CN103155243B - 可充电锂-硫电池电极用石墨烯-硫纳米复合材料 - Google Patents

可充电锂-硫电池电极用石墨烯-硫纳米复合材料 Download PDF

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CN103155243B
CN103155243B CN201180048678.1A CN201180048678A CN103155243B CN 103155243 B CN103155243 B CN 103155243B CN 201180048678 A CN201180048678 A CN 201180048678A CN 103155243 B CN103155243 B CN 103155243B
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graphene
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刘俊
J·P·莱蒙
杨振国
Y·曹
X·李
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Abstract

具有包括石墨烯-硫纳米复合材料的阴极的可充电锂-硫电池可以具有改进的特性。石墨烯-硫纳米复合材料特征为具有吸附至石墨烯片材的硫粒子的石墨烯片材。硫粒子具有小于50nm的平均直径。

Description

可充电锂-硫电池电极用石墨烯-硫纳米复合材料
关于联邦资助的研究或开发的声明
本发明在美国能源部授予的合约号为DE-AC0576RL01830的政府资助下作出。美国政府对本发明享有一定的权利。
优先权
本发明要求2010年10月7日提交的名称为“Graphene-SulfurNanocomposites for Lithium-Sulfur Batteries”的美国临时专利申请第61/390,945号，和2011年2月8日提交的名称为“Graphene-SulfurNanocomposites for Rechargeable Lithium-Sulfur Battery Electrodes”的美国申请第13/023,241号的优先权。
背景技术
高性能电池可以用作供给和储存问题的部分解决方案以及与用清洁替代能源替代化石燃料基能源有关的环境问题的部分解决方案。锂-硫电池由于其高的理论比能密度(2600Wh kg-1)、高的理论比容量(1680mAhg-1)、低的材料成本和低的安全性风险而特别受关注。然而，元素硫的差的导电性、多硫化物中间体的溶解和往复，以及得到的差的循环性能限制了Li-S电池的应用和用途。因此，需要在可逆容量、速率容量（ratecapability）和循环稳定性方面改进的Li-S电池。
发明内容
本发明包括具有阴极的可充电锂-硫电池，所述阴极的特征为一种纳米复合材料，所述纳米复合材料包括石墨烯片材，并且具有吸附至该石墨烯片材的含硫粒子。硫粒子具有小于50nm的平均直径。发明还包括制备石墨烯片材的方法。基于本发明实施方案的电池可以在甚至100次循环后具有大于950m Ah g-1的可逆容量。在某些实施方案中，石墨烯-硫纳米复合材料粉末的振实密度优选大于0.92g cm-3。此外，纳米复合材料中的硫含量优选大于约70wt%。
石墨烯片材可以随机、伪随机或以层状堆叠方式排列。在随机排列中，石墨烯片材和/或具有吸附硫粒子的石墨烯片材的区域在石墨烯片材的排列上不具有可识别的图案。层状堆叠可以包括在石墨烯片材之间和/或石墨烯片材的各层之间的硫层中排列的吸附的粒子，其中硫层和石墨烯层大体上交替。伪随机排列可以包括随机石墨烯片材和堆叠相石墨烯片材的混合物。
在优选的实施方案中，阴极包括与纳米复合材料接触的聚合物以使多硫化物进入电解质中的扩散最小化。可以施加聚合物以涂覆纳米复合材料表面。或者，聚合物、石墨烯片材和硫粒子可以构成混合物。优选地，聚合物为阳离子膜。一个具体实例包括但不限于基于磺化四氟乙烯的含氟聚合物-共聚物。具有该聚合物的电池可以在0.1C甚至经过50个循环后具有至少74%初始容量的放电容量。聚合物的可替代实例包括但不限于聚环氧乙烷(PEO)。
