Multi-Step Lithiation of Tin Sulfide: An Investigation Using In Situ Electron Microscopy

Hwang, Sooyeon; Yao, Zhenpeng; Zhang, Lei; Fu, Maosen; He, Kai; Mai, Liqiang; Wolverton, Chris; Su, Dong

doi:10.1021/acsnano.8b00758

Title: Multi-Step Lithiation of Tin Sulfide: An Investigation Using In Situ Electron Microscopy

Journal Article · Tue Apr 03 04:00:00 UTC 2018 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.8b00758 · OSTI ID:1431452

Hwang, Sooyeon ^[1]; Yao, Zhenpeng ^[2]; Zhang, Lei ^[3]; Fu, Maosen ^[4]; He, Kai ^[2]; Mai, Liqiang ^[3]; Wolverton, Chris ^[2]; Su, Dong ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
Wuhan Univ. of Technology (China). State Key Lab. of Advanced Technology for Materials Synthesis and Processing
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Northwestern Polytechnical Univ., Xi'an (China). Shanxi Materials Analysis and Research Center and School of Materials Science and Engineering

Two-dimensional metal sulfides have been widely explored as promising electrodes for lithium ion batteries since their two-dimensional layered structure allows lithium ions to intercalate between layers. For tin disulfide, the lithiation process proceeds via a sequence of three different types of reactions: intercalation, conversion, and alloying but the full scenario of reaction dynamics remains nebulous. In this paper, we investigate the dynamical process of the multi-step reactions using in situ electron microscopy and discover an intermediate rock-salt phase with the disordering of Li and Sn cations, after the initial 2-dimensional intercalation. The disordered cations occupy all the octahedral sites and block the channels for intercalation, which alter the reaction pathways during further lithiation. Our first principles calculations of the non-equilibrium lithiation of SnS2 corroborate the energetic preference of the disordered rock-salt structure over known layered polymorphs. The in situ observations and calculations suggest a two-phase reaction nature for intercalation, disordering, and following conversion reactions. In addition, in situ de-lithiation observation confirms that the alloying reaction is reversible while the conversion reaction is not, which is consistent to the ex situ analysis. This work reveals the full lithiation characteristic of SnS2 and sheds light on the understanding of complex multistep reactions in two-dimensional materials.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704; AC02-06CH11357

