CN112382745B - 一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料及其制备方法 - Google Patents
一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料，该材料为PMo10V2@CN‑RGO，其具体的制备步骤如下：A．将多巴胺粉末和氧化石墨烯溶液加入到PMo10V2水溶液中，并将混合物进一步搅拌1小时；B．将所得混合物转移到衬有特氟龙的高压釜中，并在160℃下热处理16小时，冷却至室温后，获得黑色粉末状的PMo10V2@CN‑RGO。本发明通过加入多巴胺聚合，使多金属氧酸盐簇可以均匀地固定在碳载体氧化石墨烯板上，提高了阳极材料的电导率和可加工性，具有极高的机械强度和化学稳定性。本发明的制备方法步骤少，反应条件温和，成本低，产率高。
Description
技术领域
本发明涉及钠金属电池技术领域，具体是一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料及其制备方法。
背景技术
由于可靠且经济地存储电的需求已被确定为广泛领域中的关键因素，电化学储能领域的研究越来越受到社会的重视。钠离子电池是一种很有前途的候选产品，这是由于地壳中钠的含量相对较高，因此其成本较低。然而，当前的阳极材料具有低的活性和较窄的层间间距，这严重限制了SIB的进一步应用。因此，设计和制造层间间距增大，活性位点丰富，电子/离子传递能力快，结构稳定性好的高级阳极材料具有重要意义。
在现有的高级阳极材料中，基于多金属氧酸盐的复合材料在储能领域受到了广泛关注。多金属氧酸盐是一类众所周知的离散的早期过渡金属氧化物纳米团簇，具有无与伦比的通用物理性质化学性质，包括引人入胜的分子和电子结构，化学可调性以及独特的电化学氧化还原行为。由于多金属氧酸盐分子具有复杂的多电子传输特性，因此已被视为电子储存器或海绵，并且是钠离子电池中电极材料的理想选择。但是，多金属氧酸盐的电导率低，电解质的部分降解以及可加工性差，这阻碍了它们作为电极材料的应用。多金属氧酸盐与合适的有机碳基材材料的组合是克服这些缺点的有效策略。多金属氧酸盐/有机碳基材复合材料能实现无机和有机部分的增强的稳定性和协同功能，不仅提供更大的表面积，而且还能大大提高复合材料的导电性，特别是用于氧化石墨烯，具有独特的性能，例如高机械强度和化学稳定性，对电极支架有利。但是，带负电荷的多金属氧酸盐簇很难固定在带负电荷的碳载体氧化石墨烯板上。此外，负载的多金属氧酸盐很容易堆叠在氧化石墨烯上或从氧化石墨烯上剥离，这不可避免地减少了与电解质接触的氧化还原活性位。
发明内容
为解决上述问题，本发明的目的是提供一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料，使多金属氧酸盐簇可以均匀地固定在碳载体氧化石墨烯板上，增加其与电解质接触的氧化还原活性位。本发明的另一个目的是提供一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料的制备方法，该方法步骤少，反应条件温和，成本低，产率高。
为实现上述目的，本发明采用的技术方案是：一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料，该材料为PMo10V2@CN-RGO，由黏附性聚多巴胺的非晶形态和磷钼十钒二多酸分子结合成微球型结构均匀负载在氧化石墨烯中，其具体的制备步骤如下：
A．将多巴胺粉末和氧化石墨烯溶液加入到PMo10V2水溶液中，并将混合物进一步搅拌1小时；
B．将所得混合物转移到衬有特氟龙的高压釜中，并在160℃下热处理16小时，冷却至室温后，获得黑色粉末状的PMo10V2@CN-RGO。
优选地，所述步骤A中的多巴胺粉末的质量为20 mg；所述氧化石墨烯溶液的质量为4.4mg，其浓度为2mg/mL；所述PMo10V2水溶液的浓度为2mM，体积为10mL。
本发明的一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料，通过加入多巴胺聚合，使多金属氧酸盐簇可以均匀地固定在碳载体氧化石墨烯板上，增加其与电解质接触的氧化还原活性位，提高了阳极材料的电导率和可加工性，具有极高的机械强度和化学稳定性。
本发明的一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料的制备方法，该方法步骤少，反应条件温和，成本低，产率高。
附图说明
图1是实施例1制备PMo10V2@CN-RGO的流程图。
图2是实施例1制得的PMo10V2@CN-RGO、PMo10V2@CN、PMo10V2的X-射线粉末衍射图。
图3是实施例1制得的PMo10V2@CN-RGO的扫描电镜图。
图4是实施例1制得的PMo10V2@CN-RGO的小电流50mA g-1图。
具体实施方式
下面结合实施例和附图对本发明作进一步详细说明。
实施例1
按如下步骤制备PMo10V2@CN-RGO：
A．将多巴胺粉末和氧化石墨烯溶液加入到PMo10V2水溶液中，并将混合物进一步搅拌1小时；
B．将所得混合物转移到衬有特氟龙的高压釜中，并在160℃热处理16小时。冷却至室温后，获得黑色粉末状的PMo10V2@CN-RGO。(图1)
如图2所示，PMo10V2的X射线衍射(XRD)图谱中，Keggin型多金属氧酸盐的特征峰，在PMo10V2@CN和PMo10V2@CN-RGO中，出现“面包”形的衍射峰，并且PMo10V2的特征衍射峰不可见，表明粘附性聚多巴胺的非晶形态和PMo10V2分子的均匀分散。
如图3所示，用扫描电子显微镜(SEM)研究了PMo10V2@CN-RGO复合材料的形貌和结构。放大的SEM图像显示，具有均匀微球(PMo10V2@CN)包覆在还原氧化石墨烯中。
将PMo10V2@CN-RGO与乙炔黑、PVDF以7：2：1的比例混合，使用N-甲基吡咯烷酮制备成电极材料浆液均匀涂抹在铜箔上，在100摄氏度下真空干燥12小时。使用新威纽扣电池进行电化学性能测试。该材料在测试的过程中表现出了良好电化学性能，具有较高的可逆容量和优良的循环稳定性。如图4所示，化合物在作为钠离子电池阳极材料时表现出了良好的电化学性能，在50mA/g的电流密度下，在100次循环后放电容量稳定在约258 mAh/g。这表明PMo10V2@CN-RGO在钠离子电池方面具有良好的应用潜力。
Claims (2)
1.一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料，其特征在于，该材料为PMo10V2@CN-RGO，由黏附性聚多巴胺的非晶形态和磷钼十钒二多酸分子结合成微球型结构均匀负载在氧化石墨烯中，其具体的制备步骤如下：
A．将多巴胺粉末和氧化石墨烯溶液加入到PMo10V2水溶液中，并将混合物进一步搅拌1小时；
B．将所得混合物转移到衬有特氟龙的高压釜中，并在160℃下热处理16小时，冷却至室温后，获得黑色粉末状的PMo10V2@CN-RGO。
2.根据权利要求1所述的一种还原氧化石墨烯包覆的多金属氧酸盐基聚多巴胺钠离子电池阳极材料，其特征在于，所述步骤A中的多巴胺粉末的质量为20mg；所述氧化石墨烯溶液的质量为4.4mg，其浓度为2mg/mL；所述PMo10V2水溶液的浓度为2mM，体积为10mL。
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| CN110314671A (zh) * | 2019-07-31 | 2019-10-11 | 东北大学 | 一种磷酸化蛋白富集材料的制备方法及其应用方法 |
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