根据本发明的一个实施方案，具有含吸附硫粒子的石墨烯片材的石墨烯-硫纳米复合材料可以通过首先使石墨氧化物热膨胀以产生石墨烯片材以及随后将石墨烯片材与包括硫和二硫化碳的第一溶液混合而制备。之后蒸发二硫化碳以产生固体纳米复合材料，将其研磨以得到含有平均直径小于约50nm的初级硫粒子的石墨烯-硫纳米复合材料粉末。
根据一个实施方案，本文在他处所述的聚合物可以通过将石墨烯-硫纳米复合材料与包括聚合物和溶剂的第二溶液混合并且然后移除溶剂而施加。
之前摘要的目的在于使美国专利和商标局以及通常而言的公众，特别是对专利或法律术语或表达不熟悉的本领域科学家、工程师和从业者能够由初步审查而快速确定本申请的技术公开内容的性质和实质。摘要不意欲定义本申请的发明（这通过权利要求而确定），也不意欲以任何方式限制发明的范围。
本发明的各种优点和新的特征在本文中记载并且将由以下详细的描述而进一步对本领域人员显而易见。在前述和以下的描述中，已经示出和记载了各种实施方案（包括优选的实施方案）。本文包括对实施本发明所设想的最佳实施方式的描述。如将会意识到的，本发明能够在不偏离本发明的情况下在各个方面作出改变。因此，以下提出的优选的实施方案的附图和说明应理解为实际上是示例说明性而不是限制性的。
附图说明
参考以下附图对本发明的实施方案作如下描述。
图1是根据本发明一个实施方案以有序堆叠排列方式排列的石墨烯-硫纳米复合材料的示意图。
图2a和2b为根据本发明实施方案以层状堆叠方式排列的石墨烯-硫纳米复合材料在两个不同的放大率下的横截面透射电子显微镜(TEM)图像。
图3a-3d包括提供关于根据本发明实施方案合成的石墨烯-硫纳米复合材料阴极的电化学特性的数据的图。
图4为具有根据本发明实施方案施加的聚合物的石墨烯-硫纳米复合材料阴极的电压-比容量图。
具体实施方式
以下描述包括本发明一个实施方案的优选最佳方式。由该发明描述可以清楚的是本发明不限于这些说明的实施方案，而是本发明还包括各种修改及其实施方案。因此本描述应看作是说明性的而不是限制性的。尽管本发明易于进行各种修改和具有替代的结构，应理解的是不旨在限制本发明为公开的具体形式，而是，与之相反，本发明包括落入权利要求所定义的本发明精神和范围内的所有修改、替代结构和等价物。
根据本发明的实施方案合成了包括石墨烯片和硫粒子的交替层堆叠的石墨烯-硫纳米复合材料。将由石墨氧化物热膨胀制备的80mg石墨烯片材和3.2g的10重量%的含有硫的二硫化碳(CS2)溶液混合在一起。将混合物超声处理10-15分钟并且在氮气中在搅拌下于通风橱内蒸发以排除CS2。将干燥样品在氮气保护下155℃加热以更好的将硫负载至石墨烯表面。一旦CS2已经基本被移除，从而形成固体纳米复合材料，将所述固体纳米复合材料通过使用高能球磨机研磨8小时。研磨后，石墨烯-硫纳米复合材料中的硫含量通过热重分析仪在氩气中以10℃/min的扫描速率从室温至800℃测定为约71.8重量%。
还合成了聚合物涂覆的石墨烯-硫纳米复合材料。将根据本发明实施方案形成的100mg的石墨烯硫纳米复合材料与0.5g的0.1重量%的（例如，基于磺化四氟乙烯的含氟聚合物-共聚物）溶液混合。将混合物连续搅拌过夜并且然后在搅拌下加热至80℃以将溶剂从溶液中蒸发除去。涂覆的石墨烯-硫纳米复合材料通过在真空下干燥以移除任何残留溶剂而获得。
为了进行电化学表征，将根据本发明实施方案合成的石墨烯-硫纳米复合材料粉末用于制备阴极。将80重量%石墨烯-硫纳米复合材料粉末、10重量%SP型炭黑和10重量%的溶解于N-甲基-2-吡咯烷酮(NMP)的聚偏二氟乙烯(PVDF)结合以形成浆体。然后将电极浆体浇注至Al箔。电极材料的电化学测试使用具有石墨烯-硫纳米复合材料阴极和作为反电极和参比电极的锂金属的纽扣电池进行。电解质为溶解于1,3-二氧戊环(DOL)和二甲氧基乙烷(DME)（1:1体积）混合物的1M锂双(三氟甲烷)磺胺锂(LiTFSI)。使用的隔膜为多微孔膜(2400)并且将电池在氩气填充的手套箱中组装。恒流充电-放电测试在1.0～3.0V电压间隔下通过电池测试体系而进行。循环电压测试也用纽扣电池在0.1mV s-1的扫描速率下使用电化学界面而进行。
