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Nanoporous selenium as a cathode material for rechargeable lithiumselenium batteries Lili Liu,a Yuyang Hou,a Shiying Xiaoa Zheng Chang, a Yaqiong Yang a and Yuping Wu*a 5
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x A nanoporous selenium was prepared by a simple mechanical method adopting nano-CaCO3 as a template. When used as cathode, it can deliver relative high capacity and good cycling behaviour. These results present a great promise for this new cathode material for rechargeable lithium batteries of high energy density.
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Since the birth of rechargeable lithium batteries, they have been employed as a promising power source in various fields such as hybrid and plug-in hybrid electric vehicles, solar and wind electricity generation systems owing to the advantages of high energy densities, high operating voltages, low self-discharge and friendliness to environment.1,2 However, portable electronic devices and pure electric vehicles urgently need power sources of higher energy denisties,3 and many efforts have been made. Among these strategies, searching for novel electrode materials with high energy density 4-9 and adopting electrode materials with tunable morphologies such as nanoporous architecture 10-19 are mostly employed since porous architectures present large surface areas and thin walls, which are beneficial to the transportation of lithium ions in the active materials and the decrease of the polarization. 20-24 Selenium, a d-electron containing member of group 16 with high electrical conductivity (approximately 20 orders of magnitude greater than S) and Se-based materials have been explored as an electrode material for solar cells 25,26 and rechargeable batteries. 6,27,28 The redox reaction of Se electrode with lithium is as follows: 6 Se + 2Li+ + 2e- ↔ Li2Se (1) So this kind of lithium/selenium battery, which uses selenium as a cathode and Li as an anode, shows superior advantages over the widely studied lithium/sulfur systems: a) better rate and cycling performance without applying large quantities of additives such ad carbon due to the higher electric conductivity of Se in comparison with S; b) higher output voltages (approximately 0.5 V higher than that for Li/S) and the corresponding higher energy densities, which is quite important for commercial applications. 6 All these superiorities from the pioneering work of Amine’s laboratory indicate that Se will be an attractive new class cathode material for rechargeable lithium batteries. 6 In this study, we report a nanoporous Se prepared by a simple mechanical method adopting nano-CaCO3 as a template, and its electrochemical performance as a cathode material for lithium ion batteries is very good. This journal is © The Royal Society of Chemistry [year]
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The preparation procedure of the nanoporous Se is described as follows. All the reagents were analytical grade. The mixture of 1.0 g nano-CaCO3 (about 50 nm, Enping Jiawei Chemical Industrial Co., Ltd.) and 0.5 g commercial Se particles (Shanghai Meixing Chemical Industrial Co., Ltd.) were loaded into a 50 ml steel bowl containing 18 steel balls of 10 mm in diameter. After the high-energy ball-milling of the mixture at a rotation rate of 400 rpm for 12 h on a planetary ball mill, the obtained composite was calcined at 260 oC for 12 h at a heating rate of 2 oC/min under flowing nitrogen (99.99%, 200 mL min-1). Then the collected material was etched with 1 mol L-1 HCl solution for 2 h followed by centrifugation, washing with distilled water and ethanol and drying under vacuum overnight, the nanoporous Se product was prepared and denoted as NP-Se while the commercial Se particles were denoted as CP-Se for a control. Crystal structure of the prepared nanoporous Se was characterized by X-ray powder diffraction (XRD) using a Bruker Analytical X-ray System with CuKα radiation source filtered by a nickel thin plate. Scanning electron micrographs (SEM) and transmission electron micrographs (TEM) were obtained on a Philips XL30 scanning electron microscope and a JEOL JEM2010 transmission electron microscope, respectively. N 2 adsorption-desorption isotherms were collected on a Micromeritics ASAP 2010 adsorption analyzer at 196 oC (77 K), and the BET specific surface area was calculated. The electrochemical performances of the as-obtained NP-Se and CP-Se were tested as a cathode for the rechargeable lithium battery. The