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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

An effective strategy for shielding polysulfides and regulating lithium deposition in lithium–sulfur batteries

Qi Jin,Kaixin Zhao,Xitian Zhang

The lithium–sulfur (Li–S) battery is an appealing choice for the next-generation high-energy-density energy storage systems . However, side reactions between lithium polysulfides (LiPSs) and Li metal anode cause the growth of Li dendrites, loss of active materials, and safety issues, which severely hinders the practical application of Li–S batteries. Constructing a protection layer on the surface of Li anode is an effective strategy to shield LiPSs and regulate lithium uniform deposition in Li–S batteries. Herein, we design and fabricate a lithiated Nafion protective layer to alleviate the side reactions between LiPSs and the Li anode and guide uniform deposition of Li, in which, their mechanism is investigated. The optimal protective layer effectively protects the Li anode from the detrimental side reactions, which boosts the stability of the Li anode. Li–Li and Li-stainless steel cells with 4 M [S] Li 2 S 8 electrolyte can last for more than 400 cycles and 100 cycles at current density of 1 mA cm −2 . A Li–S full cell also exhibits a high reversible capacity of 791.5 mA h g −1 after 250 cycles at 0.5 C. This work reveals the vital role of the artificial protective layer in enhancing the stability of the Li anode in Li–S batteries.

研究领域: 电化学 · 能源材料 · 电化学储能 · 电池技术 · 界面化学
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SN Applied Sciences · 2020 ·Vol. 2 ·期 7 ·1156 · IF 0

Multifunctional hosts of Zinc sulfide coated carbon nanotubes for lithium sulfur batteries

Liu Honghong,Thomas Tiju,Li Rongrong,Shen Hangjia,Wang Jiacheng,Yang Minghui

Lithium sulfur (Li–S) batteries are next general energy storage systems due to their high thereotical energy density, low cost and environmental friendly. Herein, we develop a composite polysulfide mediator based on carbon nanotubes enwrapped by zinc sulfide (CNTs@ZnS) nanoparticles as multifunctional host materials for sulfur cathode. The ZnS nanoparticles is uniformed coating on the outside layer of functionalized carbon nanotubes. The unique structure of CNTs@ZnS ensure the chemical adsorption on ZnS and fast electron transfer from ZnS to carbonnanotubes. The presence of ZnS efficiently alleviates the shuttle effect of soluble lithium polysulfide intermediates and hence offers a mean to further enhancing the reaction activity via sulfophilic property of ZnS and catalytically accelerate the conversion of polysulfides to insoluable Li 2 S. The high conductivity of carbon nanotubes results in rapid electron transfer. The CNTs@ZnS cathode offers an excellent specific capacity of ~ 1003 mAh g −1 after 100 cycles at 0.2C. Furthermore significant cycling performance at 0.2C with 3.1 mg cm −2 sulfur loading for 500 cycles is observed with 0.05% capacitance decay per cycle. The results provide insights to develop high-performance Li–S batteries based on multifunctional host materials.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米科技 · 功能材料
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JOURNAL OF POWER SOURCES · 2019 · IF 7.467

Metallically conductive TiB2 as a multi-functional separator modifier for improved lithium sulfur batteries

Liming Jin,Jie Ni,Chao Shen,Fenglai Peng,Qiang Wu,Donghao Ye,Junsheng Zheng,Gaoran Li,Cunman Zhang,Zhoupeng Li,Jim P. Zheng

A metallically conductive TiB 2 is developed to construct multifunctional separator toward improved lithium-sulfur (Li–S) battery performance. Coupled with two-dimensional graphene, the obtained TiB 2 @G separator fulfills a synergistic combination of strong physical and chemical sulfur immobilization as well as a high-efficiency sulfur reutilization, thus establishing a robust barrier against the polysulfide shuttling and enabling a fast and durable sulfur electrochemistry . As a result, cells based on TiB 2 @G separator exhibit a high sulfur utilization with 1350 mA h g −1 capacity at 0.05C, superb rate capability up to 5.0C, and excellent cyclability with a high capacity retention over 85% after 300 cycles at 0.5C. Moreover, significantly mitigated self-discharge and considerably high areal capacity of 5.8 mA h cm −2 can be also achieved, indicating the great promise of this separator design for the development of high-performance Li–S batteries.

