CN117577804A - 一种金属多酚阵列包覆石墨烯的制备方法及其应用 - Google Patents
一种金属多酚阵列包覆石墨烯的制备方法及其应用 Download PDFInfo
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- CN117577804A CN117577804A CN202311541493.5A CN202311541493A CN117577804A CN 117577804 A CN117577804 A CN 117577804A CN 202311541493 A CN202311541493 A CN 202311541493A CN 117577804 A CN117577804 A CN 117577804A
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Abstract
本发明涉及一种金属多酚配合物包覆氧化石墨烯的普适性制备方法,所述制备方法包括如下步骤:(1)氧化石墨烯均匀分散到去离子水中,分别加入多酚和金属离子溶液,得到多酚金属配合物包覆的石墨烯复合粗产品;(2)将步骤(1)所得粗产品用去离子水多次洗涤,得到多酚金属配合物包覆的石墨烯复合物纯相物质。本发明通过简单的液相合成法可有效制备多酚金属配合物与氧化石墨烯的复合材料,多酚金属配合物通过氧化还原反应机制在石墨烯表面原位生长,具有较强的异质界面稳定性。作为锂电负极,该电极材料具有优异的电子导电率和离子扩散性能,且长循环稳定,倍率性能优异;同时该方法工艺简单,绿色环保,材料来源广,操作安全性高,具有规模化生产的基础和广阔的应用前景。
Description
技术领域
本发明涉及一种金属多酚阵列包覆石墨烯的制备方法,,并将其应用于锂离子电池负极,属于锂离子电池技术领域。
背景技术
锂离子电池经过不断的开发与改进,作为一种高能的化学电源,因其良好的综合性能,已成为人们生产生活中不可或缺的能量存储与转换设备。随着经济和科技的不断发展,锂离子电池迎来了巨大的机遇,同时也是巨大的挑战,如何在现有基础上实现能量密度的大幅提高将是未来决定锂离子电池发展的决定性关键因素。其中负极作为锂离子电池的关键组成部分,对锂离子电池的能量密度及性能的提升至关重要。
现阶段锂离子电池已经不断趋近其理论能量密度的上限,为实现大规模的能源需求,开发并设计高能量密度,高倍率性能的新型锂离子电池负极材料是解决能源需求的关键。其中,有机电极材料作为锂离子电池负极已被广泛研究。Yao等人指出[Joule.2018,2,1690-1706],相比于无机电极材料,有机电极材料仅由资源丰富的轻质元素组成,具有成本低和污染小的优点。此外,有机分子结构多样且易于设计和调控,有利于实现更高的理论比容量和电化学性能的可控调节,非常适合大规模电力储能应用。
虽然有机材料用作锂离子电池负极具有优异的电化学性能,但在实现其工业化生产应用之前仍存在两个巨大阻碍:有机材料易溶解于有机溶剂和导电性差。因为有机材料导电性差,极度依赖导电剂的添加,大量导电剂的加入降低了循环的稳定性和实际的能量密度,导致难以应用。同时大部分提高导电性的方法都是加入高导电的材料,其复合方式大多为物理混合,难以均匀分散,同时在长期的循环过程中难以保持稳定的接触,不利于循环稳定性,且制备工艺复杂,不利于工业化应用和实施。
得益于多酚化合物对基材的高亲和力,它们与金属离子具有多种相互作用,金属多酚组装材料发展迅速,已广泛应用于化学、材料科学、生物医学等领域。
专利CN115998762A公开了一种柚皮素-锌金属多酚网络材料的制备方法和应用,所述制备方法为将柚皮素和醋酸锌与dSiO2与水溶液中反应,离心收集沉淀,利用柚皮素与锌金属离子配位与二氧化硅表面形成金属多酚网络涂层,并将其应用于生物抗菌材料。
