CN114242982A - 石墨烯包覆二维金属化合物电极材料及其制备方法和应用 - Google Patents
石墨烯包覆二维金属化合物电极材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种石墨烯包覆二维金属化合物电极材料及其制备方法和应用,该方法将金属单质粉末置于真空管式炉中,然后在惰性气体与CX2气体的混合气氛中进行煅烧,煅烧后随炉冷却即得到,其中,所述X选自S、Se、Te中的一种或多种。本发明利用金属单质与CX2型化合物的金属热反应,原位合成了碳包覆二维金属硫化物电极,碳层的存在形式为石墨烯,有效提升了材料的结构稳定性和导电性,从而提高了负极材料的循环稳定性。本发明提供的合成方法仅需一步完成,方法便捷,成本低廉,适合工业化大规模生产使用。
Description
技术领域
本发明涉及锂离子电池材料制备技术领域,特别涉及一种石墨烯包覆二维金属化合物电极材料及其制备方法和应用。
背景技术
锂离子电池作为一种二次储能器件,广泛应用于小型便携式电子产品和电动交通工具,具有极高的应用前景。锂离子电池由正极、负极、隔膜和电解液四大主要原材料构成,其中负极材料是影响锂离子电池容量、循环性能和倍率性能发挥的关键因素之一。当前市场上主流应用的商业石墨负极理论容量仅为372mAh/g,研发具有更高比容量的负极材料是二次电池领域的重要任务。其中,二维金属化合物MX2(M=Mo/W/Sn等,X=S/Se/Te等)独特的层状结构和储锂特性使其可以提供超过600mAh/g的理论比容量,成为一类具有发展前景的新型负极材料。单独的二维金属化合物在电池循环过程中普遍存在着体积膨胀、副产物溶解等问题,导致循环性能不佳,将金属化合物与碳材料复合可以有效缓解上述问题。截止目前,已经有报道采用水热法、化学气相沉积等方法成功合成了具有较高比容量和较稳定的循环性能的相关二维金属化合物/碳材料复合负极材料(如MoS2、WS2、MoSe2等),但目前已报道的方法大多存在制备过程繁琐、产率低、成本高等缺陷,既停留在实验室阶段。
中国专利CN 109671937A公开了一种过渡型金属氧化物/石墨烯复合材料的原位合成方法,其工艺大致为:将可溶性铁盐、可溶性过渡金属盐以及可溶性铈盐于去离子水中溶解混合,得到均匀溶液,向均匀溶液中滴加沉淀剂,陈化后过滤、水洗、烘干,得到过渡金属氢氧化物复合物沉淀;称取石墨和高锰酸钾,混合后加入浓硫酸和磷酸混合酸液中,反应得到灰绿色溶液,冰浴处理后,加入过渡金属氢氧化物复合物沉淀,然后再缓慢加入过氧化氢,搅拌分散后,得到相互包覆生长的过渡型金属氢氧化物/氧化石墨烯的悬浊液,悬浊液经过洗涤、离心、干燥、焙烧后,即得到过渡型金属氧化物/石墨烯复合材料。该专利技术采用原位合成氧化石墨烯的过程中,直接加入过渡金属氢氧化物的复合物,得到具有多孔结构的过渡型金属氧化物/石墨烯复合材料,比表面积达到100-200m2/g,其中,CeO2的加入有利于纳米棒的生成,石墨烯均匀分散在产物颗粒缝隙之间,这种结构能够缓冲金属氧化物在充放电循环过程中的体积膨胀效应,并提高电极反应动力学性能。然而,该专利技术依然存在制备过程繁琐、产率低、成本高等缺陷,无法工业应用。
发明内容
本发明的发明目的在于:针对上述存在的问题,提供一种石墨烯包覆二维金属化合物电极材料及其制备方法和应用,本发明利用金属单质与CX2型化合物的金属热反应,原位合成了碳包覆二维金属硫化物电极,碳层的存在形式为石墨烯,有效提升了材料的结构稳定性和导电性,从而提高了负极材料的循环稳定性,本发明提供的合成方法仅需一步完成,方法便捷,成本低廉,适合工业化大规模生产使用,克服了现有技术所存在的不足。
本发明采用的技术方案如下:一种原位合成石墨烯包覆二维金属化合物电极材料的方法,所述原位合成方法是将金属单质粉末置于真空管式炉中,然后在惰性气体与CX2气体的混合气氛中进行煅烧,煅烧后随炉冷却即得到,其中,所述X选自S、Se、Te中的一种或多种。
进一步,所述金属单质为Mo、W、Sn等中的一种或多种,不限于前三种金属单质。
进一步,煅烧温度为600-1000℃,煅烧时间为4-6h。
