In-situ PECVD-enabled graphene-V₂O₃ hybrid host for lithium–sulfur batteries

Song, Yingze,Zhao, Wen,Wei, Nan,Zhang, Li,Ding, Feng,Liu, Zhongfan,Sun, Jingyu Elsevier 2018 Nano energy Vol.53 No.-

<P><B>Abstract</B></P> <P>Lithium–sulfur (Li–S) batteries have been regarded as promising candidates for current energy-storage technologies due to their remarkable advantages in energy density and theoretical capacity. However, one of the daunting challenges remained for advanced Li–S systems thus far deals with the synchronous suppression of polysulfide (LiPS) shuttle and acceleration of redox kinetics. Herein, a cooperative interface bridging adsorptive V<SUB>2</SUB>O<SUB>3</SUB> and conductive graphene is constructed <I>in-situ</I> by virtue of direct plasma-enhanced chemical vapor deposition (PECVD), resulting in the design of a novel V<SUB>2</SUB>O<SUB>3</SUB>-graphene hybrid host to synergize the LiPS entrapment and conversion. The redox kinetics and electrochemical performances of thus-derived cathodes were accordingly enhanced owing to the smooth adsorption-diffusion-conversion of LiPSs even at a sulfur mass loading of 3.7 mg cm<SUP>–2</SUP>. Such interfacial engineering offers us a valuable opportunity to gain insight into the comprehensive regulation of LiPS anchoring ability, electrical conductivity and ion diffusive capability in hybrid hosts on suppressing the LiPS shuttle and propelling the redox kinetics. Our devised PECVD route might pave a new route toward the facial and economic design of hetero-phased multi-functional hosts for high-performance Li–S systems.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Graphene-V<SUB>2</SUB>O<SUB>3</SUB> hybrid host was designed <I>in-situ</I> based on PECVD route. </LI> <LI> Thus-derived cathode showed a low capacity decay of merely 0.046% per cycle at 2 C after 1000 cycles. </LI> <LI> Cathodes with a relatively high sulfur mass loading (3.7 mg cm<SUP>–2</SUP>) were fabricated. </LI> <LI> The smooth adsorption-diffusion-conversion of polysulfides was thoroughly probed <I>via</I> experimental studies and DFT simulations. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Synthesis of full concentration gradient cathode studied by high energy X-ray diffraction

Li, Yan,Xu, Rui,Ren, Yang,Lu, Jun,Wu, Huiming,Wang, Lifen,Miller, Dean J.,Sun, Yang-Kook,Amine, Khalil,Chen, Zonghai Elsevier 2016 Nano energy Vol.19 No.-

<P><B>Abstract</B></P> <P>Nickel-rich metal oxides have been widely pursued as promising cathode materials for high energy-density lithium-ion batteries. Nickel-rich lithium transition metal oxides can deliver a high specific capacity during cycling, but can react with non-aqueous electrolytes. In this work, we have employed a full concentration gradient (FCG) design to provide a nickel-rich core to deliver high capacity and a manganese-rich outer layer to provide enhanced stability and cycle life. <I>In situ</I> high-energy X-ray diffraction was utilized to study the structural evolution of oxides during the solid-state synthesis of FCG lithium transition metal oxide with a nominal composition of LiNi<SUB>0.6</SUB>Mn<SUB>0.2</SUB>Co<SUB>0.2</SUB>O<SUB>2</SUB>. We found that both the pre-heating step and the sintering temperature were critical in controlling phase separation of the transition metal oxides and minimizing the content of Li<SUB>2</SUB>CO<SUB>3</SUB> and NiO, both of which deteriorate the electrochemical performance of the final material. The insights revealed in this work can also be utilized for the design of other nickel-rich high energy-density cathode materials.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Solid-state synthesis of FCG cathode is investigated by <I>in situ</I> XRD. </LI> <LI> Covariance analysis and Rietveld refinement are used to analyze the HEXRD data. </LI> <LI> Synthetic optimization of FCG cathode with excellent electrochemical performance. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>Benefit from the covariance analysis and Rietveld refinement of <I>in situ</I> HEXRD data during the solid state synthesis, we can optimized the solid state synthesis conditions in a short time. And the full concentration gradient cathode composites (nickel-rich core and manganese-rich outer layer) with excellent electrochemical performance are obtained.</P> <P>[DISPLAY OMISSION]</P>

