Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides
Abstract
Abstract Lithiation of van der Waals tetrel‐arsenides, GeAs and SiAs, has been investigated. Electrochemical lithiation demonstrated large initial capacities of over 950 mAh g −1 accompanied by rapid fading over successive cycling in the voltage range 0.01–2 V. Limiting the voltage range to 0.5–2 V achieved more stable cycling, which was attributed to the intercalation process with lower capacities. Ex situ powder X‐ray diffraction confirmed complete amorphization of the samples after lithiation, as well as recrystallization of the binary tetrel‐arsenide phases after full delithiation in the voltage range 0.5–2 V. Solid‐state synthetic methods produce layered phases, in which Si‐As or Ge‐As layers are separated by Li cations. The first layered compounds in the corresponding ternary systems were discovered, Li 0.9 Ge 2.9 As 3.1 and Li 3 Si 7 As 8 , which crystallize in the Pbam (No. 55) and P 2/ m (No. 10) space groups, respectively. Semiconducting layered GeAs and SiAs accommodate the extra charge from Li cations through structural rearrangement in the Si‐As or Ge‐As layers and eventually by replacement of the tetrel dumbbells with sets of Li atoms. Ge and Si monoarsenides demonstrated high structural flexibility and a mild ability for reversible lithiation.
- Publication Date:
- Research Org.:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
- OSTI Identifier:
- 1526289
- Alternate Identifier(s):
- OSTI ID: 1506712
- Report Number(s):
- IS-J-9942
Journal ID: ISSN 0947-6539
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 25; Journal Issue: 25; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; layered materials; lithium; pnictides; solid-state NMR spectroscopy; tetrel
Citation Formats
Mark, Justin, Hanrahan, Michael P., Woo, Katherine E., Lee, Shannon, Rossini, Aaron J., and Kovnir, Kirill. Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides. United States: N. p., 2019.
Web. doi:10.1002/chem.201900339.
Mark, Justin, Hanrahan, Michael P., Woo, Katherine E., Lee, Shannon, Rossini, Aaron J., & Kovnir, Kirill. Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides. United States. https://doi.org/10.1002/chem.201900339
Mark, Justin, Hanrahan, Michael P., Woo, Katherine E., Lee, Shannon, Rossini, Aaron J., and Kovnir, Kirill. Mon .
"Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides". United States. https://doi.org/10.1002/chem.201900339. https://www.osti.gov/servlets/purl/1526289.
@article{osti_1526289,
title = {Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides},
author = {Mark, Justin and Hanrahan, Michael P. and Woo, Katherine E. and Lee, Shannon and Rossini, Aaron J. and Kovnir, Kirill},
abstractNote = {Abstract Lithiation of van der Waals tetrel‐arsenides, GeAs and SiAs, has been investigated. Electrochemical lithiation demonstrated large initial capacities of over 950 mAh g −1 accompanied by rapid fading over successive cycling in the voltage range 0.01–2 V. Limiting the voltage range to 0.5–2 V achieved more stable cycling, which was attributed to the intercalation process with lower capacities. Ex situ powder X‐ray diffraction confirmed complete amorphization of the samples after lithiation, as well as recrystallization of the binary tetrel‐arsenide phases after full delithiation in the voltage range 0.5–2 V. Solid‐state synthetic methods produce layered phases, in which Si‐As or Ge‐As layers are separated by Li cations. The first layered compounds in the corresponding ternary systems were discovered, Li 0.9 Ge 2.9 As 3.1 and Li 3 Si 7 As 8 , which crystallize in the Pbam (No. 55) and P 2/ m (No. 10) space groups, respectively. Semiconducting layered GeAs and SiAs accommodate the extra charge from Li cations through structural rearrangement in the Si‐As or Ge‐As layers and eventually by replacement of the tetrel dumbbells with sets of Li atoms. Ge and Si monoarsenides demonstrated high structural flexibility and a mild ability for reversible lithiation.},
doi = {10.1002/chem.201900339},
journal = {Chemistry - A European Journal},
number = 25,
volume = 25,
place = {United States},
year = {Mon Mar 18 00:00:00 EDT 2019},
month = {Mon Mar 18 00:00:00 EDT 2019}
}
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Works referenced in this record:
Two-dimensional GeAs with a visible range band gap
journal, January 2018
- Jung, Chan Su; Kim, Doyeon; Cha, Seunghwan
- Journal of Materials Chemistry A, Vol. 6, Issue 19
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
The Crystal Structures of SiP2, SiAs2, and GeP.
journal, January 1967
- Wadsten, Tommy; Vikan, M.; Krohn, C.
