中空碳双面修饰的隔膜在高性能锂硫电池中的应用

为减少多硫化锂(LIPs)“穿梭效应”及锂枝晶对锂硫电池的影响,采用刮涂法制备中空碳材料修饰隔膜。接触角测试表明修饰隔膜对LIPs具有更强的吸引力,其对LIPs“穿梭”的有效抑制也可以通过渗透性实验进一步得到印证。在隔膜的正极对称电池测试中,电流响应显示中空碳材料的催化使LIPs快速转化为Li₂S。通过隔膜的负极对称电池测试发现修饰隔膜呈现出更稳定的电压-时间曲线。为证明隔膜修饰对锂硫电池性能改进的效果,分别采用聚丙烯(PP)隔膜、单面改性和双面改性的PP隔膜组装成纽扣电池并进行电化学测试,其中电极材料的硫负载量为1.8~2.0 mg·cm^-2。GITT(恒电流间歇滴定法)测试和锂离子扩散系数计算表明,改性隔膜的离子传输更快且阻抗较小。通过分析第1、5、10、50及100次的充放电循环阻抗谱图发现,中空碳材料的多通道能够为锂离子的传输提供更多的通道,因此能够使锂离子具有更加稳定的扩散行为。在电流密度为0.2C时,由双面改性隔膜组装的锂硫电池在首次充放电时有1 035 mAh·g^-1的可逆比容量,700圈后仍有500 mAh·g^-1的高比容量,并在高硫负载时表现出500 mAh·g^-1的可逆比容量。双面修饰隔膜赋予了锂硫电池优异的电化学性能,这是由于中空碳材料的修饰加速了LIPs的转化和吸附,有效缓解了LIPs的穿梭效应,且对锂枝晶有很好的抑制作用,提高了锂硫电池的安全性。     

锂硫电池隔膜功能化设计

锂硫电池具有较高的理论比容量(以硫计1675 mAh·g^-1和2600 Wh·kg^-1),以及低成本和绿色环保等优势,成为最有前景的下一代可充电储能器件之一。然而,锂硫电池内部严重的多硫化锂穿梭现象导致了电池容量的下降和使用寿命的快速降低。为实现锂硫电池的商业化,其严重的“穿梭效应”亟需改善。普通的商业隔膜有很大的孔径(500 nm),且不具有阻碍多硫化锂迁移的功能。因此,对隔膜进行表面修饰,引入功能化修饰层就成为了一种很有效的策略。本文综述了近年来隔膜表面修饰所遵循的方法以及在此基础上开发的新型隔膜,并对功能化的隔膜在提升锂硫电池性能上的前景进行了展望。     

多功能锂硫电池隔膜

锂硫电池具有远超锂离子电池的高理论比容量（1675 mAh ·g^-1）,并且兼具硫资源丰富、生产成本低廉以及环境友好等优势。然而,多硫离子的穿梭效应造成金属锂负极钝化、引起电池容量和库仑效率下降、循环稳定性变差等严重问题,限制锂硫电池的实际应用。从正极和负极之间的隔膜层出发,引入多硫离子穿梭的阻挡层被认为是极为有效的研究策略。这些研究策略在缓解多硫离子穿梭、提高活性物质利用效率、延长循环寿命和循环稳定性方面具有显著效果。本文分类综述了近年来锂硫电池隔膜功能化的研究进展,并对未来隔膜功能化的研究趋势进行了预测。     

氧缺位结构介孔二氧化钛/聚乙烯复合隔膜在锂硫电池中的应用

采用两步溶液法合成了一种具有高度氧缺位的黑色介孔二氧化钛, 并将其涂覆在隔膜表面作为锂硫电池复合隔膜, 研究了其在锂硫电池中的电化学性能. 结果表明, 氧缺位的黑色介孔二氧化钛材料不仅展现出良好的导电性, 还能加强对多硫化物的物理和化学吸附能力, 从而显著提高锂硫电池的放电比容量(0.1C倍率下首次放电比容量为1257 mA·h/g)和循环性能(循环100次后放电比容量为821 mA·h/g).     

锂硫电池先进功能隔膜的研究进展

随着电子设备和电动汽车对储能设备性能要求的不断提高,锂硫电池因其多电子转化化学赋予的高能量密度受到广泛关注.当前锂硫电池的实用化受到库伦效率低、正极容量快速衰减、负极循环性能差等问题的制约.针对锂硫电池上述瓶颈,设计多功能电解质系统有望大幅提升活性材料的利用效率及循环寿命.本文综述了近年来锂硫电池中多功能隔膜系统的研究进展,具体包括面向抑制副反应的选择性透过隔膜、面向正极的低界面电阻隔膜以及面向稳定负极界面的隔膜.并展望了锂硫电池多功能隔膜系统面临的科学挑战与未来发展的机遇.     