electrode was prepared by pressing a powder mixture of NP-Se or CP-Se, acetylene black, and poly(vinylidene fluoride) (PVDF) in a weight ratio of 70:20:10 onto an Al foil. After drying, the foil was cut into pellets, about 2.0 mg for every pellet. Then the pellets were dried at 80 oC overnight under vacuum. Coin-type cells were assembled in a glove box, with lithium foil as the counter and reference electrode, Celgard 2400 as the separator, and LIB315 (a standard 1 mol L-1 LiPF6 solution in a 1:1:1 mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate, Guotaihuarong Chemical Plant) as the electrolyte. Galvanostatic cycling was performed using a LANDct 3.3 battery tester. The XRD patterns of the NP-Se and CP-Se are shown in Fig.1. Several peaks at 23.5 (100), 29.7 (101), 41.3 (110), 43.6 (102), 45.4 (111), 51.8 (201), 55.7 (112), and 61.5 (202) are in good accord with the diffraction peaks of selenium, which can be indexed to the trigonal phase of Se (JCPDS 06-0362).27,29 [journal], [year], [vol], 00–00 | 1
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plateaus (at 2.0 V and 3.9 V) while the CP-Se presents only one plateau at high voltage, 4.2 V. This means that the nanoporous Se
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Fig. 2 SEM micrograph of (a) CP-Se and (b) CaCO3 template, (c) TEM micrograph of NP-Se, and (d) illustration of the preparation process for NP-Se.
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Galvanostatic discharge-charge voltage profiles and cycling performances for NP-Se and CP-Se are shown in Fig. 3, in which the current density is fixed at 100 mA g-1 and the potential is in the range 0.8 to 4.3 V. For both two materials, the initial discharge (Li insertion) involves one well-defined plateau (at 1.5 V) indicative of a single phase transition. During the ensuing charge process (Se oxidation), the prepared NP-Se shows two 2 | Journal Name, [year], [vol], 00–00
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can partially activate the redox process and reduce the overpotential.27 However, it is no stable during cycling. The prepared NP-Se exhibits a reversible capacity of 338 mAh g-1, which is much higher than that of CP-Se (123 mAh g-1). The reason may lie in the special porous structure of the NP-Se and the large contact area between the building blocks and the electrolyte offers more active sites for Li+ insertion/removal, 31 thus resulting in high specific capacity. One thing to be noted is that the total charge capacity exceeds the discharge capacities for these two materials, which may be attributed to the “redox shuttle”
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The SEM micrograph of the commercial Se particles and the CaCO3 template as well as the TEM micrograph of the prepared nanoporous Se are shown in Fig. 2. From these micrographs, it can be seen that CP-Se is non-porous and the particle size is about 500 nm. Different from the CP-Se, there are lots of nanopores with a size of 50 nm in the NP-Se that are ascribed to the dissolution of CaCO3 template in the etching process from the composite of CaCO3/Se (see Fig. 2d). Pore-size distribution of N2 adsorption-desorption isotherms (Fig. S1a and b of the ESI) of the NP-Se also shows a large amount of pores with average size of 50-60 nm, which demonstrates its nanoporous structure. The BET surface area of the NP-Se is 40.9 m2 g-1, larger than that of the CP-Se (only 0.3 m2 g-1).
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effect.32 Interestingly, after the initial process, the oxidative reaction of the NP-Se shifts to higher potential, and a single plateau stabilizes at about 4.0 V in the 10th cycle, corresponding to the oxidation of Li2Se to Se.6 Similar trends are observed for the CP-Se material. After 20 cycles, the prepared NP-Se sustains a capacity of 206 mAh g-1 while the CP-Se only remains a capacity of 60 mAh g-1 (Fig. 3c). This is due to that the prepared NP-Se is hierarchically built up with nanopores and nanowalls that can avoid the aggregation and retain small dimensions and large surface area. 11,13
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In summary, a new kind of nanoporous Se material was prepared as a cathode material for rechargeable lithium batteries. It can deliver a high capacity of 284 mAh g-1, and maintain 230 mAh g-1 even after 20 cycles, which provides a new direction to explore new Se-based cathode materials for rechargeable lithium batteries. The authors acknowledge the financial supports from STCSM (12JC1401200).
