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JOURNAL OF NANOPARTICLE RESEARCH · 2016 ·Vol. 18 ·期 7 ·1-8 · IF 2.101

Synthesis of selenium/EDTA-derived porous carbon composite as a Li–Se battery cathode

Zhao Chenhao,Fang Shuzhen,Hu Zhibiao,Qiu Sheng’en,Liu Kaiyu

The carbon substrate with unique 3D macroporous structure has been prepared through the immediate carbonization of ethylenediaminetetraacetic acid (EDTA) and KOH mixture. The porous carbon composed of micro- and small mesoporous (2–5 nm) structure has a BET specific surface area of 1824.8 m 2  g −1 . The amorphous and nanosized Se is uniformly encapsulated into the porous structure of porous carbon using melting diffusion route, and the weight content of Se in target Se/C composite can be as high as ~50 %. As an Li–Se battery cathode, the Se/C composite delivers a reversible (2nd) discharge capacity of 597.4 mAh g −1 at 0.24C and retains a discharge capacity of 538.4 mAh g −1 at 0.24C after 100 cycles. Furthermore, the composite also has a stable capacity of 291.0 mAh g −1 at a high current of 4.8C. The high specific area and good porous size of EDTA-derived carbon substrate may a be responsibility for the excellent electrochemical performances of Se/C composite.

CAS / MDL: 7782-49-2
研究领域: 材料科学 · 能源存储
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Nanoscale · 2019 ·Vol. 11 ·期 14 ·6970-6981 · IF 6.97

MOF-derived nitrogen-doped core–shell hierarchical porous carbon confining selenium for advanced lithium–selenium batteries

Jian-Ping Song,Liang Wu,Wen-Da Dong,Chao-Fan Li,Li-Hua Chen,Xin Dai,Chao Li,Hao Chen,Wei Zou,Wen-Bei Yu,Zhi-Yi Hu,Jing Liu,Hong-En Wang,Yu Li,Bao-Lian Su

The lithium–selenium (Li–Se) battery has attracted growing interest recently due to its high energy density and theoretical capacity. However, the shuttle effect and volume change during cycling severely hinder its further application. In this work, we report a metal–organic framework (MOF)-derived nitrogen-doped core–shell hierarchical porous carbon (N-CSHPC) with interconnected meso/micropores to effectively confine Se for high-performance Li–Se batteries. The micropores were located at the ZIF-8-derived core and the ZIF-67-derived shell, while mesopores appeared at the core–shell interface after the pyrolysis of the core–shell ZIF-8@ZIF-67 precursor. Such a special hierarchical porous structure effectively confined selenium and polyselenides to prevent their dissolution from the pores and also alleviated the volume change. In particular, in situ nitrogen doping, which afforded N-CSHPC, not only improved the electrical conductivity of Se but also provided strong chemical adsorption on Li2Se, as confirmed by density functional theory calculations. On the basis of dual-physical confinement and strong chemisorption, Se/N-CSHPC-II (molar ratio of Co source to Zn source of 1.0 in the core–shell ZIF-8@ZIF-67 precursor) exhibited reversible capacities of up to 555 mA h g−1 after 150 cycles at 0.2 C and 462 mA h g−1 after 200 cycles at 0.5 C and even a discharge capacity of 432 mA h g−1 after 200 cycles at 1 C. Our demonstration here suggests that the carefully designed Se/C composite can improve the reversible capacity and cycling stability of Se cathodes for Li–Se batteries.

研究领域: 材料科学 · 电化学
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RSC Advances · 2014 ·Vol. 4 ·期 74 ·39312-39315 · IF 3.708

Encapsulation of selenium in porous hollow carbon spheres for advanced lithium–selenium batteries

Yanqing Lai,Fuhua Yang,Zhian Zhang,Shaofeng Jiang,Jie Li

Porous hollow carbon spheres (PHCSs) with high surface area and large pore volume were synthesised using a facile template method. After selenium (Se) encapsulation, Se/PHCS composite was formed. The obtained Se/PHCS composite was demonstrated as a suitable cathode material for lithium–selenium batteries.