Nano/Microstructured Silicon-Graphite Composite Anode for High-Energy-Density Li-Ion Battery

Li, Peng,Hwang, Jang-Yeon,Sun, Yang-Kook American Chemical Society 2019 ACS NANO Vol.13 No.2

<P>With the ever-increasing demand for lithium-ion batteries (LIBs) with higher energy density, tremendous attention has been paid to design various silicon-active materials as alternative electrodes due to their high theoretical capacity (ca. 3579 mAh g<SUP>-1</SUP>). However, totally replacing the commercially utilized graphite with silicon is still insurmountable owing to bottlenecks such as low electrode loading and insufficient areal capacity. Thus, in this study, we turn back to enhanced graphite electrode through the cooperation of modified silicon via a facile and scalable blending process. The modified nano/microstructured silicon with boron doping and carbon nanotube wedging (B-Si/CNT) can provide improved stability (88.2% retention after 200 cycles at 2000 mA g<SUP>-1</SUP>) and high reversible capacity (∼2426 mAh g<SUP>-1</SUP>), whereas the graphite can act as a tough framework for high loading. Owing to the synergistic effect, the resultant B-Si/CNT-graphite composite (B-Si/CNT@G) shows a high areal capacity of 5.2 mAh cm<SUP>-2</SUP> and excellent cycle retention of 83.4% over 100 cycles, even with ultrahigh active mass loading of 11.2 mg cm<SUP>-2</SUP>,which could significantly surpass the commercially used graphite electrode. Notably, the composite also exhibits impressive application in Li-ion full battery using 2 mol % Al-doped full-concentration-gradient Li[Ni<SUB>0.76</SUB>Co<SUB>0.09</SUB>Mn<SUB>0.15</SUB>]O<SUB>2</SUB> (Al2-FCG76) as the cathode with excellent capacity retention of 82.5% even after 300 cycles and an outstanding energy density (8.0 mWh cm<SUP>-2</SUP>) based on the large mass loading of the cathode (12.0 mg cm<SUP>-2</SUP>).</P> [FIG OMISSION]</BR>

Controllable Synthesis of Co-Doped Spinel LiMn2O4 Nanotubes as Cathodes for Li-Ion Batteries

Li-Xin Zhang,Yuan-Zhong Wang,Hong-Fang Jiu,Ya-Lei Wang,Yi-Xin Sun,Zhenzhong Li 대한금속·재료학회 2014 ELECTRONIC MATERIALS LETTERS Vol.10 No.2

Spinel Co-LiMn2O4 nanotubes have been synthesized via solid state reaction using α-MnO2 nanotubes as selftemplates. The as-prepared powders were investigated by XRD, TEM, and galvanostatic discharge/charge analysis. The optimal doping amount was confirmed by galvanostatic charge/discharge measurements. The results indicate that about 67% of initial capacity (115 mAh/g) of LiMn2O4 nanotubes can be retained after 50 cycles. For Co-LiMn2O4 nanotubes, the initial reversible capacity is 126.6 mAh/g and 100 mAh/g can be maintained after 50 cycles. The capacitance retention rate of Co-LiMn2O4 nanotubes is as high as 79%. These results indicate that the doping Co can effectively improve circle stability and electrochemical performance of LiMn2O4 nanotubes.

Structural, magnetic and dielectric properties of (Li1+, Al3+) co-doped Ni0.5Zn0.5Fe2O4 ferrite ceramics prepared by the sol-gel auto-combustion method

Qing Ni,Li Sun,Ensi Cao,Wentao Hao,Yongjia Zhang,Lin Ju 한국물리학회 2020 Current Applied Physics Vol.20 No.9

(Li1+, Al3+) co-doped Ni0.5Zn0.5Fe2O4 ferrites, Ni0.5-xZn0.5-xLixAlxFe2O4 (x = 0.000, 0.025, 0.050 and 0.100), were synthesized by the sol-gel auto-combustion method. X-ray diffraction (XRD), field emission scanning electronic microscope (FESEM), vibrating sample magnetometer (VSM) and LCR meter were used to investigate the structural, magnetic and dielectric properties. Results of XRD and SEM indicate that both doping amount and calcination temperature play significant roles in crystal structure and grain growth. Also, it can be observed that the saturation magnetization and the coercivity change in a noticeable manner. The Ni0.475Zn0.475Li0.025Al0.025Fe2O4 ferrite sintered at 1200 °C has a relatively low coercivity value (62.93 Oe) and the largest saturation magnetization (110.95 emu/g). Besides, dielectric behavior is also improved by Li1+ and Al3+ co-doping