Notes and references
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New Energy and Materials Laboratory (NEML), Department of Chemistry & Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China. Fax: +86-21-55664223; E-mail: [email protected]. †Electronic Supplementary Information (ESI) available: N2 adsorptiondesorption isotherms and Pore-size distribution of the nanoporous Se; See DOI: 10.1039/b000000x/ 1 Y. P. Wu, C. R. Wan and C. Y. Jiang, Lithium Ion Secondary Batteries, Chemical Industry Press, Beijing, 2002. 2 Y. Oumellal, A. Rougier, G. A. Nazri, J. M. Tarascon, and L. Aymard. Nat. Mater., 2008, 7, 916. 3 (a) F. Wu, J. Z. Chen, L. L, T. Zhao and R. J. Chen. J. Phys. Chem. C, 2011, 115, 24411; (b) X.J. Wang, Y.Y. Hou, Y.S. Zhu, Y.P. Wu, R. Holze, Sci. Rep., 2013, 3, 1401; (c) X.J. Wang, Q.T. Qu Y.Y. Hou, F.X. Wang, Y.P. Wu, Chem. Commun., 2013, 49, 6179; (d) Z.Q. Peng, S.A. Freunberger, Y.H. Chen, P.G. Bruce, Science, 2012, 337, 563; (e) Y. Zhao, L.N. Wang, H.R. Byon, Nat. Commun., 2013, 4, 1896. 4 (a) T. Zhang, L. J. Fu, J. Gao, L. C. Yang, Y. P. Wu and H. Q. Wu, Pure Appl. Chem., 2006, 78, 1889; (b) Y.H. Lu, J.B. Goodenough, and Y. Kim, J. Am. Chem. Soc., 2011, 133, 5756; (c) H.Q. Li, Y.G. Wang, H.T. Na, H.M. Liu, and H.S. Zhou, J. Am. Chem. Soc., 2009, 131, 15098.
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Nanoporous selenium as a cathode material for rechargeable lithium- selenium batteries Lili Liu, Yuyang Hou, Shiying Xiao Zheng Chang, Yaqiong Yang and Yuping Wu
Chemical Communications Accepted Manuscript
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A novel nanoporous Se prepared by a simple mechanical method adopting nano-CaCO3 as template exhibits relative high capacity and good cycling behaviour. 15
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Nanoporous selenium as a cathode material for rechargeable lithium batteries of high capacity Lili Liu,a Yuyang Hou,a Shiying Xiaoa Zheng Chang, a Yaqiong Yang a and Yuping Wu*a
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This journal is © The Royal Society of Chemistry [year]
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Accepted Manuscript This article can be cited before page numbers have been issued, to do this please use: Y.P. Wu, L. Liu, Y. Hou, S. Xiao, Z. Chang and Y. Yang, Chem. Commun., 2013, DOI: 10.1039/C3CC46943C.
Volume 46 | Number 32 | 2010
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This is an Accepted Manuscript, which has been through the RSC Publishing peer review process and has been accepted for publication. Chemical Communications www.rsc.org/chemcomm
Volume 46 | Number 32 | 28 August 2010 | Pages 5813–5976
ChemComm
the chemical
to therapeutic
etic and
Accepted Manuscripts are published online shortly after acceptance, which is prior to technical editing, formatting and proof reading. This free service from RSC Publishing allows authors to make their results available to the community, in citable form, before publication of the edited article. This Accepted Manuscript will be replaced by the edited and formatted Advance Article as soon as this is available. To cite this manuscript please use its permanent Digital Object Identifier (DOI®), which is identical for all formats of publication.
analytical ques for use
es and tools to s.
