CN105810888B - 一种电化学贮钠的复合电极及其制备方法 - Google Patents
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Abstract
本发明公开了一种电化学贮钠的复合电极及其制备方法,该复合电极用SnCoS4复合纳米晶‑石墨烯复合材料作为电化学贮钠活性物质。其制备步骤是:在氧化石墨烯存在的条件下,通过SnCl4、CoCl2和L‑半胱氨酸的混合溶液在水热条件下的水热反应,制备得到SnCoS4复合纳米晶‑石墨烯的复合材料,将得到的SnCoS4复合纳米晶‑石墨烯的复合材料作为电化学贮钠活性物质,与乙炔黑、羧甲基纤维素的乙醇和水的混合溶液充分搅拌混合调成均匀的糊状物,涂到铜箔上,烘干并滚压得到电化学贮钠的复合电极。该复合电极具有电化学贮钠可逆比容量高,循环性能稳定和显著增强的高倍率充放电特性。
Description
技术领域
本发明涉及一种电化学贮钠复合电极及其制备方法,尤其涉及用SnCoS4复合纳米晶-石墨烯复合材料作为电化学贮钠活性物质的复合电极及其制备方法,属于钠离子电极材料及其在电化学贮钠复合电极应用的技术领域。
背景技术
锂离子电池以其具有高的比容量和长的循环寿命等优点在移动通讯、电动助力车、电动汽车和储能等领域得到了广泛的应用,但是,锂离子电池的大量应用导致锂资源的相对短缺和锂资源原材料的价格不断上涨,如碳酸锂的价格在过去一年已经上涨了2倍左右。与锂资源相比,钠具有更加丰富的资源和价格低廉的优势,因此,最近关于钠离子电池及其电化学贮钠材料和电极的研发引起了人们极大兴趣。SnS2纳米材料具有较高的电化学贮钠容量,在钠离子电池中具有良好的应用前景。但是,由于其较低的电导率和充放电过程中体积较大的变化,导致用SnS2纳米材料制备的电化学贮钠电极在充放电过程中其电化学贮钠容量会快速衰减。硫化钴纳米材料也具有电化学贮钠性能,但是单一的硫化钴纳米材料贮钠容量较低,充放电循环稳定性也较差。
石墨烯具有高的电导率和荷电迁移率、极大的比表面积、良好的柔性和化学稳定性。通过将金属氧化物或硫化物纳米材料与石墨烯复合所制备的复合材料不经具有搞的电化学贮钠容量,并具有增强的充放电循环性能和高倍率充放电特性。如SnS2-石墨烯复合材料,硫化钴-石墨烯复合材料等均显示了比单纯SnS2或硫化钴具有更高的电化学贮钠容量和更稳定的充放电循环性能。但是这些复合材料制备的复合电极的电化学贮钠性能还有进一步改善的空间。
本发明提供了一种电化学贮钠复合电极及其制备方法,该复合电极用SnCoS4复合纳米晶-石墨烯的复合材料为电化学贮钠活性物质。与用SnS2-石墨烯和CoS2-石墨烯复合材料为电化学贮钠活性物质制备的复合电极相比,本发明用SnCoS4复合纳米晶-石墨烯的复合材料为电化学活性物质制备的电化学贮钠复合电极具有更高的电化学贮钠比容量和显著增强的高倍率充放电特性。但是,到目前为止,这种用SnCoS4复合纳米晶-石墨烯的复合材料为电化学贮钠活性物质的复合电极及其制备方法还未见公开报道。
发明内容
本发明的目的在于提供一种电化学贮钠复合电极及其制备方法,该复合电极的电化学贮钠活性物质为SnCoS4复合纳米晶-石墨烯的复合材料,该复合材料是由SnCoS4复合纳米晶负载在石墨烯上形成,其中SnCoS4复合纳米晶与石墨烯的物质的量之比为1:2,复合电极的组分及其质量百分比含量为:SnCoS4复合纳米晶-石墨烯的复合材料为80%,乙炔黑10%,羧甲基纤维素10%。该电化学贮钠复合电极的制备方法的步骤如下:
(1)将计量的SnCl4·5H2O、CoCl2·6H2O和L-半胱氨酸加入到去离子水中,并充分搅拌,得到均匀的混合溶液,溶液中SnCl4与CoCl2的物质的量之比为1:1,L-半胱氨酸的物质的量为SnCl4与CoCl2的物质的量之和的5倍,然后将氧化石墨烯超声分散在去离子水中,得到均匀的悬浮液,在不断搅拌下将氧化石墨烯悬浮液滴加到上述混合溶液中,并继续搅拌2h,氧化石墨烯的物质的量(以碳的物质的量计算)等于SnCl4与CoCl2的物质的量之和的2倍,最后将得到的反应混合物转移到带有聚四氟乙烯内胆的水热反应釜中,密封,在180℃的恒温箱中反应24h,待自然冷却至室温后,将水热得到的沉淀产物离心分离,并用去离子水和无水乙醇充分洗涤,最后在80℃下真空干燥12h后得到SnCoS4复合纳米晶-石墨烯复合材料;
(2)将上述制备得到的SnCoS4复合纳米晶-石墨烯复合材料作为复合电极的电化学贮钠活性物质,与乙炔黑及质量分数10%羧甲基纤维素的乙醇和水的混合溶液(乙醇和水的的体积比为1:1)在搅拌下充分混合调成均匀的糊状物,各组分质量百分比为:SnCoS4复合纳米晶-石墨烯复合材料80%,乙炔黑10%,羧甲基纤维素10%,将该糊状物均匀地涂到作为集流体的铜箔上,干燥,滚压后得到电化学贮钠复合电极。
与现有技术比较,本发明用SnCoS4复合纳米晶-石墨烯的复合材料为电化学贮钠活性物质制备的电化学贮钠复合电极及其制备方法具有以下显著的优点和效果:尽管研究表明,与单纯的SnS2或流化钴纳米材料相比较,用SnS2-石墨烯复合材料和流化钴-石墨烯复合材料为电化学贮钠活性物质制备的复合电极具有更高的电化学贮钠比容量,其电化学贮钠比容量可以达到600-700mAh/g(基于电化学贮钠活性物质的质量),并具有改善的充放电循环稳定性能和改善的高倍率充放电特性,但是其电化学贮钠性能还具有进一步提升的空间。本发明的结果表明,用SnCoS4复合纳米晶-石墨烯的复合材料为电化学贮钠化学物质制备的复合电极比用SnS2-石墨烯复合材料和SnS2-石墨烯复合材料制备的复合电极具有更高的电化学贮钠比容量和显著增强的高倍率充放电特性。其原因是由于:SnS2为典型的层状结构晶体,而CoS2晶体不是层状的,这两种不同结构的晶体在水热溶液中同时产生时,互相存在相互间的干扰,导致生成的SnCoS4与SnS2或CoS2晶体都不相同。这种不同晶体材料在水热溶液中的生长的相互影响导致所得到的负载在石墨烯表面的SnCoS4纳米粒子具有更小的尺寸,进一步还发现石墨烯上负载的SnCoS4复合纳米晶粒子是由更细的纳米晶粒子组成复合纳米晶。这种SnCoS4复合纳米晶与石墨烯复合形成的复合材料作为电化学贮钠活性化学物质制备的复合电极可以显示进一步增强的电化学贮钠性能,尤其是显示了比SnS2-石墨烯和CoS2-石墨烯复合材料复合电极具有更高的电化学贮钠比容量和显著增强的高倍率充放电特性。
附图说明
图1:本发明制备的(a)SnS2/石墨烯复合材料,(b)CoS2/石墨烯复合材料,(c)SnCoS4复合纳米晶-石墨烯复合材料的XRD图;
图2:本发明制备的(a)SnS2/石墨烯复合材料,(b)CoS2/石墨烯复合材料和(c)SnCoS4复合纳米晶-石墨烯复合材料的SEM形貌照片;
图3:本发明制备的(a,b)SnS2/石墨烯复合材料,(c,d)CoS2/石墨烯复合材料和(e,f)SnCoS4复合纳米晶-石墨烯复合材料的TEM/HRTEM照片。
具体实施方式
以下结合实施例进一步说明本发明。
(1)SnCoS4复合纳米晶-石墨烯复合材料的水热法制备:将1.5mmol的SnCl4·5H2O、1.5mmol的CoCl2·6H2O和15.0mmol L-半胱氨酸加入到100mL去离子水中,并充分搅拌形成均匀的混合溶液;将6.0mmol的氧化石墨烯超声分散到60mL去离子水中,得到均匀的悬浮液,在不断搅拌下,将氧化石墨烯的悬浮液滴加到前面的混合溶液中,室温下再搅拌2h;将最后得到的混合反应物转移到200mL带有聚四氟乙烯内胆的水热反应釜中,密封,在180℃的恒温箱中反应24h,待自然冷却至室温后,将沉淀离心分离,并用去离子水和无水乙醇充分洗涤,将得到水热黑色产物在80℃下真空干燥12h后,最后准备的得到SnCoS4复合纳米晶-复合纳米晶石墨烯复合材料;