OSTI ID:: 1431452

Report Number(s):: BNL--203452-2018-JAAM

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 4 Vol. 12; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions Cabana, Jordi; Monconduit, Laure; Larcher, Dominique Advanced Materials, Vol. 22, Issue 35 https://doi.org/10.1002/adma.201000717	journal	August 2010
Atomic-Scale Monitoring of Electrode Materials in Lithium-Ion Batteries using In Situ Transmission Electron Microscopy Shang, Tongtong; Wen, Yuren; Xiao, Dongdong Advanced Energy Materials, Vol. 7, Issue 23 https://doi.org/10.1002/aenm.201700709	journal	October 2017
Strain Coupling of Conversion-type Fe ₃ O ₄ Thin Films for Lithium Ion Batteries Hwang, Sooyeon; Meng, Qingping; Chen, Ping-Fan Angewandte Chemie International Edition, Vol. 56, Issue 27 https://doi.org/10.1002/anie.201703168	journal	May 2017
Growth and the Crystal Characteristics of Dichalcogenides Having Layer Structures Balchin, A. A. Crystallography and Crystal Chemistry of Materials with Layered Structures https://doi.org/10.1007/978-94-010-1433-5_1	book	January 1976
Chemical and electrochemical lithium intercalation and staging in 2HSnS2 Morales, J.; Perezvicente, C.; Tirado, J. Solid State Ionics, Vol. 51, Issue 3-4 https://doi.org/10.1016/0167-2738(92)90190-Z	journal	April 1992
Intercalation chemistry of molybdenum disulfide Benavente, E. Coordination Chemistry Reviews, Vol. 224, Issue 1-2 https://doi.org/10.1016/S0010-8545(01)00392-7	journal	January 2002
Electrochemical lithiation of tin and tin-based intermetallics and composites Winter, Martin; Besenhard, Jürgen O. Electrochimica Acta, Vol. 45, Issue 1-2, p. 31-50 https://doi.org/10.1016/S0013-4686(99)00191-7	journal	September 1999
The alloy theoretic automated toolkit: A user guide van de Walle, A.; Asta, M.; Ceder, G. Calphad, Vol. 26, Issue 4 https://doi.org/10.1016/S0364-5916(02)80006-2	journal	December 2002
SnS2 anode for rechargeable lithium battery Momma, Toshiyuki; Shiraishi, Nobuhiro; Yoshizawa, Atsuhito Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00723-6	journal	July 2001
Novel SnS2-nanosheet anodes for lithium-ion batteries Kim, Tae-Joon; Kim, Chunjoong; Son, Dongyeon Journal of Power Sources, Vol. 167, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.02.040	journal	May 2007
A review of the electrochemical performance of alloy anodes for lithium-ion batteries Zhang, Wei-Jun Journal of Power Sources, Vol. 196, Issue 1 https://doi.org/10.1016/j.jpowsour.2010.07.020	journal	January 2011
One-pot synthesis of three-dimensional SnS2 hierarchitectures as anode material for lithium-ion batteries Wu, Qiong; Jiao, Lifang; Du, Juan Journal of Power Sources, Vol. 239 https://doi.org/10.1016/j.jpowsour.2013.03.062	journal	October 2013
Structure-mediated electrochemical performance of SnS 2 anode for Li-ion batteries Wu, Karen; Wu, Chia-Jung; Tseng, Chuan-Ming Journal of the Taiwan Institute of Chemical Engineers, Vol. 66 https://doi.org/10.1016/j.jtice.2016.07.003	journal	September 2016
Engineering nano-composite Li4Ti5O12 anodes via scanning electron-probe fabrication Su, Dong; Wang, Feng; Ma, Chao Nano Energy, Vol. 2, Issue 3 https://doi.org/10.1016/j.nanoen.2012.10.009	journal	May 2013
Intermediate phases in sodium intercalation into MoS2 nanosheets and their implications for sodium-ion batteries Li, Qianqian; Yao, Zhenpeng; Wu, Jinsong Nano Energy, Vol. 38 https://doi.org/10.1016/j.nanoen.2017.05.055	journal	August 2017
Nanostructured transition metal sulfides for lithium ion batteries: Progress and challenges Xu, Xiaodong; Liu, Wen; Kim, Youngsik Nano Today, Vol. 9, Issue 5 https://doi.org/10.1016/j.nantod.2014.09.005	journal	October 2014