More information about Accepted Manuscripts can be found in the Information for Authors.
inical systems.
and
les. ion
Registered Charity Number 207890
Pages 5813–5976
org/journals
ISSN 1359-7345
COMMUNICATION J. Fraser Stoddart et al. Directed self-assembly of a ring-in-ring complex
FEATURE ARTICLE Wenbin Lin et al. Hybrid nanomaterials for biomedical applications
1359-7345(2010)46:32;1-H
Please note that technical editing may introduce minor changes to the text and/or graphics contained in the manuscript submitted by the author(s) which may alter content, and that the standard Terms & Conditions and the ethical guidelines that apply to the journal are still applicable. In no event shall the RSC be held responsible for any errors or omissions in these Accepted Manuscript manuscripts or any consequences arising from the use of any information contained in them.
www.rsc.org/chemcomm Registered Charity Number 207890
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Cite this: DOI: 10.1039/c0xx00000x
COMMUNICATION
Nanoporous selenium as a cathode material for rechargeable lithiumselenium batteries Lili Liu,a Yuyang Hou,a Shiying Xiaoa Zheng Chang, a Yaqiong Yang a and Yuping Wu*a 5
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x A nanoporous selenium was prepared by a simple mechanical method adopting nano-CaCO3 as a template. When used as cathode, it can deliver relative high capacity and good cycling behaviour. These results present a great promise for this new cathode material for rechargeable lithium batteries of high energy density.
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Since the birth of rechargeable lithium batteries, they have been employed as a promising power source in various fields such as hybrid and plug-in hybrid electric vehicles, solar and wind electricity generation systems owing to the advantages of high energy densities, high operating voltages, low self-discharge and friendliness to environment.1,2 However, portable electronic devices and pure electric vehicles urgently need power sources of higher energy denisties,3 and many efforts have been made. Among these strategies, searching for novel electrode materials with high energy density 4-9 and adopting electrode materials with tunable morphologies such as nanoporous architecture 10-19 are mostly employed since porous architectures present large surface areas and thin walls, which are beneficial to the transportation of lithium ions in the active materials and the decrease of the polarization. 20-24 Selenium, a d-electron containing member of group 16 with high electrical conductivity (approximately 20 orders of magnitude greater than S) and Se-based materials have been explored as an electrode material for solar cells 25,26 and rechargeable batteries. 6,27,28 The redox reaction of Se electrode with lithium is as follows: 6 Se + 2Li+ + 2e- ↔ Li2Se (1) So this kind of lithium/selenium battery, which uses selenium as a cathode and Li as an anode, shows superior advantages over the widely studied lithium/sulfur systems: a) better rate and cycling performance without applying large quantities of additives such ad carbon due to the higher electric conductivity of Se in comparison with S; b) higher output voltages (approximately 0.5 V higher than that for Li/S) and the corresponding higher energy densities, which is quite important for commercial applications. 6 All these superiorities from the pioneering work of Amine’s laboratory indicate that Se will be an attractive new class cathode material for rechargeable lithium batteries. 6 In this study, we report a nanoporous Se prepared by a simple mechanical method adopting nano-CaCO3 as a template, and its electrochemical performance as a cathode material for lithium ion batteries is very good. This journal is © The Royal Society of Chemistry [year]