- Acta Chemica Scandinavica, Vol. 21
Solvothermal preparation of tin phosphide as a long-life anode for advanced lithium and sodium ion batteries
journal, February 2016
- Liu, Shuling; Zhang, Hongzhe; Xu, Liqiang
- Journal of Power Sources, Vol. 304
Free-standing molybdenum disulfide/graphene composite paper as a binder- and carbon-free anode for lithium-ion batteries
journal, August 2015
- Yang, MinHo; Ko, Seunghyun; Im, Ji Sun
- Journal of Power Sources, Vol. 288
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
NaGe6As6: Insertion of sodium into the layered semiconductor germanium arsenide GeAs
journal, May 2016
- Khatun, Mansura; Mar, Arthur
- Zeitschrift für Naturforschung B, Vol. 71, Issue 5
A Zintl phase with a layered network structure, potassium silicon arsenide (KSi3As3)
journal, July 1987
- Hurng, Weir Mirn; Corbett, John D.; Wang, Sue Lein
- Inorganic Chemistry, Vol. 26, Issue 15
Computational exploration of two-dimensional silicon diarsenide and germanium arsenide for photovoltaic applications
journal, January 2018
- Matta, Sri Kasi; Zhang, Chunmei; Jiao, Yalong
- Beilstein Journal of Nanotechnology, Vol. 9
Ternary arsenides ATt3As3 (A=K, Rb; Tt=Ge, Sn) with layered structures
journal, June 2016
- Khatun, Mansura; Stoyko, Stanislav S.; Mar, Arthur
- Journal of Solid State Chemistry, Vol. 238
Darstellung, Kristallstruktur und Eigenschaften von KLi2As
journal, February 1996
- Gil, Ra�l Hector Cardoso; H�nle, Wolfgang; Von Schnering, Hans-Georg
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 622, Issue 2
Über Zweistoffsysteme mit Germanium. II. Germanium/Arsen, Germanium/Antimon, Germanium/Wismut
journal, July 1940
- Stöhr, Herbert; Klemm, Wilhelm
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 244, Issue 2
Li 15 Si 4 Formation in Silicon Thin Film Negative Electrodes
journal, November 2015
- Iaboni, D. S. M.; Obrovac, M. N.
- Journal of The Electrochemical Society, Vol. 163, Issue 2
Exceptional Thermoelectric Properties of Layered GeAs 2
journal, October 2017
- Wang, Fancy Qian; Guo, Yaguang; Wang, Qian
- Chemistry of Materials, Vol. 29, Issue 21
Highly In-Plane Optical and Electrical Anisotropy of 2D Germanium Arsenide
journal, February 2018
- Yang, Shengxue; Yang, Yanhan; Wu, Minghui
- Advanced Functional Materials, Vol. 28, Issue 16
On the choice of graphite for lithium ion batteries
journal, September 1999
- Simon, B.; Flandrois, S.; Guerin, K.
- Journal of Power Sources, Vol. 81-82
Highly In‐Plane Anisotropic 2D GeAs 2 for Polarization‐Sensitive Photodetection
journal, August 2018
- Li, Liang; Gong, Penglai; Sheng, Daopeng
- Advanced Materials, Vol. 30, Issue 50
Perpendicular Optical Reversal of the Linear Dichroism and Polarized Photodetection in 2D GeAs
journal, November 2018
- Zhou, Ziqi; Long, Mingsheng; Pan, Longfei
- ACS Nano, Vol. 12, Issue 12
Tern�re Phosphide und Arsenide des Lithiums mit Elementen der 3. und 4. Gruppe
journal, February 1954
- Juza, Robert; Schulz, Werner
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 275, Issue 1-3
Solution-Grown Silicon Nanowires for Lithium-Ion Battery Anodes
journal, March 2010
- Chan, Candace K.; Patel, Reken N.; O’Connell, Michael J.
