Anhydrous Liquid-Phase Exfoliation of Pristine Electrochemically Active GeS Nanosheets

Lam, David; Chen, Kan-Sheng; Kang, Joohoon; Liu, Xiaolong; Hersam, Mark C.

doi:10.1021/acs.chemmater.7b04652

Anhydrous Liquid-Phase Exfoliation of Pristine Electrochemically Active GeS Nanosheets

Journal Article · Tue Mar 20 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b04652· OSTI ID:1470441

Lam, David ^[1]; ^[1]; Kang, Joohoon ^[1]; ^[2]; ^[3]

Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
Northwestern Univ., Evanston, IL (United States). Applied Physics Graduate Program
Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering; Northwestern Univ., Evanston, IL (United States). Applied Physics Graduate Program

Germanium sulfide (GeS) is an emerging layered material with high promise in its two-dimensional (2D) exfoliated form for energy storage applications. While liquid-phase exfoliation (LPE) has been utilized for the low-cost, scalable production of related 2D materials, it has not yet been demonstrated for GeS nanosheets due to its chemical instability in ambient conditions. Here, GeS LPE is achieved in anhydrous N-methyl-2-pyrrolidone using a customized sealed-tip sonication system, yielding sub-10 nm thick GeS nanosheets that are structurally pristine with minimal chemical degradation as revealed by atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Lithium-ion battery anodes based on these high-quality GeS nanosheets possess superlative electrochemical performance including high cycling stability over 1000 cycles and high rate capability in excess of 10 A g^–1. Finally, overall, this work establishes a scalable LPE pathway for the production of pristine electrochemically active GeS nanosheets that are well-suited for high-power lithium-ion battery applications.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1470441

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 7 Vol. 30; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

