CN110846888B - 一种硫掺杂二氧化钛纳米纤维的制备方法 - Google Patents
一种硫掺杂二氧化钛纳米纤维的制备方法 Download PDFInfo
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Abstract
本发明公开了一种硫掺杂二氧化钛纳米纤维的制备方法，本发明中以钛酸四丁酯为主要原料溶于N,N‑二甲基甲酰胺、乙醇和乙酸的混合溶剂中，加入聚乙烯吡咯烷酮，得到前驱体混合物溶液；在一定的电压与流率下，利用同轴技术进行静电纺丝；将静电纺丝产品进行烧结得到TiO2纳米管，将TiO2纳米管与升华硫混合进行熔融渗硫，将渗硫后的TiO2纳米管加入到钛酸四丁酯的乙醇溶液中，加入氨水使钛酸四丁酯水解产生TiO2包覆在硫单质和TiO2纳米管的外部，从而形成硫掺杂二氧化钛纳米纤维。本发明制得的硫掺杂二氧化钛纳米纤维具有良好的电化学性能，在整个制备过程中，操作简单，原料成本低，设备投资少，适合批量生产。
Description
技术领域
本发明属于材料化学领域，具体涉及到一种硫掺杂二氧化钛纳米纤维的制备方法。
背景技术
锂硫电池因其理论能量密度高、原料廉价、环境友好等优点，被认为是最具发展潜力的新型高性能电池体系之一。虽然裡硫电池的研究已经有几十年的历史，并且在近年间取得了显著的研究进展，但由于单质硫和金属锂组成的电化学体系本身存在的一些特殊反应性质，以及多硫化物与电解液的匹配问题，导致锂硫电池距离真正实用化还有不小距离。目前，锂硫电池的开发应用仍面临诸多技术问题(N.Jayaprakash等人，Angew Chem IntEdit,50(2011)5904-5908；K.T.Lee等人，Advanced Energy Materials,2(2012)1490-1496)，具体为：1)硫自身导电性极差，25℃时其电导率仅为5×10-30S/cm，属于典型的电子和离子绝缘体；放电产物硫化锂也是绝缘体，而且硫化锂不能全部可逆地转化为硫，很容易失去电化学活性；2)单质硫在充放电过程中生成的中间产物多硫化物易溶解于电解液中，从而造成了部分电极活性物质的损失，同时，多硫化物的大量溶解还会引起电解液粘度增大，使锂离子在电解液中的迁移阻力增大，电解液的离子导电性变差，影响了硫电极的电极动力学过程；3)溶于电解液的长链多硫化物在浓度梯度作用下能够透过隔膜扩散到负极，在负极表面与金属锂发生自放电反应，被还原生成短链多硫化物，短链多硫化物又会扩散回到正极重新被氧化生成长链多硫化物，这种多硫化物在正负极之间来回穿梭自放电的现象是锂硫电池特有的现象，即所谓的“穿梭效应”，穿梭效应会影响电池正常充电的完成，降低电池的库伦效率。此外，长链的多硫化物在负极表面反应会引起负极表面腐蚀现象，影响锂电极的电化学性能；4)单质硫的密度(2.07g/cm3)和放电产物硫化锂的密度(1.66g/cm3)相差较大，充放电过程中材料的体积会发生明显变化，而反应中负极会因为锂被消耗而体积缩减。正负极材料体积反复发生变化会一定程度上破坏电极的物理结构，产生微裂纹，最终可能出现粉末化现象而导致电极失效。
为了解决锂硫电池目前存在的诸多问题和挑战，研究者们从正极方面进行了深入研究。正极材料一直是电池性能研究中最为关键的部分。对于含硫正极材料，研究主要集中在制备硫基复合材料。复合材料中引入的基质材料要满足二个基本要求：一是基质材料本身要具有优秀的导电性，弥补硫的绝缘性；二是通过一定的复合制备方法可以使硫单质在基质材料上均匀分散，以提高活性物质的利用率；三是引入的基质材料要对硫及多硫化物起到容纳和限域作用，可以抑制穿梭效应。而纳米过渡金属氧化物材料与单质硫复合也是锂硫电池正极材料的一个重要研究方向。过渡金属氧化物作为添加剂直接添加到单质硫中，与硫制备成复合材料后在一定程度上可以起到提高硫导电性、抑制穿梭效应、提高循环性能的改性作用，近来，过渡金属氧化物被作为壳层包覆在硫或者其他硫基复合材料表面，起到了很好的改性效果。为了解决硫正极活性物质利用率低和循环性能差等问题，我们先用静电纺丝法制备了TiO2纳米管，然后将硫单质渗入到TiO2纳米管的内部和外部，最后用TiO2包覆住TiO2纳米管外部的硫单质，从而形成一个多层纤维结构。