研究领域: 电化学 · 能源材料 · 纳米材料科学 · 储能技术 · 电池化学
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ELECTROCHIMICA ACTA · 2018 · IF 5.116

Gelatin-polyethylenimine composite as a functional binder for highly stable lithium-sulfur batteries

Naseem Akhtar,Hongyuan Shao,Fei Ai,Yuepeng Guan,Qifan Peng,Hao Zhang,Weikun Wang,Anbang Wang,Bingyin Jiang,Yaqin Huang

Lithium-sulfur (Li-S) batteries with high specific capacity are expected to be a new generation of energy storage devices. However, the shuttle effect of lithium polysulfide makes it difficult to commercialize stable Li-S batteries. In this work, we designed a gelatin-polyethylenimine composite (GPC) as functional binder for Li-S batteries to improve the stability of electrode during discharge-charge process. GPC binder combines the dispersion and adhesion ability of gelatin, which keeps cathode homogeneous and stable during electrochemical reaction , and adsorption capability of PEI for polysulfide , which suppresses the “shuttling effect”. The result shows that GPC used as a binder remarkably enhanced cyclic performance of Li-S battery with good capacity retention of about 100% at current density of 1C (sulfur loading 1.5 mg cm −2 ) after 100 cycles. We believe that GPC would be a promising binder for highly stable Li-S batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 高分子化学 · 纳米复合材料
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2016 · IF 2.822

(De)Lithiation of tubular polypyrrole-derived carbon/sulfur composite in lithium-sulfur batteries

Xinhe Zhang,Bo Jin,Linlin Li,Tuo Cheng,Huanhuan Wang,Peiming Xin,Xingyou Lang,Chuncheng Yang,Wang Gao,Yongfu Zhu,Qing Jiang

Non-graphitizable carbon (NGC) has been obtained by carbonizing tubular polypyrrole (T-PPy) synthesized through a self-degraded template method . K-NGC/S composite has been prepared by mixing S with K-NGC via melt-diffusion method where NGC has been activated by potassium hydroxide (denoted as K-NGC) and is used as a conductive additive. The as-prepared K-NGC/S composite shows good specific discharge capacity and rate capability with an initial specific discharge capacity of 1121.9   mAh   g −   1 and a specific discharge capacity of 729.7   mAh   g −   1 after 50   cycles at a current density of 335   mA   g −   1 , which is better than pure S. This improvement in the specific discharge capacity and the rate capability of the cell with K-NGC/S composite as a cathode material is realized by the existence of K-NGC, which can offers a superb conductive environment for S, effectively encapsulate S, restrain the outward diffusion of polysulfides , buffer volume change upon cycling and reduce the dissolution of lithium polysulfides into the electrolyte. The good electrochemical performance of K-NGC/S composite would make it become a promising cathode material for lithium-sulfur batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米材料 · 电池技术
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RSC Advances · 2015 ·Vol. 5 ·期 117 ·96862-96869 · IF 3.84

PEDOT-PSS coated sulfur/carbon composite on porous carbon papers for high sulfur loading lithium–sulfur batteries

Zhijie Gong,Qixing Wu,Fang Wang,Xu Li,Xianping Fan,Hui Yang,Zhongkuan Luo

Increasing the sulfur loading in the cathode of a lithium–sulfur battery is an important way to improve its capacity for practical applications. To achieve this, the present work proposes using PEDOT-PSS to encapsulate sulfur/carbon black (S/BP) by a facile solution mixing method and the formed composite is then coated on a porous carbon paper. It is believed that the formation of a core/shell structure in the PEDOT@S/BP composite can promote the electron transport and effectively impede the diffusion of polysulfides, and the porous carbon paper is able to retain the electrolyte containing the dissolved polysulfides in the cathode and alleviate the adverse effect of sulfur volumetric expansion. Due to such advantages, the proposed cathode, with a high sulfur loading of 3 mg cm−2, can yield a high reversible capacity of 1041 mA h g−1 and an excellent cycle stability with a capacity retention of 868 mA h g−1 after 100 cycles and an average coulombic efficiency of 99.4%.