锂硫电池中的催化作用

锂硫电池理论能量密度高达2600 Wh·kg-1,单质硫的理论容量可达1675 mAh·g-1,远高于商业化的锂离子电池正极材料,但多硫化锂的"穿梭效应"等问题对其性能影响严重.目前研究主要采用基于"阻挡"的物理限制和化学吸附策略将多硫化锂限制在正极侧.而基于"疏导"的催化转化策略则通过加快氧化还原反应动力学,在抑制"...     

高性能锂硫电池研究进展

锂硫电池具有理论比容量高(1675 m Ah·g~(-1))、能量密度高(2600 Wh·kg~(-1))、环境友好、价格低廉等性质,是一种高性能的新型储能电池。这些性能使其在电动汽车和便携式设备领域具有重要意义。然而,快速的容量衰减以及较差的循环性能,使锂硫电池还达不到商业应用的要求。本文全面总结了锂硫电池的最新研究进展,详细阐述了锂硫电池的正极、电解质、隔膜以及负极保护,分析了现有锂硫电池存在的缺陷和问题。最后,对锂硫电池未来的发展方向进行了展望。     

锂硫电池用碳化钛涂层隔膜性能探究

为提高锂硫电池的比容量和循环性能,本文使用纳米碳化钛（TiC）作为涂层制备得到TiC/Celgard涂层隔膜,并探究其对锂硫电池性能的影响. 电化学性能测试结果表明,涂层隔膜能有效提高电池在不同倍率下的比容量以及电池的循环性能,在2C倍率下仍表现出650 mAh·g-1的比容量,0.5C循环100周容量仍能保持在843.1 mAh·g-1.     

氮硫共掺杂多孔碳材料的制备及其在锂硫电池中的应用

锂硫电池因其较高的理论容量和对环境友好等优势被视为极具发展潜力的储能装置,但是多硫化物的穿梭效应极大地限制了锂硫电池的实际应用。本文以葡萄糖为碳源,离子液体为氮源和硫源,KCl和ZnCl₂为模板剂,KOH为活化剂,通过热解工艺合成了氮硫共掺杂多孔碳（NSPC）。XPS和极性吸附实验表明N、S杂原子成功引入并且提高了碳材料对多硫化物的吸附能力,有效缓解多硫化物的穿梭效应,而较高的比表面积（1290.67 m²·g^-1）有助于提高硫负载量。负载70.1wt.%的硫后（S@NSPC）作为锂硫电池的正极材料表现出了良好的电化学性能。在167.5 mA·g^-1的电流密度下S@NSPC的首次放电容量为1229.2 mAh·g^-1,远高于S@PC的861.6 mAh·g^-1,且S@NSPC循环500圈后容量为328.1 mAh·g^-1。当电流密度从3350 mA·g^-1恢复至167.5 mA·g^-1时,可逆容量达到首圈放电比容量的80%,几乎恢复至其初始值。     

CoSe2/C复合电催化材料修饰隔膜对高载量锂硫电池性能的影响

以具有菱形十二面体结构的ZIF-67为模板, 采用两步烧结法合成了CoSe₂/C复合材料, CoSe₂纳米颗粒直径约30 nm, 均匀分散在碳骨架上. 电化学测试结果表明, CoSe₂/C复合材料在放电过程中可以加快可溶性聚硫离子的还原反应动力学, 还能够促进不溶性Li₂S的沉积过程, 同时加速充电过程中Li₂S的氧化分解. 将CoSe₂/C作为电催化材料与碳材料混合后用于隔膜修饰, 修饰层面载量仅为0.15 mg/cm², 其中CoSe₂/C的质量分数仅占30%时, 电池依然表现出优异的电化学性能; 当硫载量为4.8 mg/cm²时, 在0.2C倍率下电池初始放电比容量为756 mA·h/g, 经过180次循环后, 容量依然能够维持715 mA·h/g, 每次衰减率仅为0.031%.     