CAS / MDL: 7782-49-2
研究领域: 材料科学 · 能源存储
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CHEMISTRY-A EUROPEAN JOURNAL · 2017 ·Vol. 24 ·期 9 ·2151-2156 · IF 5.317

A Self-Repairing Cathode Material for Lithium–Selenium Batteries: Se−C Chemically Bonded Selenium–Graphene Composite

Linna Sha,Peng Gao,Xiaochen Ren,Qianqian Chi,Yujin Chen,Piaoping Yang

Graphical Let it Se : An Se−C-bonded interface has been constructed in a Se–graphene (GE) composite through facile high-energy ball-milling. Due to the presence of Se−C bonds, a new self-repairing Se-GE cathode material has been obtained (see graphic). It shows high reversible capacity, long cycle life, and high coulombic efficiency. Lithium–selenium batteries, employing selenium as a cathode material, exhibit some notable advantages, such as high discharge rates and good cycling performance, due to their high electrical conductivity, high output voltages, and high volumetric capacity density. However, an important problem, termed the “shuttle effect”, can lead to capacity decay in Li-Se cells (and in Li-S cells), which arises from aggregation and the loss of Se or S from the cathode into the electrolyte. In this work, in order to solve this problem, a new self-repairing system has been devised, in which some Se atoms are chemically bonded to the carbon atoms of graphene and act as reclaiming points for dissociated Se atoms through the establishment of -Se-Se-Se- chains. Se-decorated graphene (Se-GE) was first constructed through a facile high-energy ball-milling process. Its formation was confirmed by XRD, SEM, HRTEM, XPS, and Raman analyses. As we anticipated, in examining cell properties, the as-prepared Se-GE composite underwent an initial capacity decay in the first 20 cycles (from 1050 mAh g −1 to 750 mAh g −1 , ca. 29 % loss), but the capacity then reverted to 970 mAh g −1 (ca. 92 % of the initial value). Other measurements were also consistent with the recapture of dissociated Se atoms.

研究领域: 材料科学 · 电化学
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JOURNAL OF POWER SOURCES · 2015 · IF 6.217

Selenium/carbon-rich core–shell composites as cathode materials for rechargeable lithium–selenium batteries

Zhian Zhang,Xing Yang,Zaiping Guo,Yaohui Qu,Jie Li,Yanqing Lai

Selenium/carbon-rich (Se/carbon-rich) core–shell composites are prepared by a one-step hydrothermal synthesis method as a cathode for rechargeable lithium batteries . The Se/carbon-rich composites are characterized and examined by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetry (TGA) measurements. It is demonstrated from galvanostatic discharge/charge process that the Se/carbon-rich composites exhibit the discharge capacity of 558 mA h g −1 in the first cycle and maintain capacity of 181 mA h g −1 after 80 cycles at a rate of 0.5C, which is better than that of the pristine selenium. The result demonstrates that the unique core–shell structure is effective in suppressing the dissolution of polyselenides into the electrolyte and in maintaining high utilization of the active materials during the charge/discharge process. It provides a new selenium-based cathode material for rechargeable lithium batteries .

研究领域: 材料科学 · 电化学
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SOLID STATE IONICS · 2015 · IF 2.561

A bimodal porous carbon with high surface area supported selenium cathode for advanced Li–Se batteries

Yaohui Qu,Zhian Zhang,Yanqing Lai,Yexiang Liu,Jie Li

A novel bimodal porous carbon (BPC) with high surface area was prepared by a simple hydrothermal route and KOH activation process , and the Se–BPC composite was synthesized for lithium–selenium batteries by the melt-diffusion method. It is found that the elemental selenium was dispersed inside the pores of BPC based on the analyses. Electrochemical tests reveal that the Se–BPC composite has a large reversible capacity and high rate performance as cathode materials . The Se–BPC (45.1   wt.% Se) composite displays an initial discharge capacity of 552   mAh   g −   1 and a reversible discharge capacity of 264   mAh   g −   1 after 80   cycles at 1   C charge/discharge rate. In particular, the Se–BPC composite presents a durable cycling performance at high rate of 2   C. These outstanding electrochemical features of Se–BPC composite cathode should be attributed to the uniform BPC with high surface area and bimodal porous structure . The bimodal porous carbon would be a promising carbon matrix to develop high performance lithium–selenium batteries.