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The preparation procedure of the nanoporous Se is described as follows. All the reagents were analytical grade. The mixture of 1.0 g nano-CaCO3 (about 50 nm, Enping Jiawei Chemical Industrial Co., Ltd.) and 0.5 g commercial Se particles (Shanghai Meixing Chemical Industrial Co., Ltd.) were loaded into a 50 ml steel bowl containing 18 steel balls of 10 mm in diameter. After the high-energy ball-milling of the mixture at a rotation rate of 400 rpm for 12 h on a planetary ball mill, the obtained composite was calcined at 260 oC for 12 h at a heating rate of 2 oC/min under flowing nitrogen (99.99%, 200 mL min-1). Then the collected material was etched with 1 mol L-1 HCl solution for 2 h followed by centrifugation, washing with distilled water and ethanol and drying under vacuum overnight, the nanoporous Se product was prepared and denoted as NP-Se while the commercial Se particles were denoted as CP-Se for a control. Crystal structure of the prepared nanoporous Se was characterized by X-ray powder diffraction (XRD) using a Bruker Analytical X-ray System with CuKα radiation source filtered by a nickel thin plate. Scanning electron micrographs (SEM) and transmission electron micrographs (TEM) were obtained on a Philips XL30 scanning electron microscope and a JEOL JEM2010 transmission electron microscope, respectively. N 2 adsorption-desorption isotherms were collected on a Micromeritics ASAP 2010 adsorption analyzer at 196 oC (77 K), and the BET specific surface area was calculated. The electrochemical performances of the as-obtained NP-Se and CP-Se were tested as a cathode for the rechargeable lithium battery. The electrode was prepared by pressing a powder mixture of NP-Se or CP-Se, acetylene black, and poly(vinylidene fluoride) (PVDF) in a weight ratio of 70:20:10 onto an Al foil. After drying, the foil was cut into pellets, about 2.0 mg for every pellet. Then the pellets were dried at 80 oC overnight under vacuum. Coin-type cells were assembled in a glove box, with lithium foil as the counter and reference electrode, Celgard 2400 as the separator, and LIB315 (a standard 1 mol L-1 LiPF6 solution in a 1:1:1 mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate, Guotaihuarong Chemical Plant) as the electrolyte. Galvanostatic cycling was performed using a LANDct 3.3 battery tester. The XRD patterns of the NP-Se and CP-Se are shown in Fig.1. Several peaks at 23.5 (100), 29.7 (101), 41.3 (110), 43.6 (102), 45.4 (111), 51.8 (201), 55.7 (112), and 61.5 (202) are in good accord with the diffraction peaks of selenium, which can be indexed to the trigonal phase of Se (JCPDS 06-0362).27,29 [journal], [year], [vol], 00–00 | 1
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plateaus (at 2.0 V and 3.9 V) while the CP-Se presents only one plateau at high voltage, 4.2 V. This means that the nanoporous Se
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Fig. 2 SEM micrograph of (a) CP-Se and (b) CaCO3 template, (c) TEM micrograph of NP-Se, and (d) illustration of the preparation process for NP-Se.
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Galvanostatic discharge-charge voltage profiles and cycling performances for NP-Se and CP-Se are shown in Fig. 3, in which the current density is fixed at 100 mA g-1 and the potential is in the range 0.8 to 4.3 V. For both two materials, the initial discharge (Li insertion) involves one well-defined plateau (at 1.5 V) indicative of a single phase transition. During the ensuing charge process (Se oxidation), the prepared NP-Se shows two 2 | Journal Name, [year], [vol], 00–00
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can partially activate the redox process and reduce the overpotential.27 However, it is no stable during cycling. The prepared NP-Se exhibits a reversible capacity of 338 mAh g-1, which is much higher than that of CP-Se (123 mAh g-1). The reason may lie in the special porous structure of the NP-Se and the large contact area between the building blocks and the electrolyte offers more active sites for Li+ insertion/removal, 31 thus resulting in high specific capacity. One thing to be noted is that the total charge capacity exceeds the discharge capacities for these two materials, which may be attributed to the “redox shuttle”
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The SEM micrograph of the commercial Se particles and the CaCO3 template as well as the TEM micrograph of the prepared nanoporous Se are shown in Fig. 2. From these micrographs, it can be seen that CP-Se is non-porous and the particle size is about 500 nm. Different from the CP-Se, there are lots of nanopores with a size of 50 nm in the NP-Se that are ascribed to the dissolution of CaCO3 template in the etching process from the composite of CaCO3/Se (see Fig. 2d). Pore-size distribution of N2 adsorption-desorption isotherms (Fig. S1a and b of the ESI) of the NP-Se also shows a large amount of pores with average size of 50-60 nm, which demonstrates its nanoporous structure. The BET surface area of the NP-Se is 40.9 m2 g-1, larger than that of the CP-Se (only 0.3 m2 g-1).