专利CN115463564A公开了一种金属多酚网络超滤膜表面原位生长二氧化锰的改性方法,所制备的超滤膜由单宁酸与醋酸锰于水溶液中合成,改性的金属多酚超滤膜在对含油污水的处理方面具有较大的应用前景。
专利CN113394414A公开了一种基于金属多酚改性海藻酸钠/纳米纤维素复合气凝胶构建花蕊型S掺杂锰铜电催化剂的制备方法,构建单宁酸与金属锰和铜的金属多酚网络,在氮气下热处理退火后用作质子膜燃料电池的S掺杂锰铜电催化剂。
但受限于有机材料导电性差的固有特性,金属多酚配合物在储能领域的应用较少。石墨烯具有高导电性、高比表面的特点,且易与多酚化合物反应。鉴于此,本发明旨在通过简单的液相合成法制备多酚金属配合物阵列包覆石墨烯的复合材料,提高金属多酚配合物的电子导电率,使金属多酚材料在储能领域的应用得到开发,拓展金属多酚材料的应用范围。
发明内容
为解决现有技术问题,本发明的目的在于克服已有技术存在的不足,提供一种金属多酚阵列包覆石墨烯的制备方法,并将其应用于锂离子电池负极。多酚类化合物一般由一个或多个酚、邻苯二酚或邻苯三酚(PG)基团组成,这些基团通过不同作用力(包括氢键、配位键、分子间作用力等)与不同的有机分子、金属离子相互结合。其中,多酚分子可以通过原位氧化还原反应与氧化石墨烯进行复合,并同时与金属离子结合,形成金属多酚阵列包覆的石墨烯复合材料。该复合材料可以实现氧化石墨烯与金属多酚的化学结合,保证了优异的导电率和稳定的循环,适用于大规模生产。
为达到上述目的,本发明采用如下技术方案:
一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,包括以下制备步骤:
S1:以加入的多酚前驱体总质量百分比为100%计算,量取不超过30wt%氧化石墨烯,将氧化石墨烯放入容器中,加入去离子水稀释,得到分散均匀的氧化石墨烯分散液;
S2:将多酚前驱体(以没食子酸为例)0.17-1.7g和金属离子弱酸盐(以醋酸锌为例)0.18-1.83g加入步骤S1中的氧化石墨烯分散液中,反应0.5-24h;
S3:将步骤S2获得的粗产品用去离子水多次洗涤,抽滤,冷冻干燥得到金属多酚阵列包覆石墨烯复合材料;
进一步地,步骤S1和S2中反应温度范围为-20-200℃。
进一步地,步骤S1和S2中反应的气氛环境可以为空气、氮气或氩气等惰性气体。
进一步地,步骤S2中的多酚前驱体选自天然或人工合成的多羟基类化合物,包括但不仅限于没食子酸、焦性没食子酸、均苯三酚酸等酚酸,以及槲皮素、山柰酚、儿茶素、单宁酸等类黄酮类和多酚酰胺等多酚种类中的一种或几种。进一步地,步骤S2中的金属弱酸盐包括但不仅限于乙酸盐、丙酸盐、碳酸盐、次氯酸盐、柠檬酸盐、硼酸盐、偏硅酸盐、苯酚盐等弱酸盐中的一种或几种。进一步地,步骤S2中金属弱酸盐中的金属包括但不仅限于锂、钠、钾、钛、钒、铬、锰、铁、钴、镍、锌、铜、铝、镓、锆、钼、钌、铑、镉、铟、铪、铼、锡等中的一种或几种。
进一步地,步骤S2中反应时间控制在0.5-24h。
进一步地,步骤S2中多酚前驱体与金属弱酸盐的摩尔比为1:10-10:1。
一种金属多酚阵列包覆石墨烯的应用,其特征在于,用于制备锂离子电池,电池包含基于上述复合材料的锂离子电池负极材料和电解液,所述电解液含有锂盐LiPF6、LiClO4和LiTFSI中的至少一种,所述电解液含有添加剂碳酸亚乙烯酯、氟代碳酸乙烯酯和碳酸乙烯亚乙酯中的至少一种,所述电解液还含有选自非水溶剂碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸丙烯酯、二甘醇二甲醚、乙二醇二甲醚和碳酸二甲酯中的至少一种。
作为本发明优选的技术方案,上述复合储锂负极材料的应用,将金属多酚阵列包覆石墨烯材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1的质量比混合均匀,制成负极浆料,涂覆在铜箔上,放入真空烘箱中以不低于100℃下干燥至少12h,即得复合负极极片。
