ACS Nano
·
2022
·
IF 18.027
Lanxiang Feng,Peng Yu,Xuewei Fu,Zheng-Min Zhang,Kenneth Davey,Yu Wang,Zaiping Guo,Wei Yang
Polar host materials with strong adsorption capacity of polysulfides are designed to limit the shuttle effect in sulfur cathodes. However, a critical problem is to control diffusion and deposition of lithium polysulfides during cycling, which significantly impacts cycling stability and sulfur utilization. Here, we report using a sequential adsorption-guided self-assembly to design two types of core–shell sulfur particles with opposite polysulfide adsorption gradients to explore quantitatively the regulation of polysulfide diffusion and deposition. We show that a positive core–shell design of sulfur particles (PCSD@SP), i.e., polysulfide adsorption capability decreasing from the interior to the exterior of the host, is more effective in restricting polysulfide diffusion and regulating polysulfide deposition than the negative core–shell counterpart (NCSD@SP). As a result, the PCSD@SP electrode with a sulfur loading of 7 mg cm–2 exhibits a stable areal capacity of 6 mAh cm–2 over 130 cycles at 0.2C. At intermittent discharge/charge, the PCSD@SP electrode retains excellent stability compared with the NCSD@SP. We conclude that rational design of positive core–shell active materials can be used to regulate polysulfide diffusion and deposition to boost electrochemical reaction dynamics and performance. The reported findings will be of immediate benefit to a range of researchers in the design of high-performance lithium–sulfur batteries.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Yanlei Shen,Boyu Li,Ziyao Zhang,Jiajing Liu,Huanhuan Ren,Yuman Zhou,Weitao Zhou,Jianxin He
Spinel-structured catalysts demonstrate significant potential for sulfur reduction reaction (SRR) catalysis in lithium-sulfur batteries (LSBs) owing to their geometrically tunable active sites, yet precise structural optimization for simultaneous enhancement of lithium polysulfides (LiPSs) adsorption and catalytic conversion remains challenging. This study addresses this gap through strategic cation occupancy regulation in Co x Mn 3-x O 4 spinels, establishing a dual-active-site system comprising tetrahedral Co 3+ (Td) and octahedral Mn 3+ (Oh) centers that drive selective LiPSs electrocatalysis via geometric synergy. Theoretical and experimental analyses confirm Co 1.2 Mn 1.8 O 4 as the optimal configuration, where optimized Td/Oh Site Distribution Enables: (i) stable covalent Co-S bonding for strong LiPSs adsorption at Td sites, and (ii) dynamic Mn³⁺ (Oh)-S d -p orbital coupling via delocalized d² electrons that critically reduce LiPSs desorption energy barriers (ΔG ≤ 0.82 eV). Leveraging this complementary functionality, a Co 1.2 Mn 1.8 O 4 -embedded carbon nanofiber interlayer delivers exceptional cycling stability—achieving 400 cycles at 1 C with 74.6 % capacity retention. This work extends the application of spinel-type SRR catalysts to high-performance lithium-sulfur batteries.