进一步,煅烧时,升温速率为2-6℃/min。
进一步,所述惰性气体为氩气,氩气与CX2的体积比为100:1-10。体积比最好在此范围内,如果CX2的体积占比过低,则反应时间较长且转换不彻底,反之,如果CX2的体积占比过高,则CS2浪费较多,成本变高,污染环境。
作为优选,所述金属单质为Mo,所述CX2为CS2。
本发明还包括一种石墨烯包覆二维金属化合物电极材料,所述电极材料通过上述方法制备得到。
进一步,所述电极材料的内层为层状金属化合物,外层为石墨烯。
本发明还包括一种锂离子电池,包括负极材料,所述负极材料为上述石墨烯包覆二维金属化合物电极材料。
综上所述,由于采用了上述技术方案,本发明的有益效果是:
1、本发明获得的碳包覆二维金属化合物电极材料,其内层为层状金属化合物,外层为石墨烯,具有良好的结构稳定性和导电性,作为二次离子电池的负极可提供较高的比容量和良好的循环稳定性;
2、本发明利用金属单质与CX2型化合物的金属热反应,原位合成了碳包覆二维金属硫化物电极,碳层的存在形式为石墨烯,有效提升了材料的结构稳定性和导电性,从而提高了负极材料的循环稳定性,本发明提供的合成方法仅需一步完成,方法便捷,成本低廉,适合工业化大规模生产使用,克服了现有技术所存在的不足。
附图说明
图1为本发明实施例1中反应前原始钼粉的SEM形貌图;
图2为本发明实施例1中反应后合成的MoS2@graphene的SEM形貌图;
图3为本发明实施例1中MoS2@graphene的TEM图;
图4为本发明实施例1中MoS2@graphene的XRD图谱;
图5为本发明实施例1 MoS2@graphene与对比例1 MoS2的循环曲线图;
图6为本发明实施例2 SnS@graphene与对比例1 SnS的循环曲线图;
图7为本发明实施例3 WS2@graphene与对比例1 WS2的循环曲线图。
具体实施方式
下面结合附图,对本发明作详细的说明。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
试验主要检测设备
X射线衍射(XRD)测试:X射线衍射仪,仪器型号:Rigaku UltimaIV-185,日本。
扫描电子显微镜(SEM)测试:扫描电子显微镜,仪器型号:FEIQuanta,荷兰。
CR2025钮扣电池的组装方法
将电极材料(实施例1、实施例2、实施例3)、乙炔黑、聚偏氟乙烯(PVDF)按照7:2:1的质量比制成浆料并涂覆在铜箔上、烘干,并用裁片机将烘干后的铜箔裁成直径约为1cm的小圆片用作负极,以金属锂片作为对电极、Celgard2500为隔膜、EC/DMC/EMC 1:1:1(W/W)+1M LiPF6为电解液,在氩气氛围的手套箱内组装成CR2025钮扣电池。
电化学性能测试:
采用LANDCT 2001A测试仪(武汉市蓝电电子有限公司)对组装的电池进行电化学性能测试,测试温度30℃,测试电压范围0.01-3V,测试过程中在100mAh/g下进行充放电。
实施例1
一种制备石墨烯包覆MoS2(M=Mo、X=S)电极材料的方法,包括以下步骤:
S1、称取1g的纳米级钼粉放置于管式炉中,然后通入氩气和CS2的混合气体,其中,CS2的体积占比为8%;
S2、设置加热程序为4℃min的升温速度煅烧钼粉,升温至900℃后保温5h,然后随炉冷却即得到石墨烯包覆的MoS2电极材料。
将得到的石墨烯包覆的MoS2电极材料制成负极极片并制作扣式电池作性能对比。其中,负极组成为:复合负极材料:导电添加剂:粘结剂=70:20:10,采用Celgard2500型号隔膜,对电极为锂金属,EC/DMC/EMC 1:1:1(W/W)+1M LiPF6为电解液。
实施例2
一种制备石墨烯包覆SnS电极材料的方法,包括以下步骤:
S1、称取1g的纳米级锡粉放置于管式炉中,然后通入氩气和CS2的混合气体,其中,CS2的体积占比为2%;
S2、设置加热程序为5℃min的升温速度煅烧锡粉,升温至800℃后保温5h,然后随炉冷却即得到石墨烯包覆的SnS2电极材料。