Sulfur/carbon composites prepared with ordered porous carbon for Li-S battery cathode

Ordered porous cabon with a 2-D hexagonal structure,high specific surface area and large pore volume was synthesized through a twostep heating method using tri-block copolymer as template and phenolic resin as carbon precursor.The results indicated the electrochemical performance of the sulfur/carbon composites prepared with the ordered porous carbon was significantly affected by the pore structure of the carbon.Both the specific capacity and cycling stability of the sulfur/carbon composites were improved using the bimodal micro/meso-porous carbon frameworks with high surface area.Its initial discharge capacity can be as high as 1200 mAh·g~(-1) at a current density of 167.5 mA·g~(-1)The improved capacity retention was obtained during the cell cycling as well.     

Rational design of perfluorinated sulfonic acid ionic sieve modified separator for high-performance Li-S battery

Journal of Solid State Electrochemistry - Practical application of Li-S battery is limited by the fast capacity decay and low coulombic efficiency caused by the shuttling phenomenon. Modification...     

Hierarchically porous nitrogen-doped carbon foams decorated with zinc nanodots as high-performance sulfur hosts for lithium-sulfur battery

To prevent polysulfides from dissolution into electrolyte, we propose a novel and simple approach to nitrogen-doped carbon foams which contain hierarchically porous structure and are decorated with zinc nanodots through one-pot carbonization and activation process. These carbon foams, which serve as hosts for sulfur in lithium battery, can provide a conducting network and shorter diffusion length for Li-ions. Specially, the zinc nanodots derived from the carbothermal reaction of ZnCl₂ at high temperature can interact with sulfur/polysulfides by strong chemisorption. In addition, the zinc nanodots can also facilitate the conversion reaction between Li₂S_x (2 < x < 8) and Li₂S/Li₂S₂. Therefore, Zn@NCFs/S cathode presents high sulfur utility and large capacity.     

TiO2/CNTs复合材料涂覆隔膜的制备及在锂硫电池中的应用

以金属有机框架材料MIL-125(Ti)为模板制备了多孔TiO₂, 同时引入碳纳米管, 得到碳纳米管交联包覆多孔TiO₂的三维导电复合材料. 将该复合材料涂覆在隔膜表面并应用于锂硫电池. 利用透射电子显微镜(TEM)、 扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等对材料的结构和组成进行了表征. 电化学测试结果表明,在0.5C(1C=1675 mA/g)倍率下, CNTs/S复合正极材料表现出高达1051.1 mA·h/g的放电容量, 循环150周后仍可保持在904.8 mA·h/g. 在1C倍率下, 放电容量最高可达1036.9 mA·h/g, 循环250周后仍有763.0 mA·h/g, 展现出了良好的倍率性能和循环稳定性.     

Impregnated Sulfur in Carbonized Nitrogen-containing Porous Organic Frameworks as Cathode with High Rate Performance and Long Cycle Life for Lithium-sulfur Batteries

The undesirable cycling performance caused by soluble poly sulfides shuttling between anode and cathode has been considered as the main challenge that has hindered its practical applications for lithium-sulfiir(Li-S) batteries. To solve tliis issue effectively, a nitrogen-containing porous carbon, namely JUC-Z2-900,developed from a porous organic framework, namely JUC-Z2, bearing a high surface area(805 m^2/g),small pore size(0.5 mil) and nitrogen doping(2.15%, mass fraction), has been used as a host material for Li-S batteries. The micropores of JUC-Z2-900 can confine the smaller sulfur molecules S2-4, which can essentially alleviate the critical problem of poly sulfide dissolution.Furthermore, nitrogen-containing JUC-Z2-900 can promote chemical adsorption of sulfur. The above two factors can improve the electrochemical performance of Li-S batteries effectively. To compare the eftects of sulfur contents and melt-difiusion strategy in JUC-Z2-900/S composites, a series of JUC-Z2-900/S composites was synthesized and tlieir electrochemical perfbnnances were explored, indicating good rate performance and excellent cycling stability of the composites contributed by both appropriate mass percentage of sulfiir and its confinement in the micropores.     

Improved disordered carbon as high performance anode material for lithium ion battery

A sulfur-substituted disordered carbon is explored as anode material for lithium-ion battery. Its physical and electrochemical properties are characterized by a variety of techniques such as powder X-ray diffraction, element analysis, Fourier transform infrared spectrum, scanning electron microscopy, and typical electrochemical tests. Electrochemical tests show the activated carbon displays a first cycle discharge capacity of 1,216 mAh·g⁻¹. It also has a remarkable cycling stability with an average capacity fade of 0.92% per cycle from 11th to 100th cycle in the range of 0.01–3.00 V versus metallic lithium at a current density of 100 mA·g⁻¹. After 100 cycles, the electrode still maintained a capacity of 420 mAh·g⁻¹.