CAS / MDL: 7782-49-2
研究领域: 材料科学 · 电化学
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CARBON · 2021 · IF 9.594

Bioderived carbon fiber conductive networks with inlaid electrocatalysts as an ultralight freestanding interlayer for working Li–SeS2 pouch cells

Yin Zhang,Boya Wang,Peng Jing,Yi Guo,Yueying Zhang,Yunhong Wei,Qian Wang,Yun Zhang,Hao Wu

Introducing a freestanding functional interlayer has been a conventional tactic to immobilize the soluble polysulfide intermediate in Li–S batteries . However, most of the designed interlayers possess extra heavy weight, casting additional technical challenges toward practical high-specific-energy batteries. Herein, an ultralight self-standing interlayer with an extremely low mass loading (∼0.14 mg cm −2 ), composed of porous curly carbon fibers derived from natural biomass with inlaid cobalt electrocatalysts (CF–Co), was engineered via a convenient way. After replacing the poor conductivity sulfur (∼10 −28  S m −1 ) by higher conductivity selenium disulfide (SeS 2 , ∼10 −6  S m −1 ) as active cathode materials , the hierarchically porous-structured, conductive CF-Co interlayer with outstanding adsorptive and electrocatalytic effects is introduced into the resulted Li–SeS 2 batteries to capture dual-intermediate polysulfides/polyselenides, boost their conversion kinetics, and ensure favorable running of Li–SeS 2 cells with high SeS 2 loading and lean electrolyte. Consequently, the coin cells deliver outstanding high-rate capability (404 mAh g −1  at 8 A g −1 ) and superior cycling stability (∼81.5% areal capacity retention in 125 cycles) under high SeS 2 loading (5.0 mg cm −2 ). Significantly, practical high-areal-capacity (>5.5 mAh cm −2 ) Li–SeS 2 pouch cells can be realized by assembling this interlayer with double-side SeS 2 -loading cathodes (132 mg), working stably at relatively lower electrolyte condition (6.0 μL mg −1 ).

CAS / MDL: 7791-13-1
研究领域: 材料科学 · 能源存储
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SOLID STATE SCIENCES · 2018 · IF 1.861

Hierarchical porous carbon/selenium composites derived from abandoned paper cup as Li-Se battery cathodes

Shaocun Liu,Qingping Lu,Chenhao Zhao

Paper cup composed of crude cellulose is a common waste in daily life. In this paper, hierarchical porous carbons have been successfully prepared by an initial hydrothermal treatment and subsequent activation route from abandoned paper cup, and then paper cup derived carbons are used as scaffolds to fabricate serial carbon/Se composites. The optimal composite presents unique 3D porous structure, with amorphous selenium uniformly confined into the micropores of carbon. As the cathode materials of Li-Se battery, this composite reveals an initial reversible discharge capacity of 517.2 mAh g −1 at 0.2C, and a capacity value of 431.9 mAh g −1 can be retained after 60 cycles. Even at a high rate of 4C, a capacity value of 295.8 mAh g −1 can be obtained. By comparison, the improved electrochemical performance of the optimal composite should be attributed to reasonable porous structure and effective encapsulation of amorphous selenium.

研究领域: 材料科学 · 能源存储
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Surface iodine modification inducing robust CEI enables ultra-stable Li-Se batteries

Mingran Zhou,Wenda Dong,Ao Xu,Zhiwen Yin,Zhi-Yi Hu,Xinling Wang,Liang Wu,Lihua Chen,Yu Li,Bao-Lian Su

Lithium-selenium batteries (LSeBs) have attracted increasing attention due to their excellent electronic conductivity and high theoretical specific capacity. However, there are still difficult problems such as low utilization rate and fast capacity decay in the actual application process. Herein, a surface iodine modified three-dimensional (3D) nano hollow carbon fiber (I-NHCF) network is designed and synthesized as Se host (Se@I-NHCF) for highly stable LSeBs. The surface iodine species induce the formation of robust cathode electrolyte interface (CEI), thus preventing the transformation of amorphous selenium to low-activity crystalline selenium and enabling stable electrochemical performance. Moreover, the surface iodine species promote rapid charge transfer, enhancing the chemical reaction kinetics and improving the utilization of the active Se species. As a result, the Se@I-NHCF cathode exhibits superior specific capacity of 581.8 mAh g −1 with a high stability (0.0054% capacity decay per cycle) after 500 cycles at 1C, and an excellent rate performance of 567.6 mAh g −1 at 2C. This work addresses the problem of rapid capacity decay by the formation of uniform and robust CEI to conserve highly reactive amorphous Se species, improve Se utilization, and achieve ultra-stable Li-Se batteries with high energy and long cycle life.

