CN111900349B - 一种锌掺杂混合型过渡金属硫化物电极材料及其制备方法 - Google Patents
一种锌掺杂混合型过渡金属硫化物电极材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种锌掺杂混合型过渡金属硫化物电极材料及其制备方法,该制备方法为:将六水合硝酸钴、六水合硝酸镍和尿素加入到去离子水中,装在水热釜中,投入去离子水超声处理后的碳布进行水热反应并多次冲洗烘干;将六水合硝酸钴和六水合硝酸锌加入到甲醇溶液中得到溶液A,将二甲基咪唑加入到甲醇溶液中得到溶液B,将冲洗烘干的产物浸入溶液A中,将溶液B滴入溶液A,取出碳布冲洗烘干;然后与硫代乙酰胺进行硫化得到电极材料。制备的电极材料微观形貌上大小均一的镍钴硫化物颗粒像糖葫芦状串联在镍钴纳米线阵列上,并且具有较高的比电容、优良的倍率性能和循环稳定性。
Description
技术领域
本发明属于锌离子电池电极材料的制备领域,具体涉及一种锌掺杂混合型过渡金属硫化物电极材料及其制备方法。
背景技术
过渡金属硫化物由于结构多样性、电化学活性强,且相较于氧化物和氢氧化物具有更高的电子传导性,作为电极材料可以得到高的比电容值和能量密度,近年来已被报道用作水系锌离子电池正极材料。混合过渡金属硫化物如NiCo2S4,CoFe2S4,ZnCo2S4,MnCo2S4等,由于其复杂的化学组成以及两种或多种金属元素之间的协同效应,通常具有很高的理论比容量以及良好的循环稳定性,同时导电性是氧化物的百倍。其中,镍钴硫化物凭借其低成本、高理论比电容值以及原材料来源丰富等优点逐渐成为十分具有前景的超级电容器电极材料。然而,镍钴硫化物的循环和倍率性能仍有待进一步提高。
金属有机框架化合物(MOFs)是一类通过有机配体把金属离子或金属簇连接在一起,自组装形成的具有周期性网络结构和多孔特征的配位聚合物。MOFs作为一种新型多孔材料,具有超高的比表面积、丰富的孔道结构以及种类的多样性,在众多领域都有着重要的应用。由于MOFs中含有丰富的过渡金属离子,因此可以在特定的转化条件下获得混合过渡金属化合物。通过MOFs前驱物衍生制得的过渡金属化合物结构合理,通常具有丰富的孔隙,这种多孔结构有利于促进电解液的充分渗透,加快离子和电子的传输。此外,该方法合成简单,可控性强,如果选择集多种过渡金属于一体的MOFs作为前躯体,有望得到混合过渡金属化合物。因此,利用MOFs前驱物衍生制备的镍钴硫化物作为锌离子电池的电极材料具有更加优异的电化学性能。
发明内容
本发明的目的在于提供一种锌掺杂混合型过渡金属硫化物电极材料及其制备方法。为了进一步提高混合型过渡金属硫化物电极材料的电化学性能,在生长ZIF-67过程中添加适量的Zn,有助于得到高质量负载的产物,生长得到的类似糖葫芦状的结构有效提高了电极材料的利用率并提高了比容量,从而提高电化学性能。制备的电极材料微观形貌上大小均一的镍钴硫化物颗粒像糖葫芦状串联在镍钴纳米线阵列上,并且具有较高的比容量、优良的倍率性能和循环稳定性。
为实现上述目的,本发明采用如下技术方案:
一种锌掺杂混合型过渡金属硫化物电极材料及其制备方法,包括如下步骤:
(1)将碳布用去离子水进行超声处理,将定量的六水合硝酸钴、六水合硝酸镍和尿素加入到去离子水中,超声溶解后装在水热釜中,投入一片先前准备好的碳布进行水热反应。自然冷却后,取出碳布多次冲洗烘干;
(2)将定量的六水合硝酸钴和六水合硝酸锌加入到甲醇溶液中得到溶液A,将定量的二甲基咪唑加入到甲醇溶液中得到溶液B,分别超声溶解,将步骤(1)产物浸入溶液A中,并在磁力搅拌器上缓慢搅拌。接着用吸管将溶液B缓慢匀速滴入溶液A,滴定完成后继续搅拌混合液。最后取出碳布用乙醇多次冲洗烘干;
(3)将定量的硫代乙酰胺加入到离子水中,超声溶解后装在水热釜中,投入一片步骤(2)产物进行水热反应。自然冷却后,取出碳布烘干,即制备得到锌掺杂混合型过渡金属硫化物电极材料。上述制备方法具体为:
1)将清洁的碳布用去离子水进行超声处理约30~90分钟。称取0.5~5.0 g六水合硝酸钴、0.3~4.0 g六水合硝酸镍和0.2~2.0 g尿素加入到20~100 ml去离子水,超声溶解后装在水热釜中,投入一片先前准备好的碳布,尽量使碳布不贴壁,在80~250 ℃下水热反应1~10小时。自然冷却后,取出碳布用乙醇多次冲洗烘干;