图1-4示出了本发明的多方面、实验结果和实施方案。图1为示意图，描绘了以有序堆叠方式排列的石墨烯-硫纳米复合材料。石墨烯片材100和吸附的硫粒子的层101在堆叠中交替排列。在替代的排列中（没有示出），具有吸附的硫粒子的石墨烯片材可随机排列。
图2a为示出大区域层状材料的石墨烯-硫纳米复合材料的横截面TEM图像。图2b中的高分辨TEM图像示出了交替的石墨烯层（低对比度/亮区域）201和吸附的硫粒子层（高对比度/暗区域）202。在该特定的实施方案中，硫粒子为直径小于或等于约20nm。
使用循环伏安法(CV)和恒定电流充电-放电测试方法测试基于本发明实施方案的石墨烯-硫纳米复合材料的电化学特性。CV曲线示于图3a。由于石墨烯仅起到作为电子导体的作用并且无助于电势区域的容量，图3a所示的CV特征仅可以归因于硫固有的还原和氧化，示出了两个还原峰和一个氧化峰。根据硫电极的电化学还原机理，约2.3V处的还原峰与溶解于电解质中的元素硫还原至多硫化锂(Li2Sn，4≤n<8)有关，并且在2.0V处的另一还原峰是由于多硫化物链长降低以及最终形成的Li2S所致。在反向的阳极扫描中，仅一个氧化峰出现在2.5V处，表明两个氧化反应的峰太接近以致不能分辨。对于第二氧化还原反应所观察到的大的超电势表明当由多硫化锂转化为Li2S时可出现高度极化。这是由于克服链长的改变需要更高的活化能。图3b示出了石墨烯-硫纳米复合材料在168mA g-1的恒定电流下（相应于0.1C速率）的第一充电-放电曲线。放电曲线示出了两步放电图形，相应于两类的放电反应，与图3a示出的CV结果非常一致。石墨烯-硫纳米复合材料具有967mAh g-1的初始放电容量但是在50个循环后显示52%的衰减，如图3c所示。这表明具有交替的石墨烯和硫层的层状纳米结构提供了高度传导、活性的框架但是可溶的多硫化物在循环过程中的迁移必须降低。
因此，在优选的实施方案中，将聚合物用于石墨烯-硫纳米复合材料以进一步控制可溶的硫物质。-涂覆的和未涂覆的纳米复合材料的扫描电镜(SEM)图像（未示出）表明聚合物可以涂覆石墨烯-硫纳米复合材料的粒子表面以抑制多硫化物的扩散。
参考图3c中容量与循环数的关系图，-涂覆的石墨烯-硫纳米复合材料在50个充电/放电循环后保持79.4%的初始容量，具有良好的循环稳定性。-涂覆的石墨烯-硫纳米复合材料的另外的稳定性和速率容量性能示于图3d。尽管在涂覆前和涂覆后初始放电容量改变极少，-涂覆的石墨烯-硫纳米复合材料在100次循环后在0.1C下保持74.3%的初始容量。图4示出了NAFION-涂覆的石墨烯-硫纳米复合材料在各种放电速率下(1C=1680mA g-1)比容量与电压的曲线。纳米复合材料阴极在0.2C、0.5C和1C下分别具有839mAh g-1、647mAh g-1和505mAh g-1，相应于在0.1C下测量的放电容量的保持率为89%、69%和54%。
-涂覆的电极的改进的速率容量和高的循环稳定性可归因于石墨烯层的高的电子电导性和由涂层提供的降低的多硫化物的溶解/迁移。施加的聚合物涂层，除改进的化学和电化学稳定性外，看起来还提供了改进的机械强度。特别地，磺化四氟乙烯含氟聚合物-共聚物可以形成致密的膜以覆盖石墨烯-硫纳米复合材料的表面，其阻止多硫化物由吸附的硫粒子扩散至电解质。此外，因为这是具有磺酸根离子基团的阳离子膜，所以Li离子容易通过膜扩散，而仍然抑制多硫化物阳离子的转运，最可能是由于静电排斥。
尽管本发明的大量的实施方案已示出并且描述，对本领域技术人员而言清楚的是许多改变和修改可以在不偏离本发明的情况下在其更广的方面做出。因此，所附权利要求旨在包括落入本发明真实的实质和范围内的所有改变和修改。