研究领域: 电化学 · 能源材料 · 纳米复合材料 · 电池技术 · 功能高分子材料
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JOURNAL OF POWER SOURCES · 2016 · IF 6.333

Flexible carbon nanofiber/polyvinylidene fluoride composite membranes as interlayers in high-performance LithiumSulfur batteries

Zhenhua Wang,Jing Zhang,Yuxiang Yang,Xinyang Yue,Xiaoming Hao,Wang Sun,David Rooney,Kening Sun

Traditionally polyvinylidene fluoride membranes have been used in applications such as membrane distillation , wastewater treatment , desalination and separator fabrication. Within this work we demonstrate that a novel carbon nanofiber/polyvinylidene fluoride (CNF/PVDF) composite membrane can be used as an interlayer for Lithium Sulfur (Li S) batteries yielding both high capacity and long cycling life. This PVDF membrane is shown to effectively separate dissolved lithium polysulfide with the high electronic conductivity CNF not only reducing the internal resistance in the sulfur cathode but also helping immobilize the polysulfide through its abundant nanospaces. The resulting Li S battery assembled with the CNF/PVDF composite membrane effectively solves the polysulfide permeation problem and exhibits excellent electrochemical performance. It is further shown that the CNF/PVDF electrode has an excellent cycling stability and retains a capacity of 768.6 mAh g −1 with a coulombic efficiency above 99% over 200 cycles at 0.5C, which is more than twice that of a cell without CNF/PVDF (374 mAh g −1 ). In addition, the low-cost raw materials and the simple preparation process of CNF/PVDF composite membrane is also amenable for industrial production.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米复合材料 · 电池技术
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ELECTROCHIMICA ACTA · 2020 · IF 6.215

CTF/MWCNT hybrid multi-functional separator as high-efficiency polysulfide tamer for high-performance Li–S battery

Qing Xuan Shi,Chen Chang,Hui Jie Pei,Xin Guan,Liang Liang Yin,Xiao Lin Xie,Yun Sheng Ye

The lithium–sulfur (Li–S) battery holds great promising for the next-generation energy storage system due to its high theoretical specific capacity and energy density . However, the poor conductivity of sulfur species and the “shuttle effect” of polysulfides (PSs) severely limit the practical application of Li–S battery. Here, a large-scaled covalent triazine framework/multiwall carbon nanotube (CTF/MWCNT) hybrid used as a multi-functional separator modifier combining strong PSs-anchor ability of CTF with high electrical conductivity of MWCNT was proposed. The ordered porous structure and large specific surface area of CTF make it good physical trap ability for PSs shuttle, and the abundant pyridinic nitrogen groups of CTF render it effectively adsorb PSs by chemical sorption , while the high electrical conductivity of MWCNT can facilitate electron transfer . As it turns out that the multi-functional separator applied in Li–S battery shows significant enhancements in the utilization of sulfur, specific capacity, Columbic efficiency, rate capability (982 mAh g −1 at 2 C) and cycling stability (0.045% specific capacity loss per cycle at 1 C along 1000 cycles) as well as suppression of self-discharge and Li dendrite growth. Furthermore, it is practicable to incorporate the slurry cast multi-functional layer onto the commercial separator, which provides ideas for constructing advanced multi-functional separators for commercially viable Li–S battery.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米复合材料 · 电池技术
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ELECTROCHIMICA ACTA · 2022 · IF 7.336

Bifunctional hydrogen-bonding cross-linked polymeric binder for high sulfur loading cathodes in lithium/sulfur batteries

Heli Yu,Mingzhu Bi,Cuijuan Zhang,Tianjie Zhang,Xiaoning Zhang,Hongtao Liu,Jianli Mi,Xiangqian Shen,Shanshan Yao

Construction of high sulfur loading electrode is one of the effective ways to achieve high specific energy density lithium/sulfur batteries. Therefore, the optimization of polymeric binders has been considered as effective strategy to improve the volume changes of sulfur electrodes during charge/discharge processes. In this work, an effective route for the preparation of three dimensional polymeric binder (PAA-PANI) via multiple hydrogen bonds was developed and fabricated through in situ polymerization between polyacrylic acid (PAA) and polyaniline (PANI), which possess bifunctional effects on high sulfur loading cathodes in lithium/sulfur batteries. The carboxyl polar groups of PAA could effectively adsorb polysulfides and the conductive PANI enhance the electronic conductivity of the sulfur electrode. The three dimensional polymeric binder of PAA-PANI has enhanced the active material adhesion, mechanical properties and electronic conductivity, which decreased overpotential polarization, improved the lithium ions diffusion coefficient, and reduced the self-discharge. More importantly, the PAA-PANI functional binder could alleviate the expansion of high sulfur loading electrode. Taking advantages of PAA-PANI binder, the carbon nanotubes modified sulfur electrode (CNTs@S; sulfur content: 84.3 wt%) with PAA-PANI binder exhibits an initial discharge capacity of 906 mAh g –1 at 2.56 mA cm –2 (0.3 C) under a sulfur loading of 5.1 mg cm –2 . Even at higher current density of 8.54 mA cm –2 (1 C), the PAA-PANI binder electrode delivers a high capacity of 846 mAh g –1 . Moreover, with an extremely high areal sulfur loading of 17 mg cm –2 , the cathode shows an areal specific capacity of 16.7 mAh cm –2 .