- ACS Nano, Vol. 4, Issue 3
NMR nomenclature. Nuclear spin properties and conventions for chemical shifts(IUPAC Recommendations 2001)
journal, January 2001
- Harris, Robin K.; Becker, Edwin D.; Cabral de Menezes, Sonia M.
- Pure and Applied Chemistry, Vol. 73, Issue 11
"Special points for Brillouin-zone integrations"—a reply
journal, August 1977
- Pack, James D.; Monkhorst, Hendrik J.
- Physical Review B, Vol. 16, Issue 4
Tin Phosphide as a Promising Anode Material for Na-Ion Batteries
journal, April 2014
- Kim, Youngjin; Kim, Yongil; Choi, Aram
- Advanced Materials, Vol. 26, Issue 24
GeAs: Highly Anisotropic van der Waals Thermoelectric Material
journal, April 2016
- Lee, Kathleen; Kamali, Saeed; Ericsson, Tore
- Chemistry of Materials, Vol. 28, Issue 8
Alkali Metals Extraction Reactions with the Silicides Li 15 Si 4 and Li 3 NaSi 6 : Amorphous Si versus allo -Si
journal, November 2014
- Zeilinger, Michael; Jantke, Laura-Alice; Scherf, Lavinia M.
- Chemistry of Materials, Vol. 26, Issue 22
Single Crystal Growth and Thermodynamic Stability of Li 17 Si 4
journal, April 2013
- Zeilinger, Michael; Benson, Daryn; Häussermann, Ulrich
- Chemistry of Materials, Vol. 25, Issue 9
Electrochemical synthesis of the allotrope allo-Ge and investigations on its use as an anode material
journal, January 2017
- Scherf, L. M.; Hattendorff, J.; Buchberger, I.
- Journal of Materials Chemistry A, Vol. 5, Issue 22
GeAs and SiAs monolayers: Novel 2D semiconductors with suitable band structures
journal, January 2018
- Zhou, Liqin; Guo, Yu; Zhao, Jijun
- Physica E: Low-dimensional Systems and Nanostructures, Vol. 95
Electrochemical Intercalation of Lithium into Carbon Materials
journal, April 1994
- Billaud, Denis; Henry, Francois; Wellmann, Patrick
- Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 245, Issue 1
The crystal structure of LiAs
journal, January 1959
- Cromer, D. T.
- Acta Crystallographica, Vol. 12, Issue 1
Synthesis of molybdenum disulfide (MoS2) for lithium ion battery applications
journal, September 2009
- Feng, Chuanqi; Ma, Jun; Li, Hua
- Materials Research Bulletin, Vol. 44, Issue 9
A reversible graphite-lithium negative electrode for electrochemical generators
journal, January 1983
- Yazami, R.; Touzain, Ph.
- Journal of Power Sources, Vol. 9, Issue 3
Black phosphorus with superior lithium ion batteries performance directly synthesized by the efficient thermal-vaporization method
journal, February 2018
- Jiang, Qianqian; Li, Jie; Yuan, Nannan
- Electrochimica Acta, Vol. 263
Ultrahigh-Resolution 7 Li Magic-Angle Spinning Nuclear Magnetic Resonance Spectroscopy by Isotopic Dilution
journal, July 2018
- Michaelis, Vladimir K.; Levin, Kirill; Germanov, Yaroslav
- Chemistry of Materials, Vol. 30, Issue 16
The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013
- Goodenough, John B.; Park, Kyu-Sung
- Journal of the American Chemical Society, Vol. 135, Issue 4
Application of silicene, germanene and stanene for Na or Li ion storage: A theoretical investigation
journal, September 2016
- Mortazavi, Bohayra; Dianat, Arezoo; Cuniberti, Gianaurelio
- Electrochimica Acta, Vol. 213
Arsenic for high-capacity lithium- and sodium-ion batteries
journal, January 2018
- Lim, Young Rok; Shojaei, Fazel; Park, Kidong
- Nanoscale, Vol. 10, Issue 15
GeP and (Ge1−Sn )(P1−Ge ) (x≈0.12, y≈0.05): Synthesis, structure, and properties of two-dimensional layered tetrel phosphides
journal, April 2015
- Lee, Kathleen; Synnestvedt, Sarah; Bellard, Maverick
- Journal of Solid State Chemistry, Vol. 224
Graphite structure and lithium intercalation
journal, October 1997
- Shi, H.; Barker, J.; Saïdi, M. Y.