研究领域:
材料科学
·
电化学
·
纳米技术
·
能量存储
·
催化
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产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2017
·
IF 4.798
Yanqing Wang,Zengqi Zhang,Masaki Haibara,Deye Sun,Xiaodi Ma,Yongcheng Jin,Hirokazu Munakata,Kiyoshi Kanamura
In this research, we demonstrate a new method for reducing the shuttle effect by confining polysulfide in separator area through the use of polyimide (PI) separator with reversible adsorption functions in lithium-sulfur batteries. As a comparison, the cells with polypropylene (PP) separators which have no function to adsorb dissoluble polysulfide show a result that the content of sulfur on lithium anode surface is increased up to 63.94% after 100th cycles with the content of N-methyl-N-butylpiperidinium bis-(trifluoromethylsulfonyl) imide (PP 14 TFSI) in the mixture electrolyte increasing. This result illustrates that the migration and reaction between dissolved polysulfide in PP 14 TFSI and lithium cannot be neglected although the solubility of polysulfide is slight in PP 14 TFSI solvent. However, when PI separators are introduced, besides improving the wettability with PP 14 TFSI-based electrolytes, experimental results also show that the PI separator has a reversible adsorption function to dissoluble polysulfide which is used to confining polysulfide in separator area to a certain extent due to the abundant nitrogen-, oxygen-containing functional groups in PI skeleton. What’s more, PI separator can decreases the sulfur content on lithium surface after cycling to 17.92% which decreases greatly than that with PP separator and improves its electrochemical performance.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Zhenwei Li,Shaoshao Jiao,Di Yu,Qian Zhang,Kang Liu,Jishu Han,Ziyang Guo,Jie Liu,Lei Wang
Because of the advantages of high theoretical capacity, low cost, and environmental friendliness, lithium–sulfur (Li–S) batteries have attracted wide attention as promising energy storage system for electric vehicles and smart power grids. However, their commercialization is still greatly restricted by their poor cycle stability, resulting from the severe shuttling of soluble lithium polysulfides (LiPSs) during cycling. Herein, we designed a CNT@cationic polymer/rGO (CNT@CP/rGO) blocking layer on a commercial PP separator. Such a blocking layer can strongly fix LiPSs by the electrostatic attraction effect between the cationic polymer backbones and the polysulfide anions. As a result, a Li–S battery equipped with a CNTs@CP/rGO-functionalized separator showed much improved cycling stability with a capacity fading rate as low as 0.06% per cycle during 700 cycles at 1 C. Especially, high areal capacity of 6.3 mAh cm–2 was also achieved with a high sulfur loading of 8.5 mg cm–2 after 50 cycles. This work highly emphasizes that the electrostatic attraction mechanism between cationic polymers and polysulfides can effectively restrain the polysulfide shuttling and thus significantly improve the electrochemical performance of Li–S batteries.
研究领域:
储能
·
电化学
·
材料科学
·
电池技术
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DOI
高影响因子
ACS Applied Nano Materials
·
2023
·
IF 5.9
Yuemin Li,Xinlong Bao,Xinwei Wang,Jianxun Zhao,Peng Chen,Heng Liu,Huan Wang,Lianshan Sun,Wanqiang Liu
The shuttling effect of polysulfide and its sluggish reaction kinetics are the primary issues with lithium–sulfur (Li–S) batteries. In this work, an improved coimpregnation technique was used to add cobalt atoms to nitrogen-doped carbon nanotubes (Co-NCNTs) and compound them onto mesoporous silicon (SiO2). Co-NCNTs/SiO2 composites were then used as modification materials for Li–S battery separators, which were capable of physical and chemical adsorption of lithium polysulfide (LiPSs). Between silica and LiPSs, there is chemical as well as physical adsorption in the mesoporous structure of the mesoporous silica. Cobalt has a significant capacity for adsorbing LiPSs, and the cobalt site possesses catalytic activity that can promote the redox kinetics of LiPSs. NCNTs have better electrical conductivity and a dense network structure, which facilitates electrolyte penetration and Li+ transfer. As a result, Li–S batteries built with a modified separator made of Co-NCNTs/SiO2 exhibit good capacity, cycle performance, and multiplier performance, with a 1314 mA h g–1 initial capacity at 0.2 C. After 200 cycles at 1 C, the capacity is 448 mA h g–1. This work proved that Co-NCNTs/SiO2 can efficiently adsorb LiPSs and accelerate their transformation, which slows down polysulfides’ shuttle effect and speeds up their slow kinetics.