Membrane technologies for Li+/Mg2+ separation from salt-lake brines and seawater: A comprehensive review

Ye Zhang,Li Wang,Wei Sun,Yue-hua Hu,Honghu Tang 한국공업화학회 2020 Journal of Industrial and Engineering Chemistry Vol.81 No.-

Recent years have seen rapid improvement of technology and large-scale applications of lithium-ionbatteries, which leads to an increasing market demand for lithium. Since the land lithium resources arediminishing drastically, the sources of lithium extraction have shifted to the large amount of waterresources containing salt-lake brines and seawater. Among the varieties of aqueous recovery approaches,membrane technology seems to have huge development potential and good application prospect. This isbecause the membrane technologies exhibit excellent Li/Mg separation selectivity, with low energyconsumption and green process owing to no addition of chemicals. The present work reviews the latestadvances in various membrane technologies, including nanofiltration membrane, electrodialysis,membrane capacitive deionization approaches, solid electrolyte electrolysis-based technology, etc. Therecent developments in positively charged nanofiltration membrane are discussed in terms of thepreparation methods, membrane properties, and Li/Mg separation coefficient. In addition, the effects ofseveral factors on electrodialysis for lithium extraction and relevant mechanisms in both simple andactual saline systems are discussed, including applied voltage, VC/VD, and coexisting ions. Theapplications of electrodialysis with novel selective membrane involving nanofiltration membrane as wellas solid electrolyte membrane and perspectives for further investigation are proposed.

Synchronous immobilization and conversion of polysulfides on a VO₂-VN binary host targeting high sulfur load Li-S batteries

Song, Yingze,Zhao, Wen,Kong, Long,Zhang, Li,Zhu, Xingyu,Shao, Yuanlong,Ding, Feng,Zhang, Qiang,Sun, Jingyu,Liu, Zhongfan The Royal Society of Chemistry 2018 ENERGY AND ENVIRONMENTAL SCIENCE Vol.11 No.9

<P>Lithium-sulfur (Li-S) batteries are deemed as one of the most promising next-generation energy storage systems. However, their practical application is hindered by existing drawbacks such as poor cycling life and low Coulombic efficiency due to the shuttle effect of lithium polysulfides (LiPSs). We herein present an <I>in situ</I> constructed VO2-VN binary host which combines the merits of ultrafast anchoring (VO2) with electronic conducting (VN) to accomplish smooth immobilization-diffusion-conversion of LiPSs. Such synchronous advantages have effectively alleviated the polysulfide shuttling, promoted the redox kinetics, and hence improved the electrochemical performance of Li-S batteries. As a result, the sulfur cathode based on the VO2-VN/graphene host exhibited an impressive rate capability with ∼1105 and 935 mA h g<SUP>−1</SUP> at 1C and 2C, respectively, and maintained long-term cyclability with a low capacity decay of 0.06% per cycle within 800 cycles at 2C. More remarkably, favorable cyclic stability can be attained with a high sulfur loading (13.2 mg cm<SUP>−2</SUP>). Even at an elevated temperature (50 °C), the cathodes still delivered superior rate capacity. Our work emphasizes the importance of immobilization-diffusion-conversion of LiPSs toward the rational design of high-load and long-life Li-S batteries.</P>

Vanadium Dioxide-Graphene Composite with Ultrafast Anchoring Behavior of Polysulfides for Lithium-Sulfur Batteries

Song, Yingze,Zhao, Wen,Zhu, Xingyu,Zhang, Li,Li, Qiucheng,Ding, Feng,Liu, Zhongfan,Sun, Jingyu American Chemical Society 2018 ACS APPLIED MATERIALS & INTERFACES Vol.10 No.18