Atomically Thin MoS ₂ : A Versatile Nongraphene 2D Material Venkata Subbaiah, Y. P.; Saji, K. J.; Tiwari, A. Advanced Functional Materials, Vol. 26, Issue 13 https://doi.org/10.1002/adfm.201504202	journal	February 2016
Two-Dimensional SnS ₂ Nanoplates with Extraordinary High Discharge Capacity for Lithium Ion Batteries Seo, Jung-wook; Jang, Jung-tak; Park, Seung-won Advanced Materials, Vol. 20, Issue 22 https://doi.org/10.1002/adma.200703122	journal	November 2008
Scalable Clean Exfoliation of High-Quality Few-Layer Black Phosphorus for a Flexible Lithium Ion Battery Chen, Long; Zhou, Guangmin; Liu, Zhibo Advanced Materials, Vol. 28, Issue 3 https://doi.org/10.1002/adma.201503678	journal	November 2015
Electrical and photoelectric properties of GeS layered crystals grown by different techniques Bletskan, D. I.; Madyar, I. I.; Mikulaninets, S. V. Inorganic Materials, Vol. 36, Issue 6 https://doi.org/10.1007/BF02757950	journal	June 2000
Anisotropic optical and electronic properties of two-dimensional layered germanium sulfide Tan, Dezhi; Lim, Hong En; Wang, Feijiu Nano Research, Vol. 10, Issue 2 https://doi.org/10.1007/s12274-016-1312-6	journal	December 2016
Hydrothermal exfoliated molybdenum disulfide nanosheets as anode material for lithium ion batteries Liu, Yundan; Ren, Long; Qi, Xiang Journal of Energy Chemistry, Vol. 23, Issue 2 https://doi.org/10.1016/S2095-4956(14)60137-6	journal	March 2014
Ultrasonication fabrication of high quality multilayer graphene flakes and their characterization as anodes for lithium ion batteries Kokai, F.; Sorin, R.; Chigusa, H. Diamond and Related Materials, Vol. 29 https://doi.org/10.1016/j.diamond.2012.07.011	journal	September 2012
Exfoliated MoO3 nanosheets for high-capacity lithium storage Zhang, Huijuan; Gao, Lijun; Gong, Yongji Electrochemistry Communications, Vol. 52 https://doi.org/10.1016/j.elecom.2015.01.014	journal	March 2015
Layer-by-Layer Hybrids of MoS2 and Reduced Graphene Oxide for Lithium Ion Batteries Jing, Yu; Ortiz-Quiles, Edwin O.; Cabrera, Carlos R. Electrochimica Acta, Vol. 147 https://doi.org/10.1016/j.electacta.2014.09.132	journal	November 2014
Liquid phase co-exfoliated MoS2–graphene composites as anode materials for lithium ion batteries Pham, Viet Hung; Kim, Kwang-Hyun; Jung, Dong-Won Journal of Power Sources, Vol. 244 https://doi.org/10.1016/j.jpowsour.2013.01.053	journal	December 2013
Solution-Based Processing of Monodisperse Two-Dimensional Nanomaterials Kang, Joohoon; Sangwan, Vinod K.; Wood, Joshua D. Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00643	journal	February 2017
Nanocomb Architecture Design Using Germanium Selenide as High-Performance Lithium Storage Material Kim, Hyungki; Son, Yeonguk; Lee, Jinho Chemistry of Materials, Vol. 28, Issue 17 https://doi.org/10.1021/acs.chemmater.6b02016	journal	August 2016
Structural Evolution of Electrochemically Lithiated MoS ₂ Nanosheets and the Role of Carbon Additive in Li-Ion Batteries George, Chandramohan; Morris, Andrew J.; Modarres, Mohammad H. Chemistry of Materials, Vol. 28, Issue 20 https://doi.org/10.1021/acs.chemmater.6b02607	journal	October 2016
Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries Del Rio Castillo, Antonio Esau; Pellegrini, Vittorio; Sun, Haiyan Chemistry of Materials, Vol. 30, Issue 2 https://doi.org/10.1021/acs.chemmater.7b04628	journal	January 2018
Hybrid, Gate-Tunable, van der Waals p–n Heterojunctions from Pentacene and MoS ₂ Jariwala, Deep; Howell, Sarah L.; Chen, Kan-Sheng Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04141	journal	December 2015
Layer-by-Layer Sorting of Rhenium Disulfide via High-Density Isopycnic Density Gradient Ultracentrifugation Kang, Joohoon; Sangwan, Vinod K.; Wood, Joshua D. Nano Letters, Vol. 16, Issue 11 https://doi.org/10.1021/acs.nanolett.6b03584	journal	October 2016
Emerging Opportunities for Two-Dimensional Materials in Lithium-Ion Batteries Chen, Kan-Sheng; Balla, Itamar; Luu, Norman S. ACS Energy Letters, Vol. 2, Issue 9 https://doi.org/10.1021/acsenergylett.7b00476	journal	August 2017
Solvent Exfoliation of Electronic-Grade, Two-Dimensional Black Phosphorus Kang, Joohoon; Wood, Joshua D.; Wells, Spencer A. ACS Nano, Vol. 9, Issue 4 https://doi.org/10.1021/acsnano.5b01143	journal	February 2015
Recent Advances in Two-Dimensional Materials beyond Graphene Bhimanapati, Ganesh R.; Lin, Zhong; Meunier, Vincent ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/acsnano.5b05556	journal	October 2015
Production of Highly Monolayer Enriched Dispersions of Liquid-Exfoliated Nanosheets by Liquid Cascade Centrifugation Backes, Claudia; Szydłowska, Beata M.; Harvey, Andrew ACS Nano, Vol. 10, Issue 1 https://doi.org/10.1021/acsnano.5b07228	journal	December 2015
Exfoliated MoS ₂ Nanocomposite as an Anode Material for Lithium Ion Batteries Xiao, Jie; Choi, Daiwon; Cosimbescu, Lelia Chemistry of Materials, Vol. 22, Issue 16 https://doi.org/10.1021/cm101254j	journal	August 2010
Single-Crystal Colloidal Nanosheets of GeS and GeSe Vaughn, Dimitri D.; Patel, Romesh J.; Hickner, Michael A. Journal of the American Chemical Society, Vol. 132, Issue 43 https://doi.org/10.1021/ja107520b	journal	October 2010
Highly Concentrated Graphene Solutions via Polymer Enhanced Solvent Exfoliation and Iterative Solvent Exchange Liang, Yu Teng; Hersam, Mark C. Journal of the American Chemical Society, Vol. 132, Issue 50, p. 17661-17663 https://doi.org/10.1021/ja107661g	journal	December 2010
Liquid Phase Production of Graphene by Exfoliation of Graphite in Surfactant/Water Solutions Lotya, Mustafa; Hernandez, Yenny; King, Paul J. Journal of the American Chemical Society, Vol. 131, Issue 10 https://doi.org/10.1021/ja807449u	journal	March 2009
Metallic VS ₂ Monolayer: A Promising 2D Anode Material for Lithium Ion Batteries Jing, Yu; Zhou, Zhen; Cabrera, Carlos R. The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp410969u	journal	November 2013