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产品关联
DOI
高影响因子
Materials Today Energy
·
2023
·
IF 9.3
Xiyun Yang,Jiamin Liu,Fulu Chu,Jie Lei,Feixiang Wu
The shuttle effect and sluggish electrochemical conversion of polysulfides have been believed to strongly influence the performances of lithium-sulfur (Li–S) batteries. Herein, we propose the synthesis of nanosized Mo x C electrocatalysts embedded on N-doped graphene and develop its application for separator modification of Li–S batteries. The N-doped graphene provides a two-dimension conductive barrier layer to chemically adsorb polysulfides and inhibit polysulfides diffusion, while Mo x C nanoparticles could serve as the functional electrocatalyst to facilitate the redox kinetics of the multiphase conversion. The Li–S coin cells with Mo x C@N-rGO-modified separator can exhibit good long-term cycling stability with a capacity decay of 0.069% per cycle after 400 cycles at 0.5C and excellent rate performance with a discharge capacity of 653 mAh/g at 4C. An area capacity of 4.5 mAh/cm 2 is also achieved with a high sulfur loading of 5.2 mg/cm 2 and a low electrolyte/sulfur ratio of ∼5 μL/mg.
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产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Qin Dong,Tao Wang,Die Su,Ruiyi Gan,Minhua Shao,Cunpu Li,Qingfei Liu,Zidong Wei
The commercialization of Li–S batteries has been seriously hampered by the infamous “shuttle effect” of soluble lithium polysulfide intermediates (LiPSs, Li 2 S x , 4 ≤ x ≤ 8) and sluggish sulfur species conversion kinetics. In this work, vinyl ferrocene and styrene were copolymerized onto a polypropylene (PP) separator to prevent LiPS shuttling based on the electrostatic and orbital interactions between ferrocene and LiPSs, which increased the reactivity of LiPSs. Therefore, the “shuttle effect” can be successfully suppressed by a separator that combines thermodynamic anchoring and kinetic acceleration for LiPSs.
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Weijie Song,Gengjie Wang,Dongbo Zhao,Yuewei Zhou,Yuying Ding,Changbin Tan,Shaochun Tang,Hao Dong,Xiangkang Meng
In this work, new insights into dependence of electrochemical performance enhancement on transition metals’ rich mixed valence and their atomic ratio as well as redox active polysulfides are proposed. Especially, the influence of atomic ratio is further demonstrated by both experiments and density functional theoretical calculation where increasing Co/S leads to the enlargement of both interatom distance and hole diameter in a MnxCoySz cell. We rationally designed and prepared novel flexible electrodes of a rich mixed-valence polysulfide MnxCoySz/carbon nanotube film (CNTF) through acid activation of a dense CNTF into a hydrogel-like conductive matrix, growth of the MnxCoy(CO3)0.5OH precursor on each CNT, and controlled sulfidation. Nanostructure control allows us to obtain fast electron/ion transfer and increased availability of active sites/interfaces. The optimal MnCo9S10/CNTF shows a specific capacitance reaching 450 F cm–3 at 10 mA cm–2, much higher than reported values for CNT-based electrodes. Also, it exhibits remarkable cycling stability with only 1.6% capacity loss after 10 000 cycles at a high current density of 80 mA cm–2. An all-solid-state asymmetric supercapacitor (ASC) applying MnCo9S10/CNTF delivers an exceptionally high volumetric energy density of 67 mW h cm–3 (at 10 W cm–3). Particularly, integrated electric sources with adjustable output voltages can be obtained by connecting several ASCs in series, and there are no structural failure and capacity loss during repeated large-angle twisting and vigorous hammering. This work provides a general route to energy storage devices with ultrahigh volumetric energy density and outstanding reliability for wearable electronics.