作为本发明进一步优选的技术方案,将所述复合负极极片作为工作电极,以金属锂片为对电极,采用EC:DMC:EMC体积比为1:1:1,含5%FEC添加剂,并且电解质浓度为1.0mol/L的混合液为电解液,在惰性气体气氛下组装成锂离子电池。
如上所述,本发明在金属多酚阵列包覆石墨烯的制备方法及其应用方面所具有的优点和积极的效果是:
1)本发明的有机多酚与金属配位阵列包覆石墨烯的制备方法,在合成中严格控制气体的环境,反应的温度,所用氧化石墨烯的量以及反应时间,能够有效避免多酚和氧化石墨烯发生自聚反应,从而使金属多酚配合物在石墨烯表面阵列生长。
2)本发明成功将高导电性的石墨烯与金属多酚配合物进行化学结合,极大程度的提高了金属多酚的导电性,构筑了具有优异电子和离子传导能力的复合材料。
3)本发明的金属多酚阵列包覆石墨烯的复合材料极大提高了有机材料本身的导电性,实现了快速的电子和离子传输,且合成简单,环境友好,可大规模生产,具有工业化应用前景。
附图说明
图1为本申请的具体实施例1中制备的没食子酸锌金属配合物(GAZn)阵列包覆氧化石墨烯材料的XRD图;
图2为本申请的具体实施例1中制备的没食子酸锌金属配合物(GAZn)阵列包覆氧化石墨烯材料的SEM图;
图3为本申请的具体实施例1中制备的没食子酸锌金属配合物(GAZn)阵列包覆氧化石墨烯材料应用与锂离子电池负极材料的循环性能曲线;
图4为本申请的具体实施例2中制备的不同比例没食子酸锌金属配合物(GAZn)阵列包覆氧化石墨烯材料的XRD图;
图5为本申请的具体实施例3中制备的没食子酸铋金属配合物(GABi)阵列包覆石墨烯材料的XRD图;
图6为本申请的具体实施例3中制备的没食子酸铋金属配合物(GABi)阵列包覆石墨烯材料应用与锂离子电池负极材料的循环性能曲线;
图7为本申请的具体实施例5中制备的鞣花酸锡金属配合物(EASn)阵列包覆石墨烯材料的XRD图;
具体实施方式
下面用具体的特定例子来描述本发明的实现,从该说明书中所公开的内容,本领域的技术人员可以容易地理解本发明的其它优势和效力。还可以通过其他不同的特定实施例来实现或者应用本发明,并且在不偏离本发明的精神的情况下,根据不同的视角和应用,还可以对该描述中的每个细节进行各种修改或者变化。
实施例1
制备没食子酸锌金属配合物(GAZn)阵列包覆石墨烯材料:
(1)称取氧化石墨烯0.051g于500mL烧瓶中,加入350mL去离子水稀释,超声分散0.5h;
(2)称取无水没食子酸0.17g和无水醋酸锌0.44g加入上述氧化石墨烯分散液中,在室温下反应12h;
(3)转移烧瓶中的固体产物,用去离子水多次洗涤,抽滤冷冻干燥得到没食子酸锌金属配合物阵列包覆石墨烯材料。
一种本发明没食子酸锌金属配合物阵列包覆石墨烯材料的应用,用于制备锂离子电池,电池包含上述复合材料的锂离子电池负极材料和电解液,所述电解液含有LiPF6、非水溶剂碳酸乙烯酯EC、碳酸二甲酯DMC、碳酸甲乙酯EMC和氟代碳酸乙烯酯FEC。
将没食子酸锌金属配合物阵列包覆石墨烯材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1并且电解质LiPF6浓度为1.0mol/L的混合液为电解液,在氩气气氛下组装成锂离子电池。
本实施例所得复合材料XRD图如图1所示,可以证明复合材料成功合成。本实例所得复合材料SEM图如图2所示,多酚金属配合物陈列包覆在氧化石墨烯表面,实现了材料的有机复合,石墨烯作为基底可以有效提高材料的导电性,与阵列生长的多酚金属配合物紧密结合,有利于稳定的循环和快速的离子扩散。
本实施例所制备的金属多酚阵列包覆石墨烯材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1的质量比混合均匀,制成负极浆料,涂覆在铜箔上,放入真空烘箱中以不低于100℃下干燥至少12h,即得复合负极极片。以所述复合负极极片作为工作电极,以金属锂片为对电极,采用EC:DMC:EMC体积比为1:1:1,含5%FEC添加剂,并且电解质浓度为1.0mol/L的混合液为电解液,在氩气气氛的手套箱中组装成纽扣电池,并测试其电化学性能。如图3所示,在0.2A/g电流密度下,电池循环100周后,比容量仍保持在553mAh/g。