High-Concentration Aqueous Dispersions of Graphene Using Nonionic, Biocompatible Block Copolymers Seo, Jung-Woo T.; Green, Alexander A.; Antaris, Alexander L. The Journal of Physical Chemistry Letters, Vol. 2, Issue 9 https://doi.org/10.1021/jz2003556	journal	April 2011
Synthesis of Surface-Functionalized WS ₂ Nanosheets and Performance as Li-Ion Battery Anodes Bhandavat, R.; David, L.; Singh, G. The Journal of Physical Chemistry Letters, Vol. 3, Issue 11 https://doi.org/10.1021/jz300480w	journal	May 2012
Solution Phase Production of Graphene with Controlled Thickness via Density Differentiation Green, Alexander A.; Hersam, Mark C. Nano Letters, Vol. 9, Issue 12, p. 4031-4036 https://doi.org/10.1021/nl902200b	journal	December 2009
Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility Liu, Han; Neal, Adam T.; Zhu, Zhen ACS Nano, Vol. 8, Issue 4 https://doi.org/10.1021/nn501226z	journal	March 2014
A roadmap for graphene Novoselov, K. S.; Fal′ko, V. I.; Colombo, L. Nature, Vol. 490, Issue 7419 https://doi.org/10.1038/nature11458	journal	October 2012
Thickness sorting of two-dimensional transition metal dichalcogenides via copolymer-assisted density gradient ultracentrifugation Kang, Joohoon; Seo, Jung-Woo T.; Alducin, Diego Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6478	journal	November 2014
Nanostructured materials for advanced energy conversion and storage devices Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno Nature Materials, Vol. 4, Issue 5, p. 366-377 https://doi.org/10.1038/nmat1368	journal	May 2005
Gate-tunable memristive phenomena mediated by grain boundaries in single-layer MoS2 Sangwan, Vinod K.; Jariwala, Deep; Kim, In Soo Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.56	journal	April 2015
Why all the fuss about 2D semiconductors? Castellanos-Gomez, Andres Nature Photonics, Vol. 10, Issue 4 https://doi.org/10.1038/nphoton.2016.53	journal	March 2016
Superior stability and high capacity of restacked molybdenum disulfide as anode material for lithium ion batteries Du, Guodong; Guo, Zaiping; Wang, Shiquan Chem. Commun., Vol. 46, Issue 7 https://doi.org/10.1039/B920277C	journal	January 2010
2D materials: to graphene and beyond Mas-Ballesté, Rubén; Gómez-Navarro, Cristina; Gómez-Herrero, Julio Nanoscale, Vol. 3, Issue 1 https://doi.org/10.1039/C0NR00323A	journal	January 2011
Fragmentation and exfoliation of 2-dimensional materials: a statistical approach Kouroupis-Agalou, Konstantinos; Liscio, Andrea; Treossi, Emanuele Nanoscale, Vol. 6, Issue 11 https://doi.org/10.1039/C3NR06919B	journal	January 2014
High photosensitivity and broad spectral response of multi-layered germanium sulfide transistors Ulaganathan, Rajesh Kumar; Lu, Yi-Ying; Kuo, Chia-Jung Nanoscale, Vol. 8, Issue 4 https://doi.org/10.1039/C5NR05988G	journal	January 2016
Solution synthesis of GeS and GeSe nanosheets for high-sensitivity photodetectors Ramasamy, Parthiban; Kwak, Dohyun; Lim, Da-Hye Journal of Materials Chemistry C, Vol. 4, Issue 3 https://doi.org/10.1039/C5TC03667D	journal	January 2016
MX (M = Ge, Sn; X = S, Se) sheets: theoretical prediction of new promising electrode materials for Li ion batteries Zhou, Yungang Journal of Materials Chemistry A, Vol. 4, Issue 28 https://doi.org/10.1039/C6TA03076A	journal	January 2016
Germanium sulfide nanosheet: a universal anode material for alkali metal ion batteries Li, Feng; Qu, Yuanyuan; Zhao, Mingwen Journal of Materials Chemistry A, Vol. 4, Issue 22 https://doi.org/10.1039/C6TA03210A	journal	January 2016
Formation of SnS nanoflowers for lithium ion batteries Vaughn, Dimitri D.; Hentz, Olivia D.; Chen, Shuru Chemical Communications, Vol. 48, Issue 45 https://doi.org/10.1039/c2cc32033a	journal	January 2012
High quality NMP exfoliated graphene nanosheet–SnO2 composite anode material for lithium ion battery Ravikumar, Raman; Gopukumar, Sukumaran Physical Chemistry Chemical Physics, Vol. 15, Issue 11 https://doi.org/10.1039/c2cp43487c	journal	January 2013
Germanium sulfide(ii and iv) nanoparticles for enhanced performance of lithium ion batteries Cho, Yong Jae; Im, Hyung Soon; Myung, Yoon Chemical Communications, Vol. 49, Issue 41 https://doi.org/10.1039/c3cc41853g	journal	January 2013
Gate-tunable carbon nanotube-MoS2 heterojunction p-n diode Jariwala, D.; Sangwan, V. K.; Wu, C. -C. Proceedings of the National Academy of Sciences, Vol. 110, Issue 45 https://doi.org/10.1073/pnas.1317226110	journal	October 2013
Stable aqueous dispersions of optically and electronically active phosphorene Kang, Joohoon; Wells, Spencer A.; Wood, Joshua D. Proceedings of the National Academy of Sciences, Vol. 113, Issue 42 https://doi.org/10.1073/pnas.1602215113	journal	April 2016
Band-structure calculation for A ⁴ B ⁶ layered crystals by the equivalent-orbital linear combination of atomic orbitals method Gashimzade, F. M.; Guliev, D. G.; Guseinova, D. A. Journal of Physics: Condensed Matter, Vol. 4, Issue 4 https://doi.org/10.1088/0953-8984/4/4/018	journal	January 1992
Infrared reflectivity and Raman scattering in GeS Wiley, J. D.; Buckel, W. J.; Schmidt, R. L. Physical Review B, Vol. 13, Issue 6 https://doi.org/10.1103/PhysRevB.13.2489	journal	March 1976
Phosphorene analogues: Isoelectronic two-dimensional group-IV monochalcogenides with orthorhombic structure Gomes, Lídia C.; Carvalho, A. Physical Review B, Vol. 92, Issue 8 https://doi.org/10.1103/PhysRevB.92.085406	journal	August 2015
Atomically Thin MoS2 A New Direct-Gap Semiconductor Mak, Kin Fai; Lee, Changgu; Hone, James Physical Review Letters, Vol. 105, Issue 13, Article No.136805 https://doi.org/10.1103/PhysRevLett.105.136805	journal	September 2010
Electric Field Effect in Atomically Thin Carbon Films Novoselov, K. S. Science, Vol. 306, Issue 5696, p. 666-669 https://doi.org/10.1126/science.1102896	journal	October 2004
Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials Coleman, J. N.; Lotya, M.; O'Neill, A. Science, Vol. 331, Issue 6017, p. 568-571 https://doi.org/10.1126/science.1194975	journal	February 2011