将上述实施例得到的SnS2@graphene电极材料按照实施例1的方法制成电极片作为负极,以金属锂片作为对电极、Celgard2500为隔膜、1M的碳酸酯溶液为电解液(其中,溶剂为体积比为1:1的碳酸乙烯酯和碳酸二甲酯的混合溶液,溶质为LiPF6),在氩气氛围的手套箱内组装成CR2025钮扣电池。在100mA·g-1充放电电流密度下,测试电池性能。
实施例3
一种制备石墨烯包覆WS2(M=W、X=S)电极材料的方法,包括以下步骤:
S1、称取1g的纳米级钨粉放置于管式炉中,然后通入氩气和CS2的混合气体,其中,CS2的体积占比为5%;
S2、设置加热程序为6℃min的升温速度煅烧钨粉,升温至700℃后保温5h,然后随炉冷却即得到石墨烯包覆的WS2电极材料。
将上述实施例得到的WS2@graphene电极材料按照实施例1的方法制成电极片作为负极,以金属锂片作为对电极、Celgard2500为隔膜、1M的碳酸酯溶液为电解液(其中,溶剂为体积比为1:1的碳酸乙烯酯和碳酸二甲酯的混合溶液,溶质为LiPF6),在氩气氛围的手套箱内组装成CR2025钮扣电池。在100mA·g-1充放电电流密度下,测试电池性能。
对比例1
对于市售MoS2样品(麦克林,≥99.5%,100nm)按照实施实例1所述的方法制成负极极片,组装成纽扣电池,在与实施例1相同的测试条件下进行电池测试。
对比例2
对于市售SnS样品(有融材料,99.99%,325目)按照实施实例1所述的方法制成负极极片,组装成纽扣电池,在与实施例1相同的测试条件下进行电池测试。
对比例3
对于市售WS2样品(阿拉丁,99.9%,2μm)按照实施实例1所述的方法制成负极极片,组装成纽扣电池,在与实施例1相同的测试条件下进行电池测试。
通过SEM测试表明,实施例1所得材料具有层状形貌。通过TEM测试表明,实施例1所得材料片层表面有石墨烯层包覆。通过XRD测试表明,实施例1所得材料的主要成分为二硫化钼。通过电池恒流充放电测试结果表明,100mA/g电流密度条件下,实施例1所述的MoS2@graphene负极材料的首次放电比容量为746.6mAh/g,循环100次后容量保持率达77%。实施例2所述的SnS2@graphene负极材料的首次放电比容量为1194mAh/g,循环20次后容量保持率为42%。实施例3所述的WS2@graphene负极材料的首次放电比容量为707mAh/g,循环20次后容量保持率达88%。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种石墨烯包覆二维金属化合物电极材料的原位合成方法,其特征在于,所述原位合成方法为:将金属单质粉末置于真空管式炉中,然后在惰性气体与CX2气体的混合气氛中进行煅烧,煅烧后随炉冷却即得到,其中,所述X选自S、Se、Te中的一种或多种。
2.如权利要求1所述的石墨烯包覆二维金属化合物电极材料的原位合成方法,其特征在于,所述金属单质为Mo、W、Sn中的一种或多种。
3.如权利要求2所述的石墨烯包覆二维金属化合物电极材料的原位合成方法,其特征在于,煅烧温度为600-1000℃,煅烧时间为4-6h。
4.如权利要求3所述的石墨烯包覆二维金属化合物电极材料的原位合成方法,其特征在于,煅烧时,升温速率为2-6℃/min。
5.如权利要求1所述的石墨烯包覆二维金属化合物电极材料的原位合成方法,其特征在于,所述惰性气体为氩气,氩气与CX2的体积比为100:1-10。
6.如权利要求1所述的石墨烯包覆二维金属化合物电极材料的原位合成方法,其特征在于,所述金属单质为Mo,所述CX2为CS2。
7.一种石墨烯包覆二维金属化合物电极材料,其特征在于,所述电极材料通过上述权利要求1-6任一所述的原位合成方法制备得到。
8.如权利要求7所述的石墨烯包覆二维金属化合物电极材料,其特征在于,所述电极材料的内层为层状金属化合物,外层为石墨烯。
9.一种锂离子电池,包括负极材料,其特征在于,所述负极材料为权利要求8所述的石墨烯包覆二维金属化合物电极材料。
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