(2)将上述制备得到的SnCoS4复合纳米晶-石墨烯复合材料作为复合电极的电化学贮钠活性物质,与乙炔黑质量分数为10%羧甲基纤维素的乙醇和水的混合溶液(乙醇和水的的体积比为1:1)在搅拌下充分混合调成均匀的糊状物,各组分质量百分比为:SnCoS4复合纳米晶-石墨烯复合材料80%,乙炔黑10%,羧甲基纤维素10%,将该糊状物均匀地涂到作为集流体的铜箔上,干燥,滚压后得到电化学贮钠复合电极。
对比例:作为对比,用类似的水热方法制备了SnCoS4纳米材料,并以其作为电化学贮钠活性物质制备相应的电化学贮钠电极。
(1)SnCoS4纳米材料及其水热制备:将1.5mmol的SnCl4·5H2O、1.5mmol的CoCl2·6H2O和15.0mmol L-半胱氨酸加入到160mL去离子水中,并充分搅拌形成均匀的混合溶液;将得到的该混合溶液转移到200mL带有聚四氟乙烯内胆的水热反应釜中,密封,在180℃的恒温箱中反应24h,待自然冷却至室温后,将沉淀离心分离,并用去离子水和无水乙醇充分洗涤,将得到水热黑色产物在80℃下真空干燥12h后,最后制备得到SnCoS4纳米材料;
(2)将上述制备得到的SnCoS4纳米材料作为复合电极的电化学贮钠活性物质,与乙炔黑及质量分数为10%羧甲基纤维素的乙醇和水的混合溶液(乙醇和水的的体积比为1:1)在搅拌下充分混合调成均匀的糊状物,各组分质量百分比为:SnCoS4纳米材料80%,乙炔黑10%,羧甲基纤维素10%,将该糊状物均匀地涂到作为集流体的铜箔上,干燥,滚压后得到电化学贮钠复合电极。
对比例:作为对比,用类似的水热方法制备了SnS2/石墨烯复合材料,并用其作为电化学贮钠活性物质制备电化学贮钠复合电极。
(1)SnS2/石墨烯复合材料及其水热制备:将3.0mmol的SnCl4·5H2O和15.0mmol L-半胱氨酸加入到100mL去离子水中,并充分搅拌形成均匀的溶液;将6.0mmol的氧化石墨烯超声分散到60mL去离子水中,得到均匀的悬浮液,在不断搅拌下,将氧化石墨烯的悬浮液滴加到前面的溶液中,室温下再搅拌2h;将最后得到的混合反应物转移到200mL带有聚四氟乙烯内胆的水热反应釜中,密封,在180℃的恒温箱中反应24h,待自然冷却至室温后,将沉淀离心分离,并用去离子水和无水乙醇充分洗涤,将得到水热黑色产物在80℃下真空干燥12h后,最后准备的得到SnS2/石墨烯复合材料;
(2)将上述制备得到的SnS2/石墨烯复合材料作为复合电极的电化学贮钠活性物质,与乙炔黑及质量分数为10%羧甲基纤维素的乙醇和水的混合溶液(乙醇和水的的体积比为1:1)在搅拌下充分混合调成均匀的糊状物,各组分质量百分比为:SnS2/石墨烯复合材料为80%,乙炔黑10%,羧甲基纤维素10%,将该糊状物均匀地涂到作为集流体的铜箔上,干燥,滚压后得到电化学贮钠复合电极。
对比例:作为对比,用类似的水热方法制备了CoS2/石墨烯复合材料,并用其作为电化学贮钠活性物质制备电化学贮钠电极。
(1)CoS2/石墨烯复合材料及其水热制备:将3.0mmol的CoCl2·6H2O和15.0mmol L-半胱氨酸加入到50mL去离子水中,并充分搅拌形成均匀的溶液;将6.0mmol的氧化石墨烯超声分散到60mL去离子水中,得到均匀的悬浮液,在不断搅拌下,将氧化石墨烯的悬浮液滴加到前面的溶液中,室温下再搅拌2h;将最后得到的混合反应物转移到200mL带有聚四氟乙烯内胆的水热反应釜中,密封,在180℃的恒温箱中反应24h,待自然冷却至室温后,将沉淀离心分离,并用去离子水和无水乙醇充分洗涤,将得到水热黑色产物在80℃下真空干燥12h后,最后准备CoS2/石墨烯复合材料;
