Electrochemistry of Selenium with Sodium and Lithium: Kinetics and Reaction Mechanism

Qianqian Li; Heguang Liu; Zhenpeng Yao; Jipeng Cheng; Tiehu Li; Yuan Li; Chris Wolverton; Jinsong Wu; Vinayak P. Dravid

doi:10.1021/acsnano.6b04519

Electrochemistry of Selenium with Sodium and Lithium: Kinetics and Reaction Mechanism

Qianqian Li, Heguang Liu, Zhenpeng Yao, Jipeng Cheng, Tiehu Li, Yuan Li, Chris Wolverton, Jinsong Wu^*, Vinayak P. Dravid

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

164 Scopus citations

Abstract

There are economic and environmental advantages by replacing Li with Na in energy storage. However, sluggishness in the charge/discharge reaction and low capacity are among the major obstacles to development of high-power sodium-ion batteries. Among the electrode materials recently developed for sodium-ion batteries, selenium shows considerable promise because of its high capacity and good cycling ability. Herein, we have investigated the mechanism and kinetics of both sodiation and lithiation reactions with selenium nanotubes, using in situ transmission electron microscopy. Sodiation of a selenium nanotube exhibits a three-step reaction mechanism: (1) the selenium single crystal transforms into an amorphous phase Na_0.5Se; (2) the Na_0.5Se amorphous phase crystallizes to form a polycrystalline Na₂Se₂ phase; and (3) Na₂Se₂ transforms into the Na₂Se phase. Under similar conditions, the lithiation of Se exhibits a one-step reaction mechanism, with phase transformation from single-crystalline Se to a Li₂Se. Intriguingly, sodiation kinetics is generally about 4-5 times faster than that of lithiation, and the kinetics during the different stages of sodiation is different. Na-based intermediate phases are found to have improved electronic and ionic conductivity compared to those of Li compounds by first-principles density functional theory calculations.

Original language	English (US)
Pages (from-to)	8788-8795
Number of pages	8
Journal	ACS nano
Volume	10
Issue number	9
DOIs	https://doi.org/10.1021/acsnano.6b04519
State	Published - Sep 27 2016

Funding

This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award No. DEAC02-06CH11357, and the Initiative for Sustainability and Energy at Northwestern (ISEN). This work was also supported by the NUANCE Center at Northwestern University, using the EPIC facility that receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. We gratefully acknowledge the computing resources from (1) the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC02-05CH11231, and (2) Blues, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory.

Keywords

DFT calculation
alloying reaction
in situ electron diffraction
in situ transmission electron microscopy
lithium-ion battery
selenium cathodes
sodium-ion battery

ASJC Scopus subject areas

General Materials Science
General Engineering
General Physics and Astronomy

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsnano.6b04519

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@article{2c17464925e5466b88fc7f9f2011e542,

title = "Electrochemistry of Selenium with Sodium and Lithium: Kinetics and Reaction Mechanism",

abstract = "There are economic and environmental advantages by replacing Li with Na in energy storage. However, sluggishness in the charge/discharge reaction and low capacity are among the major obstacles to development of high-power sodium-ion batteries. Among the electrode materials recently developed for sodium-ion batteries, selenium shows considerable promise because of its high capacity and good cycling ability. Herein, we have investigated the mechanism and kinetics of both sodiation and lithiation reactions with selenium nanotubes, using in situ transmission electron microscopy. Sodiation of a selenium nanotube exhibits a three-step reaction mechanism: (1) the selenium single crystal transforms into an amorphous phase Na0.5Se; (2) the Na0.5Se amorphous phase crystallizes to form a polycrystalline Na2Se2 phase; and (3) Na2Se2 transforms into the Na2Se phase. Under similar conditions, the lithiation of Se exhibits a one-step reaction mechanism, with phase transformation from single-crystalline Se to a Li2Se. Intriguingly, sodiation kinetics is generally about 4-5 times faster than that of lithiation, and the kinetics during the different stages of sodiation is different. Na-based intermediate phases are found to have improved electronic and ionic conductivity compared to those of Li compounds by first-principles density functional theory calculations.",

keywords = "DFT calculation, alloying reaction, in situ electron diffraction, in situ transmission electron microscopy, lithium-ion battery, selenium cathodes, sodium-ion battery",