实施例2
制备不同比例没食子酸锌金属配合物(GAZn)阵列包覆石墨烯材料:
(1)分别称取氧化石墨烯0.017g和0.034g于两个500mL烧瓶中,分别加入350mL去离子水稀释,超声分散0.5h;
(2)称取无水没食子酸0.17g和无水醋酸锌0.44g加入上述两个不同浓度的氧化石墨烯分散液中,在室温下反应12h;
(3)转移烧瓶中的固体产物,用去离子水多次洗涤,抽滤冷冻干燥得到不同比例没食子酸锌金属配合物阵列包覆石墨烯材料(分别为10%氧化石墨烯和20%氧化石墨烯)。
一种本发明没食子酸锌金属配合物阵列包覆石墨烯材料的应用,用于制备锂离子电池,电池包含上述复合材料的锂离子电池负极材料和电解液,所述电解液含有LiPF6、非水溶剂碳酸乙烯酯EC、碳酸二甲酯DMC、碳酸甲乙酯EMC和氟代碳酸乙烯酯FEC。
将没食子酸锌金属配合物阵列包覆石墨烯材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1并且电解质LiPF6浓度为1.0mol/L的混合液为电解液,在氩气气氛下组装成锂离子电池。
本实施例所得复合材料XRD图如图4所示,可以证明复合材料成功合成。
实施例3
制备没食子酸铋金属配合物(GABi)阵列包覆材料:
(1)称取氧化石墨烯0.051g于500mL烧瓶中,加入350mL去离子水稀释,超声分散0.5h;
(2)称取无水没食子酸0.17g溶于上述氧化石墨烯分散液,五水合硝酸铋0.48g溶于50mL的N,N-二甲基甲酰胺,将上述两种溶液混合,在室温下反应12h;
(3)转移烧瓶中的固体产物,用去离子水多次洗涤,抽滤冷冻干燥得到没食子酸铋金属配合物阵列包覆石墨烯材料。
一种本发明没食子酸铋金属配合物阵列包覆石墨烯材料的应用,用于制备锂离子电池,电池包含上述复合材料的锂离子电池负极材料和电解液,所述电解液含有LiPF6、非水溶剂碳酸乙烯酯EC、碳酸二甲酯DMC、碳酸甲乙酯EMC和氟代碳酸乙烯酯FEC。
将没食子酸铋金属配合物阵列包覆石墨烯材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1并且电解质LiPF6浓度为1.0mol/L的混合液为电解液,在氩气气氛下组装成锂离子电池。
本实施例所得复合材料XRD图如图4所示,可以证明复合材料成功合成。
本实施例所制备的金属多酚阵列包覆石墨烯材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1的质量比混合均匀,制成负极浆料,涂覆在铜箔上,放入真空烘箱中以不低于100℃下干燥至少12h,即得复合负极极片。以所述复合负极极片作为工作电极,以金属锂片为对电极,采用EC:DMC:EMC体积比为1:1:1,含5%FEC添加剂,并且电解质浓度为1.0mol/L的混合液为电解液,在氩气气氛的手套箱中组装成纽扣电池,并测试其电化学性能。如图5所示,在0.2A/g电流密度下,电池循环100周后,比容量仍保持在487mAh/g。
实施例4
制备单宁酸锌金属配合物(TAZn)阵列包覆材料:
(1)称取氧化石墨烯0.51g于500mL烧瓶中,加入350mL去离子水稀释,超声分散0.5h;
(2)称取单宁酸1.701g和无水醋酸锌4.4g加入上述氧化石墨烯分散液中,在室温下反应12h;
(3)转移烧瓶中的固体产物,用去离子水多次洗涤,抽滤冷冻干燥得到单宁酸锌金属配合物阵列包覆石墨烯材料。
实施例5
制备鞣花酸锡金属配合物(EASn)阵列包覆材料:
(1)称取氧化石墨烯0.09g于500mL烧瓶中,加入350mL去离子水稀释,超声分散0.5h;
(2)称取鞣花酸0.302g和硫酸亚锡0.859g加入上述氧化石墨烯分散液中,在80℃下反应12h;