Claims (23)

1.一种可充电锂-硫电池，包括阴极和电解质，所述阴极的特征为一种纳米复合材料，所述纳米复合材料包括石墨烯片材，并且具有吸附至该石墨烯片材的硫粒子，所述粒子具有小于50nm的平均直径。
2.权利要求1的电池，在0.1C下在100次循环后具有大于950mAhg-1的可逆容量。
3.权利要求1的电池，还包括与纳米复合材料接触的聚合物以使多硫化物向电解质的扩散最小化。
4.权利要求3的电池，其中所述聚合物覆盖纳米复合材料表面。
5.权利要求3的电池，其中聚合物、石墨烯片材和硫粒子构成混合物。
6.权利要求3的电池，其中所述聚合物为阳离子膜。
7.权利要求3的电池，其中所述聚合物包括基于氟化四氟乙烯的含氟聚合物-共聚物。
8.权利要求1的电池，在0.1C下在50次循环后具有至少74％初始容量的放电容量。
9.权利要求3的电池，其中所述聚合物包括聚环氧乙烷。
10.权利要求1的电池，其中所述纳米复合材料的粉末具有大于0.92g cm-3的振实密度。
11.权利要求1的电池，在所述纳米复合材料中具有大于70重量％的硫含量。
12.权利要求1的电池，其中吸附的粒子排列于以交替的石墨烯层和硫层方式堆叠的石墨烯层之间的硫层中。
13.一种可充电的锂-硫电池，包括阴极和电解质并且在0.1C下在100次循环后具有大于950mAh g-1的可逆容量，所述阴极的特征为一种纳米复合材料，所述纳米复合材料包括石墨烯片材，并且具有吸附至该石墨烯片材的硫粒子，所述粒子具有小于50nm的平均直径，其中纳米复合材料中的硫含量大于70重量％。
14.制备用作可充电锂-硫电池中阴极的石墨烯-硫纳米复合材料的方法，所述石墨烯-硫纳米复合材料包括石墨烯片材，并且具有吸附至该石墨烯片材的硫粒子，该方法特征为以下步骤：
使石墨氧化物热膨胀以产生石墨烯片材；
将石墨烯片材与包括硫和二硫化碳的第一溶液混合；
使二硫化碳蒸发以产生固体纳米复合材料；并且
研磨固体纳米复合材料以得到具有平均直径小于50nm的硫粒子的石墨烯-硫纳米复合材料。
15.权利要求14的方法，还包括石墨烯-硫纳米复合材料与包括聚合物和溶剂的第二溶液混合，并且然后移除溶剂。
16.权利要求15的方法，其中所述聚合物为阳离子膜。
17.权利要求15的方法，其中所述聚合物包括基于氟化四氟乙烯的含氟聚合物-共聚物。
18.权利要求15的方法，其中所述聚合物包括聚环氧乙烷。
19.权利要求14的方法，其中所述电池在0.1C下在50次循环后具有至少74％初始容量的放电容量。
20.权利要求14的方法，其中所述石墨烯-硫纳米复合材料的粉末具有大于0.92g cm-3的振实密度。
21.权利要求14的方法，还包括形成交替的石墨烯层和硫层的堆叠，所述硫层包括位于石墨烯层之间的吸附的粒子。
22.权利要求14的方法，其中所述可充电锂-硫电池具有大于950mAh g-1的可逆容量。
23.权利要求14的方法，其中所述石墨烯-硫纳米复合材料具有大于70重量％的硫负载。
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