发明内容
本发明是为了解决硫正极活性物质利用率低和循环性能差等问题，进一步提升提高硫导电性、抑制穿梭效应，提供了一种硫掺杂二氧化钛纳米纤维的制备方法。
本发明为解决上述技术问题所采取的技术方案为：一种硫掺杂二氧化钛纳米纤维的制备方法，所述制备方法具体包括以下步骤：
(1)将适量的钛酸四丁酯(C16H36O4Ti)溶于DMF、乙醇和乙酸的体积比为2:2:1的混合溶剂中，添加适量的PVP，搅拌3h，形成溶液A；
(2)将PVP溶于N,N’-二甲基甲酰胺(DMF)、乙醇和乙酸的体积比为2:2:1的混合溶剂，搅拌3h，形成溶液B；
(3)将两种溶液A和B在17～19kV的电压下，接收距离为15～20cm，流率为0.6mL h-1的条件下，进行同轴静电纺丝，溶液B为内层溶液，溶液A为外层溶液；
(4)将得到的静电纺丝产品置于烘箱中，100℃下干燥12h；
(5)将干燥后的静电纺丝产品转移到马弗炉中，在750～900℃下烧结5h，得到TiO2纳米管；
(6)将TiO2纳米管与升华硫以质量比为2:3的比例混合，放入封闭的容器中，在155℃下进行熔融渗硫；
(7)将渗硫后的TiO2纳米管加入到钛酸四丁酯的乙醇溶液中，滴加氨水使钛酸四丁酯水解产生TiO2包覆在硫单质和TiO2纳米管的外部，得到所述的一种硫掺杂二氧化钛纳米纤维；
所述DMF为N,N-二甲基甲酰胺；
所述为PVP为K-120型聚乙烯吡咯烷酮；
所述钛酸四丁酯与PVP在溶液A中的质量比为1:1；
所述反应的溶剂、试剂或原料均为化学纯。
与现有技术相比，本发明合成的硫掺杂二氧化钛纳米纤维的特点如下：
采用了静电纺丝技术，结合熔融渗硫以及水解化学沉积法，合成的材料具有管状、多层纳米纤维结构，材料的粒径均匀、稳定性高；本发明制备的硫掺杂二氧化钛纳米纤维作为锂电池正极材料首次放电比容量为957.9mAh g-1。
附图说明
图1是实施例1制得的纳米纤维的XRD图；
图2是实施例1制得的纳米纤维的SEM图；
图3是实施例1制得的纳米纤维作为锂离子电池正极材料，在200mA g-1的电流密度下的充放电循环性能图。
具体实施方式
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合，以下结合实施例对本发明作进一步详细描述。
实施例1
将2.0g钛酸四丁酯(C16H36O4Ti)溶于12mL的DMF、12mL的乙醇和6.0mL的乙酸的混合溶剂中，添加2.0g PVP，搅拌3h，形成溶液A；将2.0g PVP溶于12mL的DMF、12mL的乙醇和6.0mL的乙酸的混合溶剂中，搅拌3h，形成溶液B；将两种溶液A和B在17kV的电压，15cm的接收距离和0.6mL h-1的流率下进行同轴静电纺丝，溶液B为内层溶液，溶液A为外层溶液；将得到的静电纺丝产品置于烘箱中，100℃下干燥12h；将干燥后的静电纺丝产品转移到马弗炉中，在750℃下烧结5h，得到TiO2纳米管；将0.2g的TiO2纳米管与0.3g的升华硫混合，放入封闭的容器中，在155℃下进行熔融渗硫；将渗硫后的0.2g TiO2纳米管加入到含有1.0mmol(0.34g)钛酸四丁酯的10mL乙醇溶液中，加入1.0mL氨水，使钛酸四丁酯水解产生TiO2包覆在硫单质和TiO2纳米管的外部，得到所述的一种硫掺杂二氧化钛纳米纤维；将得到的纳米纤维进行X射线粉末衍射分析，与标准卡片比对显示为TiO2和硫衍射峰(图1)；用扫描电子显微镜SEM观察其形貌为纳米纤维状(图2)；将所得到的米纤维作为锂离子电池正极材料，在200mA g-1的电流密度下，测试其充放电循环性能，其首次放电比容量为957.9mAh g-1(图3)。