研究领域: 电化学 · 能源材料 · 高能电池 · 功能高分子 · 界面化学 · 储能技术
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Small · 2020 ·Vol. 16 ·期 22 ·2000870 · IF 11.459

Oxygen-Deficient Ferric Oxide as an Electrochemical Cathode Catalyst for High-Energy Lithium–Sulfur Batteries

Kezhong Lv,Pengfei Wang,Chao Wang,Zihan Shen,Zhenda Lu,Huigang Zhang,Mingbo Zheng,Ping He,Haoshen Zhou

Lithium–sulfur batteries, as one of promising next-generation energy storage devices, hold great potential to meet the demands of electric vehicles and grids due to their high specific energy. However, the sluggish kinetics and the inevitable “shuttle effect” severely limit the practical application of this technology. Recently, design of composite cathode with effective catalysts has been reported as an essential way to overcome these issues. In this work, oxygen-deficient ferric oxide (Fe 2 O 3− x ), prepared by lithiothermic reduction, is used as a low-cost and effective cathodic catalyst. By introducing a small amount of Fe 2 O 3− x into the cathode, the battery can deliver a high capacity of 512 mAh g −1 over 500 cycles at 4 C, with a capacity fade rate of 0.049% per cycle. In addition, a self-supporting porous S@KB/Fe 2 O 3− x cathode with a high sulfur loading of 12.73 mg cm −2 is prepared by freeze-drying, which can achieve a high areal capacity of 12.24 mAh cm −2 at 0.05 C. Both the calculative and experimental results demonstrate that the Fe 2 O 3− x has a strong adsorption toward soluble polysulfides and can accelerate their subsequent conversion to insoluble products. As a result, this work provides a low-cost and effective catalyst candidate for the practical application of lithium–sulfur batteries.

研究领域: 电化学 · 能源材料 · 纳米催化 · 储能技术 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Ultra-lightweight ion-sieving membranes for high-rate lithium sulfur batteries

Bin Qin,Yifei Cai,Xiaoqing Si,Chun Li,Jian Cao,Weidong Fei,Junlei Qi

The practical application of lithium-sulfur (Li-S) batteries is impeded by the shuttle effect of intermediate polysulfides and the inherent sluggish kinetics. Herein, Mo 2 C nanocatalysts anchoring on holey graphene scaffold (Mo 2 C@HGr) is explored as a lightweight and ultrathin modified separator to conquer the above issues. The artificially customized holes on holey graphene sheets facilitate ionic transfer and electrolyte penetration, and further enhance the sulfur utilization under lean electrolyte conditions. The experimental results together with theoretic calculation demonstrate the favourable chemical adsorption ability of Mo 2 C sites that blocking the diffusion of LiPSs. Abundant triple-phase interfaces among Mo 2 C nanomediators, holey graphene and electrolyte boost the conversion kinetics of the intercepted LiPSs. As a result, the cell with Mo 2 C@HGr modified separator shows superior rate capability (836 mAh g −1 ) even at 5 C current with a negligible Mo 2 C@HGr loading of 0.08 mg cm −2 . Furthermore, ultrahigh areal capacity of 5.9 mAh cm −2 is still attained with high sulfur loading of 6 mg cm −2 under lean electrolyte operation (E/S = 5.6 µL mg −1 ). This design concept can be extended to other graphene based multifunctional nanocomposite toward the development of more practical Li-S batteries.

研究领域: 电化学 · 能源材料 · 纳米催化 · 电池技术 · 功能复合材料
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