研究领域: 材料科学 · 能源存储与转换
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CHEMISTRY OF MATERIALS · 2015 · IF 8.354

Amorphous, Crystalline and Crystalline/Amorphous Selenium Nanowires and Their Different (De)Lithiation Mechanisms

Xiaoming Zhou,Peng Gao,Shuchao Sun,Di Bao,Ying Wang,Xiaobo Li,Tingting Wu,Yujin Chen,Piaoping Yang

Selenium is applied as the cathode material of lithium/selenium (Li–Se) battery, which has high theoretical volumetric capacity density (3253 mA h·cm–3) and high output voltages. However, it has a low melting point (494 K) and a large sensitivity to thermal treatment, which often result in the phase transition between crystalline Se (trigonal phase) and amorphous Se during the charge/discharge cycles of Li–Se battery as reported in literatures. In order to clarify the different chemical (de)lithiation mechanisms between them in Li–Se battery, in this work large-area amorphous selenium (a-Se) nanowires (NWs) have been successfully prepared first through a facile high-energy ball-milling method. Subsequently the crystalline (c) and crystalline/amorphous (c/a) selenium NWs have also been prepared through annealing the above as-obtained amorphous products, respectively. The affirmative composition and morphology of the as-obtained Se nanostructures have been demonstrated by the XRD, SEM, TEM, HRTEM and Raman spectra measurements. And their specific surface area and pore size distribution have also been analyzed by BET measurements. Finally, it is proved that the as-obtained NWs used as the cathode material of Li–Se battery displayed different chemical reaction processes with Li+ and the related various storage capacities (a-Se: 755 mAh·g–1; c/a-Se: 705 mAh·g–1; c-Se: 250 mAh·g–1). This work has helped us to better understand and correlate the formation of intermediate phases with the electrochemical performance of Li–Se cells and shines new light on how to improve the cell performance by turning the phase of Se.

CAS / MDL: 7782-49-2
研究领域: 材料科学 · 电化学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2014 · IF 2.726

Facile synthesis of hollow carbonized polyaniline spheres to encapsulate selenium for advanced rechargeable lithium–selenium batteries

Jie Li,Xingxing Zhao,Zhian Zhang,Yanqing Lai

A hollow carbonized polyaniline spheres/selenium (HCPS/Se) composite was prepared by a simple combination method of a self-assembly method, pyrolysis and vapor phase infusion process as a cathode material for Li–Se rechargeable batteries. The composites were characterized and examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, the X-ray photoelectron spectroscopy and electrochemical methods, such as cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge tests. The HCPS/Se composite cathode can deliver relative high capacity, high Coulombic efficiency and good cycling performance. The electrochemical results show that the HCPS/Se composite cathode exhibits an initial discharge specific capacity of 571.5   mA   h   g −1 and retains 298.7   mA   h   g −1 with high Coulombic efficiency after 100 cycles at a high rate of 0.5   C (337.5   mA   h   g −1 ), which are higher than that of the pristine selenium cathode. The excellent electrochemical properties benefit from the high conductivity and the hollow structures of the carbonized polyaniline spheres.

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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JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS · 2024 · IF 4.3

Natural okra gum as functional binder enables highly stable Lithium–Selenium batteries

Yang Xia,Jun Tong,Chengwei Lu,Xinping He,Yongping Gan,Hui Huang,Jun Zhang,Xinhui Xia,Wenkui Zhang,Zhen Xiao,Ruyi Fang

Lithium–selenium (Li–Se) batteries are garnered significant attention due to their high theoretical specific capacity, high volumetric energy density and moderate output voltage. Nevertheless, Li–Se batteries are still restricted by severe volume expansion and “shuttle effect” of polyselenides, resulting in deteriorated electrochemical performance . Binders are a crucial component of Li–Se batteries, playing a key role in addressing the mentioned issues. Herein, a non-toxic, bio-friendly, hydro-soluble binder of okra gum (OG) extracted from okra pods is proposed to ameliorate the electrochemical performance of Li–Se batteries. The as-prepared OG binders are rich in branched-chain polysaccharides (glucoside) and polar functional groups (–C–O–C–, –COOH), which not only have a good interpenetrating binding network to ensure the mechanical stability of Se cathode, but also have excellent interfacial chemical binding force for immobilizing polyselenides. Consequently, the OG binder endows Li–Se batteries with high initial discharge capacity (607 mA h g −1  at 0.2C), good cycling stability (218 mA h g −1 after 100 cycles at 0.2C), and remarkable rate performance (364 mA h g −1  at 1C), all of which are superior to Li–Se batteries with PVDF binder. Our study demonstrates the feasibility of natural mucilage as functional binder for Li–Se batteries and paves a research path in developing natural plant-based binders to stabilize electrode materials for reliable high-energy batteries.

CAS / MDL: 7580-67-8
研究领域: 材料科学 · 能源技术
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