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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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Nano Energy · 2016 · IF 11.553

Reduced graphene oxide wrapped MOFs-derived cobalt-doped porous carbon polyhedrons as sulfur immobilizers as cathodes for high performance lithium sulfur batteries

Zhaoqiang Li,Caixia Li,Xiaoli Ge,Jingyun Ma,Zhiwei Zhang,Qun Li,Chengxiang Wang,Longwei Yin

Reduced graphene oxide (RGO) wrapped metal-organic frameworks (MOFs) derived cobalt doped porous carbon polyhedrons synthesized via a carbonization process, are for the first time used for sulfur immobilizers (RGO/C–Co-S) as cathodes for high performance lithium-sulfur (Li–S) batteries. The RGO/C–Co–S cathode exhibits greatly improved electrochemical performance, showing excellent specific capacity of 949   mAh g −1 at 300th cycle at a current density 0.3   A   g −1 , displaying enhanced rate capability with specific capacity of 772, 704 and 606   mAh g −1 at current density of 0.5, 1 and 2   A   g −1 , respectively. The synergetic effect of MOFs-derived porous carbon, homogeneously distributed Co nanoparticles and RGO nanosheets simultaneously contributes to the confinement of sulfur species. The presence of abundant mesopores and micropores is conducive to immobilize large amounts of S species. The homogenously inlaid ultrafine Co nanoparticles can further immobilize sulfur by chemical interactions between Co and S/polysulfides. The RGO nanosheets tightly wrapped on carbon hosts act as barrier layers to prevent polysulfides from diffusing out of the matrix, further suppressing shuttle effect. The porous structure and the RGO can effectively alleviate the volume changes resulted from charge–discharge process. This design strategy can be inspiring for MOF-derived materials in energy storage applications .

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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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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Small · 2022 ·Vol. 18 ·期 48 ·2205163 · IF 15.153

Self-Supporting Multicomponent Hierarchical Network Aerogel as Sulfur Anchoring-Catalytic Medium for Highly Stable Lithium–Sulfur Battery

Shuhao Tian,Juanjuan Huang,Hongcen Yang,Guo Liu,Qi Zeng,Di Wang,Xiao Sun,Kun Tao,Guohan Liu,Shanglong Peng

The low utilization rate of active materials, shuttle effect of lithium polysulfides (LiPSs), and slow reaction kinetics lead to the extremely low efficiency and poor high current cycle stability of lithium sulfur batteries (Li–S batteries). In this paper, a self-supporting multicomponent hierarchical network aerogel is proposed as the modified cathode (S/GO@MX@VS 4 ). It consists of graphene (GO) and MXene nanosheets (MX) loaded with VS 4 nanoparticles. The experimental results and first-principles calculations show that the GO@MX@VS 4 aerogel has strong adsorption and reversible conversion effects on LiPSs. It can not only inhibit the shuttle effect and improve the utilization rate of active substances by keeping the chain crystal structure of VS 4 , but also promote the reversibility and kinetics of the reaction by accelerating the liquid–solid transformation in the reduction process and the decomposition of insoluble Li 2 S in the oxidation process. The GO@MX@VS 4 aerogel modified cathode with a multicomponent synergy exhibits the capacity ratios (Q 1 /Q 2 ) at different discharge stages is close to the theoretical value (1:2.8), and the capacity decay per cycle is 0.019% in 1200 cycles at 5C. Also, a high areal capacity of 6.90 mAh cm −2 is provided even at high sulfur loading (7.39 mg cm −2 ) and low electrolyte/sulfur ratio (E/S, 8.0 µL mg −1 ).

研究领域: 电化学储能 · 材料科学 · 纳米材料 · 能源化学 · 电池技术 · 表面催化
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JOURNAL OF POWER SOURCES · 2018 · IF 6.945

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

Jing Gao,Chunshui Sun,Lei Xu,Jian Chen,Chong Wang,Decai Guo,Hao Chen

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10 −4  S cm −1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li + /Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities . A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g −1  (S) at 0.05 C and 895 mAh g −1  (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte .

研究领域: 电化学 · 能源材料 · 固态电池 · 聚合物电解质 · 锂离子电池 · 电极界面工程 · 储能技术
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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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IONICS · 2020 ·Vol. 26 ·期 9 ·4257-4265 · IF 2.394

Facile synthesis of a mixed-conductive Li2S composites for all-solid-state lithium-sulfur batteries

Jiang Huize,Han Yu,Wang Hui,Zhu Yuhao,Guo Qingpeng,Jiang Haolong,Zheng Chunman,Xie Kai

The poor interface between the active materials, solid electrolytes, and conductive additives in composite cathode materials is the key factor restricting the performance of the all-solid-state lithium-sulfur battery. Here, the composite cathode material was prepared through the method of one-step ball milling. The sulfide electrolyte Li 3 PS 4 (LPS) was formed on the surface of the active material Li 2 S while the conductive additives were incorporated, and the conductive ions and electronic network were constructed simultaneously. After adding an appropriate amount of carbon nanotubes (cnt), the composite cathode exhibited high specific capacity of 1145.2 mAh g −1 after 30 times of cycling at a current density of 0.2 mA cm −2 , and the battery with ultrahigh areal Li 2 S loading also displays high capacity of 962.6 mA g −1 . The composite cathode with high Li 2 S content (56.3%) was prepared, with excellent performance exhibited: the capacity is 741 mAh g −1 after 30 times of cycling at a current density of 0.2 mA cm −2 . Without additional sulfide electrolyte, the composite cathode materials were prepared by one-step ball milling with lithium sulfide, phosphorus pentasulfide, acetylene black, and carbon nanotubes as raw materials.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 纳米复合材料
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