实施例2
将2.0g钛酸四丁酯(C16H36O4Ti)溶于12mL的DMF、12mL的乙醇和6.0mL的乙酸的混合溶剂中，添加2.0g PVP，搅拌3h，形成溶液A；将2.0g PVP溶于12mL的DMF、12mL的乙醇和6.0mL的乙酸的混合溶剂中，搅拌3h，形成溶液B；将两种溶液A和B在19kV的电压，20cm的接收距离和0.6mL h-1的流率下进行同轴静电纺丝，溶液B为内层溶液，溶液A为外层溶液；将得到的静电纺丝产品置于烘箱中，100℃下干燥12h；将干燥后的静电纺丝产品转移到马弗炉中，在900℃下烧结5h，得到TiO2纳米管；将0.2g的TiO2纳米管与0.3g的升华硫混合，放入封闭的容器中，在155℃下进行熔融渗硫；将渗硫后的0.2g TiO2纳米管加入到含有1.0mmol(0.34g)钛酸四丁酯的10mL乙醇溶液中，加入1.0mL氨水使钛酸四丁酯水解产生TiO2包覆在硫单质和TiO2纳米管的外部，得到所述的一种硫掺杂二氧化钛纳米纤维；用X射线粉末衍射XRD进行组成结构分析测试；用扫描电子显微镜观察形貌，用充放电循环测试系统分析电化学性能。
实施例3
将2.0g钛酸四丁酯(C16H36O4Ti)溶于12mL的DMF、12mL的乙醇和6.0mL的乙酸的混合溶剂中，添加2.0g PVP，搅拌3h，形成溶液A；将2.0g PVP溶于12mL的DMF、12mL的乙醇和6.0mL的乙酸的混合溶剂中，搅拌3h，形成溶液B；将两种溶液A和B在18kV的电压，19cm的接收距离和0.6mL h-1的流率下进行同轴静电纺丝，溶液B为内层溶液，溶液A为外层溶液；将得到的静电纺丝产品置于烘箱中，100℃下干燥12h；将干燥后的静电纺丝产品转移到马弗炉中，在850℃下烧结5h，得到TiO2纳米管；将0.2g的TiO2纳米管与0.3g的升华硫混合，放入封闭的容器中，在155℃下进行熔融渗硫；将渗硫后的0.2g TiO2纳米管加入到含有1.0mmol(0.34g)钛酸四丁酯的10mL乙醇溶液中，加入1.0mL氨水使钛酸四丁酯水解产生TiO2包覆在硫单质和TiO2纳米管的外部，得到所述的一种硫掺杂二氧化钛纳米纤维；用X射线粉末衍射XRD进行组成结构分析测试；用扫描电子显微镜观察形貌，用充放电循环测试系统分析电化学性能。
Claims (1)
1.一种硫掺杂二氧化钛纳米纤维的制备方法，其特征在于，所述制备方法包括以下步骤：
(1)将钛酸四丁酯溶于DMF、乙醇和乙酸的体积比为2:2:1的混合溶剂中，添加PVP，搅拌3h，形成溶液A；
(2)将PVP溶于DMF、乙醇和乙酸的体积比为2:2:1的混合溶剂，搅拌3h，形成溶液B；
(3)将两种溶液A和B在17～19kV的电压下，接收距离为15～20cm，流率为0.6mL h-1的条件下，进行同轴静电纺丝，溶液B为内层溶液，溶液A为外层溶液；
(4)将得到的静电纺丝产品置于烘箱中，100℃下干燥12h；
(5)将干燥后的静电纺丝产品转移到马弗炉中，在750～900℃下烧结5h，得到TiO2纳米管；
(6)将TiO2纳米管与升华硫以质量比为2:3的比例混合，放入封闭的容器中，在155℃下进行熔融渗硫；
(7)将渗硫后的TiO2纳米管加入到钛酸四丁酯的乙醇溶液中，滴加氨水使钛酸四丁酯水解产生TiO2包覆在硫单质和TiO2纳米管的外部，得到所述的一种硫掺杂二氧化钛纳米纤维；
所述硫掺杂二氧化钛纳米纤维作为锂电池正极材料，其首次放电比容量为957.9mAh g-1；
所述DMF为N,N-二甲基甲酰胺；
所述PVP为K-120型聚乙烯吡咯烷酮；
所述钛酸四丁酯与PVP在溶液A中的质量比为1:1；
所述反应的溶剂、试剂或原料均为化学纯。
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