2)称取0.1~1.0 g六水合硝酸钴、0.02~0.15 g六水合硝酸锌,加入到10~50 ml甲醇中,配置得到溶液A,称取0.5~2.0 g二甲基咪唑加入到10~50 ml甲醇中配置得到溶液B,分别超声溶解,将步骤(1)产物浸入溶液A中,并在磁力搅拌器上缓慢搅拌10~60分钟,接着用吸管将溶液B缓慢匀速滴入溶液A,用时5~30分钟,滴定完成后继续搅拌30~120分钟。最后取出碳布用乙醇多次冲洗烘干;
3)称取50~200 mg硫代乙酰胺放入10~100 ml去离子水,超声溶解搅拌后装在水热釜中,投入一片步骤(2)产物在80~250 ℃下水热反应1~12小时。自然冷却后,取出碳布用乙醇多次冲洗烘干,即制备得到锌掺杂混合型过渡金属硫化物电极材料。
本发明所制得的电极材料,镍钴硫化物颗粒像糖葫芦状串联在镍钴纳米线阵列上,大小均一。在生长ZIF-67过程中添加适量的Zn,得到了高质量负载的产物,生长得到的类似糖葫芦状的结构有效提高了活性材料的利用率并提高了比容量,从而提高了电化学性能。
本发明的显著优点在于:
(1)本发明通过MOFs前驱物衍生制备的镍钴硫化物纳米阵列@碳布结构合理,具有丰富的孔隙,有利于促进电解液的充分渗透,加快离子和电子的传输。制备工艺简单,操作可控性强。
(2)以碳布作为基底,制备工艺简单,操作可控性强。
(3)生长ZIF-67过程中添加适量的Zn,可以得到高质量负载的产物,生长得到的类似糖葫芦状的结构,有效提高了活性材料的利用率并提高了比容量,从而提高电化学性能。
附图说明
图1为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的XRD衍射图谱;
图2为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的扫描电镜图;
图3为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的循环伏安曲线图;
图4为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的恒流充放电曲线图;
图5为对比例1制得的混合型过渡金属硫化物电极材料不同放大倍数的扫描电镜图;
图6为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料与对比例1制得的混合型过渡金属硫化物电极材料电化学性能对比图。
具体实施方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并不限于下列实施例。
实施例1
一种锌掺杂混合型过渡金属硫化物电极材料的制备方法,具体步骤为:
(1)将碳布用去离子水进行超声处理约30分钟。称取0.5 g六水合硝酸钴、0.5 g六水合硝酸镍和0.2 g尿素加入到30 ml去离子水,超声溶解后装在水热釜中,投入一片先前准备好的碳布,在100 ℃下水热反应3小时。自然冷却后,取出碳布多次冲洗烘干;
(2)称取0.3 g六水合硝酸钴、0.08 g六水合硝酸锌,加入到30 ml甲醇得到溶液A,称取0.7 g二甲基咪唑加入到30 ml甲醇中得到溶液B,分别超声溶解,将步骤(1)产物浸入溶液A中,并在磁力搅拌器上缓慢搅拌30分钟,接着用吸管将溶液B缓慢匀速滴入溶液A,用时10分钟,滴定完成后继续搅拌60分钟。最后取出碳布用乙醇多次冲洗烘干;
(3)称取50 mg硫代乙酰胺放入40 ml去离子水,超声溶解搅拌后装在水热釜中,投入一片步骤(2)产物在100 ℃下水热反应3小时。自然冷却后,取出碳布冲洗烘干得到产物。
图2为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的扫描电镜图;从图中可以看出镍钴硫化物纳米阵列@碳布像糖葫芦状串联在镍钴纳米线阵列上,大小均一,粒径尺寸在100-130 nm;图3为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的循环伏安曲线图;从图中可以看出一对强氧化还原峰,曲线呈现出较大的积分面积;图4为实施例1制得的锌掺杂混合型过渡金属硫化物电极材料的恒流充放电曲线图;从图中可以看出一对较高的充放电平台。
实施例2
一种锌掺杂混合型过渡金属硫化物电极材料的制备方法,具体步骤为:
(1)将碳布用去离子水进行超声处理约60分钟。称取1.5 g六水合硝酸钴、0.8 g六水合硝酸镍和0.5 g尿素加入到70 ml去离子水,超声溶解后装在水热釜中,投入一片先前准备好的碳布,在180 ℃下水热反应6小时。自然冷却后,取出碳布多次冲洗烘干;
(2)称取0.5 g六水合硝酸钴、0.15 g六水合硝酸锌,加入到50 ml甲醇得到溶液A,称取1.2 g二甲基咪唑加入到50 ml甲醇中得到溶液B,分别超声溶解,将步骤(1)产物浸入溶液A中,并在磁力搅拌器上缓慢搅拌30分钟,接着用吸管将溶液B缓慢匀速滴入溶液A,用时10分钟,滴定完成后继续搅拌30分钟。最后取出碳布用乙醇多次冲洗烘干;
(3)称取100 mg硫代乙酰胺放入50 ml去离子水,超声溶解搅拌后装在水热釜中,投入一片步骤(2)产物在180 ℃下水热反应8小时。自然冷却后,取出碳布冲洗烘干得到产物。
电化学性能测试
将以上方法制备的锌掺杂混合型过渡金属硫化物电极材料进行电化学性能表征,其中活性材料电极为工作电极,商业Zn片作为负极,2 M的KOH作为电解液,测得实施例1制得的电极材料两电极体系下在0.01 mA cm-2的电流密度下面积容量可达1.07 mAh cm-2,并且有一对较高的充放电平台,具有较高的比容量。
对比例1
制备混合型过渡金属硫化物电极材料的方法:
称取0.3 g六水合硝酸钴,加入到30 ml甲醇得到溶液A,称取0.7 g二甲基咪唑加入到30 ml甲醇中得到溶液B,分别超声溶解,将实施例1中步骤(1)产物浸入溶液A中,并在磁力搅拌器上缓慢搅拌30分钟,接着用吸管将溶液B缓慢匀速滴入溶液A,用时10分钟,滴定完成后继续搅拌60分钟。最后取出碳布用乙醇多次冲洗烘干,记步骤(2);
再称取50 mg硫代乙酰胺放入40 ml去离子水,超声溶解搅拌后装在水热釜中,投入一片步骤(2)产物在100 ℃下水热反应3小时。自然冷却后,取出碳布冲洗烘干得到产物。
图5为对比例1制得的混合型过渡金属硫化物电极材料不同放大倍数的扫描电镜图。从图中可知,不添加Zn 制备得到的电极材料所生长的ZIF-67颗粒覆盖或者散落在Ni-Co 前驱物纳米线阵列表面上,分布杂乱。
将以上方法制备的混合型过渡金属硫化物电极材料按照上述同样的方法进行电化学性能测试,测得对比例1制得的电极材料在0.01 mA cm-2的电流密度下,电极材料的面积容量为0.14 mAh cm-2,而同等条件下,实施例1的面积容量为1.07 mAh cm-2,具有更大的循环伏安(CV)面积。通过对比表明,添加Zn生长得到的类似糖葫芦状的结构,有效提高了电极材料的面积比容量。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (1)
1.一种锌掺杂混合型过渡金属硫化物电极材料,其特征在于:其制备方法包括以下步骤:
(1)将清洁的碳布用去离子水进行超声处理,将六水合硝酸钴、六水合硝酸镍和尿素加入到去离子水中,超声溶解后装在水热釜中,投入超声处理后的碳布进行水热反应,自然冷却后,取出碳布用乙醇多次冲洗烘干;
(2)将六水合硝酸钴和六水合硝酸锌加入到甲醇溶液中得到溶液A,将二甲基咪唑加入到甲醇溶液中得到溶液B,分别超声溶解,将步骤(1)烘干后的碳布浸入溶液A中,并进行缓慢的磁力搅拌,接着将溶液B缓慢匀速滴入溶液A,滴定完成后继续搅拌混合液,最后取出碳布用乙醇多次冲洗烘干;
(3)将硫代乙酰胺加入到去离子水中,超声溶解后装在水热釜中,投入步骤(2)烘干后的碳布进行水热反应,自然冷却后,取出碳布用乙醇多次冲洗烘干,即制备得到锌掺杂混合型过渡金属硫化物电极材料,其用于锌离子电池的电极材料;
步骤(1)中所述六水合硝酸钴的质量为0.5~5.0 g,六水合硝酸镍的质量为0.3~4.0 g,尿素质量为0.2~2.0 g,用于溶解的去离子水体积为20~100 ml;步骤(1)中所述水热反应温度为80~250 ℃,反应时间为1~10小时;步骤(2)中所述溶液A中六水合硝酸钴质量为0.1~1.0 g,六水合硝酸锌质量为0.02~0.15 g,甲醇体积为10~50 ml;步骤(2)中所述溶液B中二甲基咪唑质量为0.5~2.0 g,甲醇体积为10~50 ml;步骤(3)中所述硫代乙酰胺的质量为50~200 mg,去离子水体积为10~100 ml;步骤(3)中所述水热反应温度为80~250 ℃,反应时间为1~12小时。
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