲基三聚氰胺和铁氰化钾加入步骤1的混合溶液中,混合溶液中,聚乙烯醇与三羟甲基三聚氰胺的加入质量比为4:1,吡咯和铁氰化钾的加入摩尔比为1:2.5,静置至体系呈凝胶状态,得到双聚合物凝胶材料。
实施例3所得的双聚合物凝胶材料也为由导电聚合物凝胶网络与粘结聚合物凝胶网络在三维方向上相互交织而成的双聚合物凝胶材料,与实施例1得到的材料结构相似。
实施例4
本发明双聚合物凝胶材料的制备方法,包括如下步骤:
步骤1,将苯胺、酞菁铜四磺酸四钠盐和聚乙烯醇溶解到水中,形成均匀的混合溶液,混合溶液中,苯胺和酞菁铜四磺酸四钠盐的加入摩尔比为1000:1,苯胺与聚乙烯醇的加入质量比为1:2;
步骤2,将戊二醛和过硫酸铵加入步骤1的混合溶液中,混合溶液中,聚乙烯醇与戊二醛的加入质量比为1:10,苯胺和过硫酸铵的加入摩尔比为1:2,搅拌至体系呈凝胶状态,得到双聚合物凝胶材料。
实施例4所得的双聚合物凝胶材料也为由导电聚合物凝胶网络与粘结聚合物凝胶网络在三维方向上相互交织而成的双聚合物凝胶材料,与实施例1得到的材料结构相似。
实施例5
本发明双聚合物凝胶材料的制备方法,包括如下步骤:
步骤1,将苯胺、植酸和壳聚糖溶解到水中,形成均匀的混合溶液,混合溶液中,苯胺和植酸的加入摩尔比为10:1,苯胺与壳聚糖的加入质量比为1:1;
步骤2,将戊二醛和过硫酸铵加入步骤1的混合溶液中,混合溶液中,壳聚糖与戊二醛的加入质量比为1:2,苯胺和过硫酸铵的加入摩尔比为1:1.2,静置至体系呈凝胶状态,得到双聚合物凝胶材料。
实施例5所得的双聚合物凝胶材料也为由导电聚合物凝胶网络与粘结聚合物凝胶网络在三维方向上相互交织而成的双聚合物凝胶材料,与实施例1得到的材料结构相似。
实施例6
本发明双聚合物凝胶材料的制备方法,包括如下步骤:
步骤1,将苯胺、植酸和聚丙烯酸溶解到水中,形成均匀的混合溶液,混合溶液中,苯胺和植酸的加入摩尔比为50:1,苯胺与聚丙烯酸的加入质量比为1:1;
步骤2,将三羟甲基三聚氰胺和铁氰化钾加入步骤1的混合溶液中,混合溶液中,聚丙烯酸与三羟甲基三聚氰胺的加入质量比为2:1,苯胺和铁氰化钾的加入摩尔比为1:5,搅拌至体系呈凝胶状态,得到双聚合物凝胶材料。
实施例6所得的双聚合物凝胶材料也为由导电聚合物凝胶网络与粘结聚合物凝胶网络在三维方向上相互交织而成的双聚合物凝胶材料,与实施例1得到的材料结构相似。
本发明制得的双聚合物凝胶材料在结构上,三维凝胶骨架可以提供持续的电子传输通道且内部互连孔结构能提供持续的离子传输通道,活性材料可以通过原位或非原位的方式均匀的固定于凝胶网络内部,三维电子/离子混合传输通道能显著加速电极反应过程中的电荷传输能力。在组成上,粘结聚合物网络凝胶能够提升复合网络凝胶材料的机械性能以及与活性材料之间的相互作用力。
为了验证本发明制得的双聚合物凝胶材料在电化学储能领域作为导电粘结剂的功效,将商业化硅纳米颗粒原位固定于该双聚合物凝胶材料中,随后直接涂覆于铜集流体上制成硅@双聚合物凝胶电极,测试硅@双聚合物凝胶电极作为锂离子电池负极的性能。由扫描电镜图(图5)可见,硅@双聚合物凝胶电极具有三维纳米多孔框架结构,而由透射电镜图(图6)可见,硅组分与导电聚合物聚吡咯和粘结聚合物聚乙烯醇在电极内部呈现高度均匀分布的状态。由首次充放电曲线(图7)可见,该硅@双聚合物凝胶电极的首次放电比容量和充电比容量分别为4444mAh·g-1和2601mAh·g-1,对应的首次库仑效率为58.5%。由循环性能图(图8)可见,该硅@双聚合物凝胶电极表现出了良好的循环寿命和高的可逆比容量,100次循环后,其放电比容量仍高达1834mAh·g-1。由倍率性能图(图9)可见,该硅@双聚合物凝胶电极表现出了优异的倍率性能,在2A·g-1和5A·g-1的大电流密度下,其平均比容量仍然分别达到1975mAh·g-1和1543mAh·g-1。
Claims (8)
1.一种双聚合物凝胶材料,其特征在于:由导电聚合物凝胶网络和粘结聚合物凝胶网络相互穿插交错而成。
2.根据权利要求1所述的双聚合物凝胶材料,其特征在于:所述导电聚合物凝胶网络由横向排布的导电聚合物凝胶和纵向排布的导电聚合物凝胶相互穿插形成三维网络框架结构;所述粘结聚合物凝胶网络由横向排布的粘结聚合物凝胶和纵向排布的粘结聚合物凝胶相互穿插形成三维网络框架结构。
3.根据权利要求1所述的双聚合物凝胶材料,其特征在于:所述导电聚合物凝胶网络由吡咯单体或苯胺单体经氧化聚合而成;所述粘结聚合物凝胶网络由含羧基、羟基或胺基的粘结聚合物与交联剂经共价缩合而成。
4.权利要求1所述的双聚合物凝胶材料的制备方法,其特征在于,具体包括如下步骤:
(1)将单体材料、掺杂剂和含羧基、羟基或胺基的粘结聚合物溶解到水中,形成混合溶液;
(2)将交联剂和氧化剂一起加入步骤(1)的混合溶液中,静置或搅拌至体系呈凝胶状态,得到双聚合物凝胶材料;其中,单体材料的氧化聚合反应与粘结聚合物的共价缩合反应为同时进行。
5.根据权利要求4所述的双聚合物凝胶材料的制备方法,其特征在于:步骤(1)中,所述单体材料为吡咯单体或苯胺单体,所述掺杂剂为酞菁铜四磺酸四钠盐或植酸,所述粘结聚合物为聚乙烯醇、壳聚糖或聚丙烯酸中的一种,所述交联剂为戊二醛、硼砂或三羟甲基三聚氰胺中的一种,所述氧化剂为过硫酸铵或铁氰化钾。
6.根据权利要求4所述的双聚合物凝胶材料的制备方法,其特征在于:步骤(1)中,所述单体材料和掺杂剂的加入摩尔比为1:1~1000:1;所述单体材料与粘结聚合物的加入质量比为1:5~5:1。
7.根据权利要求4所述的双聚合物凝胶材料的制备方法,其特征在于:步骤(2)中,单体材料和氧化剂的加入摩尔比为1:1~1:5,粘结聚合物与交联剂的加入质量比为1:10~10:1。
8.权利要求1所述的双聚合物凝胶材料作为导电粘结剂在制备锂电池负极材料方面的应用。
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