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effect.32 Interestingly, after the initial process, the oxidative reaction of the NP-Se shifts to higher potential, and a single plateau stabilizes at about 4.0 V in the 10th cycle, corresponding to the oxidation of Li2Se to Se.6 Similar trends are observed for the CP-Se material. After 20 cycles, the prepared NP-Se sustains a capacity of 206 mAh g-1 while the CP-Se only remains a capacity of 60 mAh g-1 (Fig. 3c). This is due to that the prepared NP-Se is hierarchically built up with nanopores and nanowalls that can avoid the aggregation and retain small dimensions and large surface area. 11,13
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In summary, a new kind of nanoporous Se material was prepared as a cathode material for rechargeable lithium batteries. It can deliver a high capacity of 284 mAh g-1, and maintain 230 mAh g-1 even after 20 cycles, which provides a new direction to explore new Se-based cathode materials for rechargeable lithium batteries. The authors acknowledge the financial supports from STCSM (12JC1401200).
Notes and references
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New Energy and Materials Laboratory (NEML), Department of Chemistry & Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China. Fax: +86-21-55664223; E-mail: [email protected]. †Electronic Supplementary Information (ESI) available: N2 adsorptiondesorption isotherms and Pore-size distribution of the nanoporous Se; See DOI: 10.1039/b000000x/ 1 Y. P. Wu, C. R. Wan and C. Y. Jiang, Lithium Ion Secondary Batteries, Chemical Industry Press, Beijing, 2002. 2 Y. Oumellal, A. Rougier, G. A. Nazri, J. M. Tarascon, and L. Aymard. Nat. Mater., 2008, 7, 916. 3 (a) F. Wu, J. Z. Chen, L. L, T. Zhao and R. J. Chen. J. Phys. Chem. C, 2011, 115, 24411; (b) X.J. Wang, Y.Y. Hou, Y.S. Zhu, Y.P. Wu, R. Holze, Sci. Rep., 2013, 3, 1401; (c) X.J. Wang, Q.T. Qu Y.Y. Hou, F.X. Wang, Y.P. Wu, Chem. Commun., 2013, 49, 6179; (d) Z.Q. Peng, S.A. Freunberger, Y.H. Chen, P.G. Bruce, Science, 2012, 337, 563; (e) Y. Zhao, L.N. Wang, H.R. Byon, Nat. Commun., 2013, 4, 1896. 4 (a) T. Zhang, L. J. Fu, J. Gao, L. C. Yang, Y. P. Wu and H. Q. Wu, Pure Appl. Chem., 2006, 78, 1889; (b) Y.H. Lu, J.B. Goodenough, and Y. Kim, J. Am. Chem. Soc., 2011, 133, 5756; (c) H.Q. Li, Y.G. Wang, H.T. Na, H.M. Liu, and H.S. Zhou, J. Am. Chem. Soc., 2009, 131, 15098.
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Nanoporous selenium as a cathode material for rechargeable lithium- selenium batteries Lili Liu, Yuyang Hou, Shiying Xiao Zheng Chang, Yaqiong Yang and Yuping Wu
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A novel nanoporous Se prepared by a simple mechanical method adopting nano-CaCO3 as template exhibits relative high capacity and good cycling behaviour. 15
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Nanoporous selenium as a cathode material for rechargeable lithium batteries of high capacity Lili Liu,a Yuyang Hou,a Shiying Xiaoa Zheng Chang, a Yaqiong Yang a and Yuping Wu*a
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N2 adsorption-desorption isotherms and pore-size distribution of nanoporous carbon is shown in Fig.S1. Pore-size distribution indicates that there are lots of pores with average size of 50 nm in the nanoporous Se, which is near to the particle size of the nano-CaCO3. The BET surface area is 40.89 m2/g. 0.5 0.4 0.3
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