(2)将上述制备得到的CoS2/石墨烯复合材料作为复合电极的电化学贮钠活性物质,与乙炔黑及质量分数为10%羧甲基纤维素的乙醇和水的混合溶液(乙醇和水的的体积比为1:1)在搅拌下充分混合调成均匀的糊状物,各组分质量百分比为:CoS2/石墨烯复合材料为80%,乙炔黑10%,羧甲基纤维素10%,将该糊状物均匀地涂到作为集流体的铜箔上,干燥,滚压后制备得到电化学贮钠复合电极。
用X-射线衍射(XRD),扫描电镜(SEM),透射电镜/高分辨透射电镜(TEM/HRTEM)、元素能谱仪(EDS)和XPS对上述制备得到SnCoS4复合纳米晶-石墨烯复合材料,SnCoS4纳米材料,SnS2-石墨烯复合材料和CoS2-石墨烯复合材料进行表征。
电化学贮钠性能测试:用上述制备得到电化学贮钠复合电极为工作电极,在充满氩气的手套箱中组装成钠离子电池的测试电池,金属钠片为对电极和参比电极,玻璃纤维膜为隔膜,1.0mol/L NaPF6的EC/DMC溶液(体积比1:1)为电解液。室温下的恒电流充放电实验测试和比较上述制备得到的复合电极的电化学贮钠性能,充放电电流在100mA/g或1000mA/g,充放电电压区间为3.0~0.005V。
元素组成分析表明,SnCoS4复合纳米晶-石墨烯复合材料中Sn:Co:S的物质的量之比为1:0.96:3.97,符合SnCoS4;SnS2/石墨烯中Sn:S的物质的量之比为1:1.96,符合SnS2;CoS2/石石墨烯中Co:S的物质的量之比为1:2.03,符合CoS2。
图1的XRD表征结果显示,SnS2/石墨烯复合材料显示了较强的衍射峰,并符合SnS2标准粉末衍射卡片(JCPDS Card No.23-0677),说明复合材料中SnS2为典型的层状结构;CoS2/石墨烯复合材料也显示了较强的衍射峰,并符合CoS2的标准粉末衍射卡片(JCPDSno.41-1471)。SnCoS4/石墨烯复合纳米在2θ=9.32°,17.78°,28.92°,32.56°和51.22°显示了较低强度的衍射峰,其强度大大低于SnS2/石墨烯复合纳米材和CoS2/石墨烯复合纳米材的,说明了负载在石墨烯上的SnCoS4复合纳米晶粒子具有更小的尺寸,另外SnCoS4复合纳米晶-石墨烯复合材料也没有显示属于SnS2层状结构的(001)峰。
图2的SEM形貌表征显示,SnS2/石墨烯复合材料显示片状的SnS2均匀地分散在褶皱的石墨烯纳米片表面;CoS2/石墨烯复合材料显示尺寸约100nm的类似球状的CoS2纳米粒子被包裹或分散在石墨烯纳米片上;SnCoS4复合纳米晶-石墨烯复合材料显示尺寸更小的(约35nm)的SnCoS4复合纳米晶粒子被包裹或分散在石墨烯纳米片。
图3的TEM/HRTEM表征结果显示,在SnS2/石墨烯复合材料中,层状结构的SnS2纳米片均匀的分散在褶皱的石墨烯纳米片表面,其(001)、(100)、(101)面的层间距分别为0.59、0.32和0.27nm,与层状结构的SnS2晶体相符合;在CoS2/石墨烯复合材料中,CoS2纳米粒子分散在石墨烯纳米片上,其(200)、(210)、(311)面的层间距分别为0.27、0.25、0.17nm,与CoS2晶体相符合;在SnCoS4复合纳米晶-石墨烯复合材料中,SnCoS4复合纳米晶粒子具有更细的尺寸,并均匀地分散在石墨烯纳米片中;图3(f)还进一步表明SnCoS4复合纳米晶粒子显示了有更加细小的纳米晶组成的复合纳米晶,其尺寸约为3-6nm。