author = "Qianqian Li and Heguang Liu and Zhenpeng Yao and Jipeng Cheng and Tiehu Li and Yuan Li and Chris Wolverton and Jinsong Wu and Dravid, {Vinayak P.}",

note = "Funding Information: This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award No. DEAC02-06CH11357, and the Initiative for Sustainability and Energy at Northwestern (ISEN). This work was also supported by the NUANCE Center at Northwestern University, using the EPIC facility that receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. We gratefully acknowledge the computing resources from (1) the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC02-05CH11231, and (2) Blues, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = sep,

day = "27",

doi = "10.1021/acsnano.6b04519",

language = "English (US)",

volume = "10",

pages = "8788--8795",

journal = "ACS nano",

issn = "1936-0851",

publisher = "American Chemical Society",

number = "9",

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TY - JOUR

T1 - Electrochemistry of Selenium with Sodium and Lithium

T2 - Kinetics and Reaction Mechanism

AU - Li, Qianqian

AU - Liu, Heguang

AU - Yao, Zhenpeng

AU - Cheng, Jipeng

AU - Li, Tiehu

AU - Li, Yuan

AU - Wolverton, Chris

AU - Wu, Jinsong

AU - Dravid, Vinayak P.

N1 - Funding Information: This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award No. DEAC02-06CH11357, and the Initiative for Sustainability and Energy at Northwestern (ISEN). This work was also supported by the NUANCE Center at Northwestern University, using the EPIC facility that receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. We gratefully acknowledge the computing resources from (1) the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC02-05CH11231, and (2) Blues, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/9/27

Y1 - 2016/9/27

N2 - There are economic and environmental advantages by replacing Li with Na in energy storage. However, sluggishness in the charge/discharge reaction and low capacity are among the major obstacles to development of high-power sodium-ion batteries. Among the electrode materials recently developed for sodium-ion batteries, selenium shows considerable promise because of its high capacity and good cycling ability. Herein, we have investigated the mechanism and kinetics of both sodiation and lithiation reactions with selenium nanotubes, using in situ transmission electron microscopy. Sodiation of a selenium nanotube exhibits a three-step reaction mechanism: (1) the selenium single crystal transforms into an amorphous phase Na0.5Se; (2) the Na0.5Se amorphous phase crystallizes to form a polycrystalline Na2Se2 phase; and (3) Na2Se2 transforms into the Na2Se phase. Under similar conditions, the lithiation of Se exhibits a one-step reaction mechanism, with phase transformation from single-crystalline Se to a Li2Se. Intriguingly, sodiation kinetics is generally about 4-5 times faster than that of lithiation, and the kinetics during the different stages of sodiation is different. Na-based intermediate phases are found to have improved electronic and ionic conductivity compared to those of Li compounds by first-principles density functional theory calculations.

AB - There are economic and environmental advantages by replacing Li with Na in energy storage. However, sluggishness in the charge/discharge reaction and low capacity are among the major obstacles to development of high-power sodium-ion batteries. Among the electrode materials recently developed for sodium-ion batteries, selenium shows considerable promise because of its high capacity and good cycling ability. Herein, we have investigated the mechanism and kinetics of both sodiation and lithiation reactions with selenium nanotubes, using in situ transmission electron microscopy. Sodiation of a selenium nanotube exhibits a three-step reaction mechanism: (1) the selenium single crystal transforms into an amorphous phase Na0.5Se; (2) the Na0.5Se amorphous phase crystallizes to form a polycrystalline Na2Se2 phase; and (3) Na2Se2 transforms into the Na2Se phase. Under similar conditions, the lithiation of Se exhibits a one-step reaction mechanism, with phase transformation from single-crystalline Se to a Li2Se. Intriguingly, sodiation kinetics is generally about 4-5 times faster than that of lithiation, and the kinetics during the different stages of sodiation is different. Na-based intermediate phases are found to have improved electronic and ionic conductivity compared to those of Li compounds by first-principles density functional theory calculations.

KW - DFT calculation

KW - alloying reaction

KW - in situ electron diffraction

KW - in situ transmission electron microscopy

KW - lithium-ion battery

KW - selenium cathodes

KW - sodium-ion battery

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ER -

Electrochemistry of Selenium with Sodium and Lithium: Kinetics and Reaction Mechanism

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

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