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产品关联
DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2023
·
IF 5.9
Weiwei Li,Bin Yang,Ruixue Pang,Linxin Zhong,Meiyun Zhang
Separators are essential for supplying ion transport channels and preventing short circuits. Despite considerable effort, high-performance separators with desirable overall properties such as excellent thermostability, wettability, and impressive properties for suppressing lithium dendrites and polysulfide intermediates remain elusive. Here, we present an aramid nanofiber (ANF) and metal–organic framework (MOF) composite separator (ANF@MOFs) utilizing in situ growth of MOFs onto the extremely porous ANF network substrate. Benefiting from the features of the excellent strength, modulus, and nanoporosity of the ANF network, as well as the enormous specific surface area and sufficient metal sites of MOFs, the resultant ANF@MOFs separator exhibits excellent mechanical strength (a tensile strength of 110.7 MPa and a modulus of 3.1 GPa), improved liquid electrolyte wettability (an electrolyte uptake of 258.3%), and exceptional thermal stability (dimensionally stable after heating at 200 °C for 0.5 h). The ANF@MOFs separator not only demonstrates promising capabilities for physically blocking and chemically adsorbing Li2S2/Li2S and hence suppressing the Li2Sx shuttle effect but also suppresses the perforation of lithium dendrites, resulting in remarkable electrochemical and safety features. The battery equipped with the ANF@MOFs separator has a high first-cycle discharge capacity of 1081.92 mAh g–1 and a prolonged cycling performance with a capacity of 876.36 mAh g–1 at 0.5 C after 200 cycles. As a result, the high-performance ANF@MOFs composite separator provides significant potential for future lithium–sulfur batteries.
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2022
·
IF 9.965
Jianfeng Wang,Jun Li
The traditional PP separator is failed to inhibit the polysulfide shuttle effect for the lithium-sulfur ctteries. Besides, it has poor safety porblem when used at high temperatures. Therefore, it is urgent to develop new modified separator to repalce the traditional separator. To deal with these problems, layered hierarchical C@MoS 2 spheres are prepared and modified the traditional separator. Due to the presence of the C@MoS 2 modified separator, the Li-S batteries with C@MoS 2 separator display high specific capacity and superior cycling stability even at high rate of 2C. The high electrochemical performance is attributed to efficient inhibition of shuttle effect by the adsorption and catalytic conversion of polysulfide on the C@MoS 2 separator. This work has a certain reference value for the future large-scale application of lithium-sulfur battery.
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产品关联
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2021
·Vol. 11
·期 22
·7445-7453
·
IF 6.119
Yijuan Wang,Ziyi Guo,Jianzhi Wang,Ningbo Yu,Yanan Xue,Faquan Yu
Crystal structure and morphology can be regulated by inducing the positioning growth of metal sulfide, which is an efficient strategy to improve the oxygen evolution activity of the anode. Herein, solid NiMoO4 nanoplate arrays were used as cages to immobilize the metal source, and Mo doped NiSx is obtained by in situ solvothermal sulfuration reaction with polysulfide as the sulfur source. The electronic structure, conductivity, crystallographic phase and microscopic morphology of oxygen evolution catalysts could be controlled simultaneously by polysulfide induced solid metal oxide sulfidation, thereby greatly improving their electrocatalytic oxygen evolution activity. Benefiting from these, the prepared Mo doped nickel-sulfur electrodes show great performance toward the oxygen evolution reaction with overpotentials of 184 mV and 240 mV at current densities of 50 and 100 mA cm−2 in alkaline electrolyte. This study provides a new pathway by polysulfide induced sulfidation based on solid metal oxide for developing metal sulfide electrode materials with high oxygen evolution reaction performance for overall water splitting.
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2020
·
IF 7.489
Jianfeng Wang,Jun Li
In this study, we have developed a new strategy to modify the pristine polypropylene film by using cobalt-based zeolitic imidazolate framework-67. The structure and morphology of ZIF-67 were observed via powder X-ray diffraction and scanning electron microscopy. Results indicate that the as-prepared ZIF-67 exhibits cubic structure with diameter of 80–100 nm. N 2 absorption–desorption test confirms the presence of mespores in the ZIF-67 cubes . The ZIF-67 was used to modify the polypropylene film that was tested in popular lithium-sulfur batteries . Electrochemical results indicate that the Li-S batteries used ZIF-67/PP films exhibit high initial specific capacity of 1365 mAh g −1 at 0.1C. Besides, it shows high capacity of 816 mAh g −1 after 300 cycles at 2C, displaying superior cycling stability. The excellent electrochemical performance is attributed the strong adsorption ability of ZIF-67/PP film between polysulfide and ZIF-67. Therefore, the proposed strategy could provide a promising approach to promoting the commercial applications of Li-S batteries.
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）