电化学测试结果显示:
室温下在100mA/g充放电电流密度下,SnCoS4复合纳米晶-石墨烯复合材料制备的复合电极,其电化学贮钠可逆比容量初始达到1020mAh/g,100次循环后,其可逆比容量为1015mAh/g,显示了优异的循环稳定性能;与之相比,SnS2/石墨烯复合材料电极的可逆储锂比容量初始达到650mAh/g,100次循环后为595mAh/g;CoS2/石墨烯复合材料电极的可逆容量初始达到612mAh/g,100次循环后为553mAh/g;;SnCoS4纳米材料的电化学贮钠的可逆比容量初始达到850mAh/g,100次循环后为312mAh/g。电化学测试结果说明:SnCoS4复合纳米晶-石墨烯复合材料制备的复合电极的电化学贮钠可逆比容量均明显高于SnS2/石墨烯、CoS2/石墨烯和SnCoS4制备的电极,并具有优异的充放电循环稳定性能。
在充放电电流密度1000mA/g时,上述电化学贮钠复合电极的充放电倍率特性的测试结果为:SnCoS4复合纳米晶-石墨烯复合材料制备的复合电极的电化学贮钠的倍率特性为852mAh/g;SnS2/石墨烯复合材料制备电极的电化学贮钠的倍率特性为563mAh/g;CoS2/石墨烯复合材料制备电极的电化学贮钠的倍率特性为436mAh/g;SnCoS4制备电极的电化学贮钠的倍率特性为325mAh/g。其测试结果说明:与SnS2/石墨烯、CoS2/石墨烯和SnCoS4制备的电极相比,SnCoS4复合纳米晶-石墨烯复合材料制备的复合电极显示了显著增强的电化学贮钠倍率特性。
因此,电化学测试结果表明:与用SnS2/石墨烯或CoS2/石墨烯复合材料制备的复合电极相比,用SnCoS4复合纳米晶-石墨烯复合材料制备的电化学贮钠复合电极不仅具有更高的电化学贮钠可逆比容量和显著增强的高倍率充放电特性,并具有优异的充放电循环性能。
Claims (2)
1.一种电化学贮钠复合电极,其特征在于,复合电极的电化学贮钠活性物质为SnCoS4复合纳米晶-石墨烯的复合材料,该复合材料是由SnCoS4复合纳米晶负载在石墨烯上形成,其中SnCoS4复合纳米晶与石墨烯的物质的量之比为1∶2,复合电极的组分及其质量百分比含量为:SnCoS4复合纳米晶-石墨烯的复合材料为80%,乙炔黑10%,羧甲基纤维素10%。
2.一种权利要求1所述的电化学贮钠复合电极的制备方法,其特征在于,所述制备方法的步骤如下:
(1)将计量的SnCl4·5H2O、CoCl2·6H2O和L-半胱氨酸加入到去离子水中,并充分搅拌,得到均匀的混合溶液,溶液中SnCl4与CoCl2的物质的量之比为1∶1,L-半胱氨酸的物质的量为SnCl4与CoCl2的物质的量之和的5倍,然后将氧化石墨烯超声分散在去离子水中,得到均匀的悬浮液,在不断搅拌下将氧化石墨烯悬浮液滴加到上述混合溶液中,并继续搅拌2h,氧化石墨烯的物质的量以碳的物质的量计算等于SnCl4与CoCl2的物质的量之和的2倍,最后将得到的反应混合物转移到带有聚四氟乙烯内胆的水热反应釜中,密封,在180℃的恒温箱中反应24h,待自然冷却至室温后,将水热得到的沉淀产物离心分离,并用去离子水和无水乙醇充分洗涤,最后在80℃下真空干燥12h后得到SnCoS4复合纳米晶-石墨烯复合材料;
(2)将上述制备得到的SnCoS4复合纳米晶-石墨烯复合材料作为复合电极的电化学贮钠活性物质,与乙炔黑及羧甲基纤维素的乙醇和水的混合溶液在搅拌下充分混合调成均匀的糊状物,将该糊状物均匀地涂到作为集流体的铜箔上,烘干,并辊 压后得到电化学贮钠复合电极,乙醇和水的体积比为1∶1。
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