Reactivity of transition metal (Co, Ni, Cu) sulphides versus lithium: The intriguing case of the copper sulphide Débart, A.; Dupont, L.; Patrice, R. Solid State Sciences, Vol. 8, Issue 6 https://doi.org/10.1016/j.solidstatesciences.2006.01.013	journal	June 2006
Local temperature measurement in TEM by parallel beam electron diffraction Niekiel, Florian; Kraschewski, Simon M.; Müller, Julian Ultramicroscopy, Vol. 176 https://doi.org/10.1016/j.ultramic.2016.11.028	journal	May 2017
Self-Assembled Framework Formed During Lithiation of SnS ₂ Nanoplates Revealed by in Situ Electron Microscopy Yin, Kuibo; Zhang, Minghao; Hood, Zachary D. Accounts of Chemical Research, Vol. 50, Issue 7 https://doi.org/10.1021/acs.accounts.7b00086	journal	July 2017
Revealing the Conversion Mechanism of Transition Metal Oxide Electrodes during Lithiation from First-Principles Yao, Zhenpeng; Kim, Soo; Aykol, Muratahan Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b02058	journal	October 2017
High-Resolution Tracking Asymmetric Lithium Insertion and Extraction and Local Structure Ordering in SnS ₂ Gao, Peng; Wang, Liping; Zhang, Yu-Yang Nano Letters, Vol. 16, Issue 9 https://doi.org/10.1021/acs.nanolett.6b02136	journal	August 2016
Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes He, Kai; Yao, Zhenpeng; Hwang, Sooyeon Nano Letters, Vol. 17, Issue 9 https://doi.org/10.1021/acs.nanolett.7b02694	journal	August 2017
Kinetic Phase Evolution of Spinel Cobalt Oxide during Lithiation Li, Jing; He, Kai; Meng, Qingping ACS Nano, Vol. 10, Issue 10 https://doi.org/10.1021/acsnano.6b04958	journal	September 2016
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries Reddy, M. V.; Subba Rao, G. V.; Chowdari, B. V. R. Chemical Reviews, Vol. 113, Issue 7 https://doi.org/10.1021/cr3001884	journal	March 2013
Native Defect Concentrations in NaAlH ₄ and Na ₃ AlH ₆ Michel, Kyle Jay; Ozoliņš, Vidvuds The Journal of Physical Chemistry C, Vol. 115, Issue 43 https://doi.org/10.1021/jp203672u	journal	October 2011
Fast Mass Transport Kinetics in B ₂₀ H ₁₆ : A High-Capacity Hydrogen Storage Material Michel, Kyle Jay; Zhang, Yongsheng; Wolverton, C. The Journal of Physical Chemistry C, Vol. 117, Issue 38 https://doi.org/10.1021/jp402669u	journal	September 2013
MoS ₂ Nanoplates Consisting of Disordered Graphene-like Layers for High Rate Lithium Battery Anode Materials Hwang, Haesuk; Kim, Hyejung; Cho, Jaephil Nano Letters, Vol. 11, Issue 11 https://doi.org/10.1021/nl202675f	journal	November 2011
In Situ Observation of Divergent Phase Transformations in Individual Sulfide Nanocrystals McDowell, Matthew T.; Lu, Zhenda; Koski, Kristie J. Nano Letters, Vol. 15, Issue 2 https://doi.org/10.1021/nl504436m	journal	January 2015
Transitions from Near-Surface to Interior Redox upon Lithiation in Conversion Electrode Materials He, Kai; Xin, Huolin L.; Zhao, Kejie Nano Letters, Vol. 15, Issue 2 https://doi.org/10.1021/nl5049884	journal	January 2015
In Situ TEM Study of Lithiation Behavior of Silicon Nanoparticles Attached to and Embedded in a Carbon Matrix Gu, Meng; Li, Ying; Li, Xiaolin ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn303312m	journal	August 2012
Atomic-Scale Observation of Lithiation Reaction Front in Nanoscale SnO ₂ Materials Nie, Anmin; Gan, Li-Yong; Cheng, Yingchun ACS Nano, Vol. 7, Issue 7 https://doi.org/10.1021/nn402125e	journal	June 2013
In Situ Transmission Electron Microscopy Investigation of the Electrochemical Lithiation–Delithiation of Individual Co ₉ S ₈ /Co-Filled Carbon Nanotubes Su, Qingmei; Du, Gaohui; Zhang, Jun ACS Nano, Vol. 7, Issue 12 https://doi.org/10.1021/nn405254n	journal	November 2013
Atomic Resolution Study of Reversible Conversion Reaction in Metal Oxide Electrodes for Lithium-Ion Battery Luo, Langli; Wu, Jinsong; Xu, Junming ACS Nano, Vol. 8, Issue 11 https://doi.org/10.1021/nn504806h	journal	October 2014