<P>The lithium-sulfur (Li-S) battery has been deemed as one of the most promising energy-storage systems owing to its high energy density, low cost, and environmental benignancy. However, the capacity decay and kinetic sluggishness stemming from polysulfide shuttle effects have by far posed a great challenge to practical performance. We herein demonstrate the employment of low-cost, wet-chemistry-derived VO<SUB>2</SUB> nanobelts as the effective host additives for the graphene-based sulfur cathode. The VO<SUB>2</SUB> nanobelts displayed an ultrafast anchoring behavior of polysulfides, managing to completely decolor the polysulfide solution in 50 s. Such a fast and strong anchoring ability of VO<SUB>2</SUB> was further investigated and verified by experimental and theoretical investigations. Benefitting from the synergistic effect exerted by VO<SUB>2</SUB> in terms of chemical confinement and catalytic conversion of polysulfides, the Li-S batteries incorporating VO<SUB>2</SUB> and graphene manifested excellent cycling and rate performances. Notably, the batteries delivered an initial discharge capacity of 1405 mAh g<SUP>-1</SUP> when cycling at 0.2 C, showed an advanced rate performance of ∼830 mAh g<SUP>-1</SUP> at 2 C, and maintained a stable cycling performance at high current densities of 1, 2, and 5 C over 200 cycles, paving a practical route toward cost-effective and environmentally benign cathode design for high-energy Li-S batteries.</P> [FIG OMISSION]</BR>

Antimony Selenide Nanorods Decorated on Reduced Graphene Oxide with Excellent Electrochemical Properties for Li-Ion Batteries

Wang, Xia,Wang, Hong,Li, Qiang,Li, Hongsen,Xu, Jie,Zhao, Guoxia,Li, Hongliang,Guo, Peizhi,Li, Shandong,Sun, Yang-kook The Electrochemical Society 2017 Journal of the Electrochemical Society Vol.164 No.13

<P>A promising anode material for lithium-ion batteries (LIBs) consisting of Sb2Se3 nanorods and reduced graphene oxide (rGO) sheets has been prepared by an effective solvothermal approach. The synergetic effect between Sb2Se3 nanorods and rGO matrix provides not only high conductivity paths and strong electron contact interface, but also alleviates the volume change of Sb2Se3 nanorods, resulting in excellent lithium-storage performance. When tested as an anode material for LIBs, a high capacity of 868.30 mAh g(-1) can be retained after 100 cycles at 200 mA g(-1). Even at 2000 mA g(-1), a satisfactory capacity of 430.40 mAh g(-1) after long 550 cycles can be delivered. Ex situ X-ray diffraction study suggests that the Sb2Se3/rGO composite follows the combined Li+ intercalation, conversion reaction and alloying reaction mechanism. These features suggest the Sb2Se3/rGO composite a viable choice for application as an anode material in high-performance LIBs. (C) 2017 The Electrochemical Society. All rights reserved.</P>

Superior lithium/potassium storage capability of nitrogen-rich porous carbon nanosheets derived from petroleum coke

Li, Peng,Hwang, Jang-Yeon,Park, Sang-Min,Sun, Yang-Kook The Royal Society of Chemistry 2018 Journal of Materials Chemistry A Vol.6 No.26

<P>Tremendous attention has been paid to carbon-based anodes for lithium-ion and potassium-ion batteries. Nevertheless, conferring high energy storage properties using carbon-based anodes is still challenging. In this work, petroleum coke-based nitrogen-doped porous carbon nanosheets (N-PCSs) were prepared using carbon nitride (g-C3N4) as both a template and nitrogen source and tested as advanced anode materials. The as-obtained N-PCSs constructed through an <I>in situ</I> solid-state approach possess both high capacity and excellent cycling stability. High capacities were obtained for Li-ion and K-ion batteries (407 mA h g<SUP>−1</SUP> after 500 cycles at 3720 mA g<SUP>−1</SUP> and 206 mA h g<SUP>−1</SUP> after 300 cycles at 1000 mA g<SUP>−1</SUP>, respectively); these are some of the best capacities for carbon-based electrode materials and could be ascribed to the unique microstructure of the anodes, <I>i.e.</I>, nanosheet morphology, developed porosity, ultrahigh nitrogen doping, and a high level of disorder. Meanwhile, this study represents a milestone for high-value utilization of petroleum coke and other kinds of heavy oil.</P>