Cited By (8)

Solution-Based Processing of Optoelectronically Active Indium Selenide Kang, Joohoon; Wells, Spencer A.; Sangwan, Vinod K. Advanced Materials, Vol. 30, Issue 38 https://doi.org/10.1002/adma.201802990	journal	August 2018
2D–Organic Hybrid Heterostructures for Optoelectronic Applications Sun, Jia; Choi, Yongsuk; Choi, Young Jin Advanced Materials, Vol. 31, Issue 34 https://doi.org/10.1002/adma.201803831	journal	February 2019
CuTe ₂ Cl Monolayer: An Unexplored 2D Hybrid Structure with the Coexistence of Remarkable Charge Separation and Visible Light Absorption Zhou, Yungang; He, Junjie physica status solidi (RRL) – Rapid Research Letters, Vol. 14, Issue 3 https://doi.org/10.1002/pssr.201900554	journal	December 2019
In-plane anisotropic electronics based on low-symmetry 2D materials: progress and prospects Zhao, Siwen; Dong, Baojuan; Wang, Huide Nanoscale Advances, Vol. 2, Issue 1 https://doi.org/10.1039/c9na00623k	journal	January 2020
Electronics from solution-processed 2D semiconductors Gao, Xiangxiang; Bian, Gang; Zhu, Jian Journal of Materials Chemistry C, Vol. 7, Issue 41 https://doi.org/10.1039/c9tc03935j	journal	January 2019
Emerging black phosphorus analogue nanomaterials for high-performance device applications Huang, Weichun; Li, Chao; Gao, Lingfeng Journal of Materials Chemistry C, Vol. 8, Issue 4 https://doi.org/10.1039/c9tc05558d	journal	January 2020
A type-II GaSe/GeS heterobilayer with strain enhanced photovoltaic properties and external electric field effects Zhou, Bin; Gong, Shi-Jing; Jiang, Kai Journal of Materials Chemistry C, Vol. 8, Issue 1 https://doi.org/10.1039/c9tc05840k	journal	January 2020
Recent progress in 2D group IV–IV monochalcogenides: synthesis, properties and applications Hu, Ziyu; Ding, Yingchun; Hu, Xuemin Nanotechnology, Vol. 30, Issue 25 https://doi.org/10.1088/1361-6528/ab07d9	journal	April 2019

Similar Records

Anhydrous liquid-phase exfoliation of pristine electrochemically-active GeS nanosheets

Patent · Mon Feb 26 23:00:00 EST 2024 · OSTI ID:2541867

Ion-Conductive, Viscosity-Tunable Hexagonal Boron Nitride Nanosheet Inks

Journal Article · Wed Jul 31 20:00:00 EDT 2019 · Advanced Functional Materials · OSTI ID:1767455

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
42 ENGINEERING
77 NANOSCIENCE AND NANOTECHNOLOGY
charge transport
energy storage (including batteries and capacitors)
materials and chemistry by design
synthesis (novel materials)

Anhydrous Liquid-Phase Exfoliation of Pristine Electrochemically Active GeS Nanosheets

Citation Formats

References (52)

Cited By (8)

Similar Records

Related Subjects