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries Poizot, P.; Laruelle, S.; Grugeon, S. Nature, Vol. 407, Issue 6803, p. 496-499 https://doi.org/10.1038/35035045	journal	September 2000
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3 Muller, David A.; Nakagawa, Naoyuki; Ohtomo, Akira Nature, Vol. 430, Issue 7000 https://doi.org/10.1038/nature02756	journal	August 2004
High rate capabilities Fe₃O₄-based Cu nano-architectured electrodes for lithium-ion battery applications Taberna, P. L.; Mitra, S.; Poizot, P. Nature Materials, Vol. 5, Issue 7, p. 567-573 https://doi.org/10.1038/nmat1672	journal	June 2006
Lithium ion battery applications of molybdenum disulfide (MoS ₂ ) nanocomposites Stephenson, Tyler; Li, Zhi; Olsen, Brian Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE42591F	journal	January 2014
A novel SnS ₂ @graphene nanocable network for high-performance lithium storage Kong, Debin; He, Haiyong; Song, Qi RSC Adv., Vol. 4, Issue 45 https://doi.org/10.1039/C4RA03052D	journal	January 2014
A facile, relative green, and inexpensive synthetic approach toward large-scale production of SnS2 nanoplates for high-performance lithium-ion batteries Du, Yaping; Yin, Zongyou; Rui, Xianhong Nanoscale, Vol. 5, Issue 4 https://doi.org/10.1039/c2nr33458e	journal	January 2013
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Lithium insertion mechanism in SnS 2 Lefebvre-Devos, I.; Olivier-Fourcade, J.; Jumas, J. C. Physical Review B, Vol. 61, Issue 4 https://doi.org/10.1103/PhysRevB.61.3110	journal	January 2000
Algorithm for generating derivative structures Hart, Gus L. W.; Forcade, Rodney W. Physical Review B, Vol. 77, Issue 22 https://doi.org/10.1103/PhysRevB.77.224115	journal	June 2008
Generating derivative structures from multilattices: Algorithm and application to hcp alloys Hart, Gus L. W.; Forcade, Rodney W. Physical Review B, Vol. 80, Issue 1 https://doi.org/10.1103/PhysRevB.80.014120	journal	July 2009
Special quasirandom structures Zunger, Alex; Wei, S.-H.; Ferreira, L. G. Physical Review Letters, Vol. 65, Issue 3, p. 353-356 https://doi.org/10.1103/PhysRevLett.65.353	journal	July 1990
A rapid method for analysing the breadths of diffraction and spectral lines using the Voigt function Langford, J. I. Journal of Applied Crystallography, Vol. 11, Issue 1 https://doi.org/10.1107/S0021889878012601	journal	February 1978
New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design Belsky, Alec; Hellenbrandt, Mariette; Karen, Vicky Lynn Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3 https://doi.org/10.1107/S0108768102006948	journal	May 2002
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Electrical Energy Storage and Intercalation Chemistry Whittingham, M. S. Science, Vol. 192, Issue 4244 https://doi.org/10.1126/science.192.4244.1126	journal	June 1976
Nanoscale temperature mapping in operating microelectronic devices Mecklenburg, Matthew; Hubbard, William A.; White, E. R. Science, Vol. 347, Issue 6222 https://doi.org/10.1126/science.aaa2433	journal	February 2015
Carbon Metal Fluoride Nanocomposites: High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries Badway, F.; Cosandey, F.; Pereira, N. Journal of The Electrochemical Society, Vol. 150, Issue 10, p. A1318-A1327 https://doi.org/10.1149/1.1602454	journal	January 2003

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Phase evolution of conversion-type electrode for lithium ion batteries Li, Jing; Hwang, Sooyeon; Guo, Fangming Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09931-2	journal	May 2019
Unveiling the structural evolution of 1T SnS ₂ anode upon lithiation/delithiation by TEM Xie, Ruicong; Cui, Ying; Zhou, Tong Chemical Communications, Vol. 55, Issue 54 https://doi.org/10.1039/c9cc03320c	journal	January 2019
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