(3)转移烧瓶中的固体产物,用去离子水多次洗涤,抽滤冷冻干燥得到鞣花酸锡金属配合物阵列包覆石墨烯材料。
以上所述实施例仅表达本发明的实施方式,但并不能因此而理解为对本发明专利的范围的限制,应当指出,对于本领域的技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些均属于本发明的保护范围。
Claims (11)
1.一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,包括以下制备步骤:
S1:称取一定质量的氧化石墨烯于去离子水中均匀分散;
S2:称取多酚前驱体和金属弱酸盐加入步骤(1)稀释分散后的溶液中,搅拌得到金属多酚配合物阵列包覆石墨烯的粗产品;
S2:将上述所得粗产品用去离子水多次洗涤,抽滤,冷冻干燥得到多酚金属复合材料。
2.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S1和S2中反应温度范围为-20-200℃。
3.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S1和S2中反应的气氛环境可以为空气、氮气或氩气等惰性气体。
4.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S1中的氧化石墨烯选择粉末或浓缩液进行分散稀释。
5.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S2中的多酚前驱体选自天然或人工合成的多羟基类化合物,包括但不仅限于没食子酸、焦性没食子酸、均苯三酚酸等酚酸,以及槲皮素、山柰酚、儿茶素、单宁酸等类黄酮类和多酚酰胺等多酚种类中的一种或几种。
6.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S2中的金属弱酸盐包括但不仅限于乙酸盐、丙酸盐、碳酸盐、次氯酸盐、柠檬酸盐、硼酸盐、偏硅酸盐、苯酚盐等弱酸盐中的一种或几种。
7.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S2中金属弱酸盐中的金属包括但不仅限于锂、钠、钾、钛、钒、铬、锰、铁、钴、镍、锌、铜、铝、镓、锆、钼、钌、铑、镉、铟、铪、铼、锡等中的一种或几种。
8.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S2中反应时间控制在0.5-24h。
9.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的制备方法,其特征在于,步骤S2中多酚前驱体与金属弱酸盐的摩尔比为1:10-10:1。
10.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的应用,其特征在于,用于制备锂离子电池,电池包含基于上述复合材料的锂离子电池负极材料和电解液,所述电解液含有锂盐LiPF6、LiClO4和LiTFSI中的至少一种,所述电解液含有添加剂碳酸亚乙烯酯、氟代碳酸乙烯酯和碳酸乙烯亚乙酯中的至少一种,所述电解液还含有选自非水溶剂碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸丙烯酯、二甘醇二甲醚、乙二醇二甲醚和碳酸二甲酯中的至少一种。
11.根据专利要求1所述的一种金属多酚阵列包覆石墨烯的应用,其特征在于,
将复合材料作为负极活性物质,与聚偏氟乙烯和导电剂按照8:1:1的质量比混合均匀,制成负极浆料,涂覆在铜箔上,放入真空烘箱中以不低于100℃下干燥至少12h,即得复合负极极片,在惰性气体气氛下组装成锂离子电池。
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