- Journal of Power Sources, Vol. 68, Issue 2
Few-Layer GeAs Field-Effect Transistors and Infrared Photodetectors
journal, April 2018
- Guo, Jian; Liu, Yuan; Ma, Yue
- Advanced Materials, Vol. 30, Issue 21
Structural and thermodynamic similarities of phases in the Li–Tt (Tt = Si, Ge) systems: redetermination of the lithium-rich side of the Li–Ge phase diagram and crystal structures of Li 17 Si 4.0−x Ge x for x = 2.3, 3.1, 3.5, and 4 as well as Li 4.1 Ge
journal, January 2014
- Zeilinger, Michael; Fässler, Thomas F.
- Dalton Trans., Vol. 43, Issue 40
Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries
journal, January 2018
- Del Rio Castillo, Antonio Esau; Pellegrini, Vittorio; Sun, Haiyan
- Chemistry of Materials, Vol. 30, Issue 2
Porous silaphosphorene, silaarsenene and silaantimonene: a sweet marriage of Si and P/As/Sb
journal, January 2018
- Lin, Shiru; Gu, Jinxing; Wang, Yu
- Journal of Materials Chemistry A, Vol. 6, Issue 8
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
6Li nuclear magnetic resonance chemical shifts, coordination number and relaxation in crystalline and glassy silicates
journal, October 1995
- Xu, Z.; Stebbins, Jonathan F.
- Solid State Nuclear Magnetic Resonance, Vol. 5, Issue 1
Clathrate III of Group 14 Exists After All
journal, April 2001
- Bobev, Svilen; Sevov, Slavi C.
- Journal of the American Chemical Society, Vol. 123, Issue 14
High Field Multinuclear NMR Investigation of the SEI Layer in Lithium Rechargeable Batteries
journal, January 2005
- Meyer, Benjamin M.; Leifer, Nicole; Sakamoto, Sarah
- Electrochemical and Solid-State Letters, Vol. 8, Issue 3
Electrochemical Lithiation of Ge: New Insights by Operando Spectroscopy and Diffraction
journal, February 2018
- Loaiza, Laura C.; Louvain, Nicolas; Fraisse, Bernard
- The Journal of Physical Chemistry C, Vol. 122, Issue 7
A facile high-yield solvothermal route to tin phosphide Sn4P3
journal, December 2006
- Kovnir, Kirill A.; Kolen’ko, Yury V.; Ray, Sugata
- Journal of Solid State Chemistry, Vol. 179, Issue 12
Optical Absorption, Reflectivity, and Electrical Conductivity in GeAs and Ge
journal, April 1971
- Rau, John W.; Kannewurf, C. R.
- Physical Review B, Vol. 3, Issue 8
SnAs-Based Layered Superconductor NaSn 2 As 2
journal, December 2017
- Goto, Yosuke; Yamada, Akira; Matsuda, Tatsuma D.
- Journal of the Physical Society of Japan, Vol. 86, Issue 12
A Hydride Route to Ternary Alkali Metal Borides: A Case Study of Lithium Nickel Borides
journal, February 2019
- Gvozdetskyi, Volodymyr; Hanrahan, Michael P.; Ribeiro, Raquel A.
- Chemistry – A European Journal, Vol. 25, Issue 16
Improving the cycling stability of Sn 4 P 3 anode for sodium-ion battery
journal, October 2017
- Wang, Wenhui; Zhang, Jiaolong; Yu, Denis Y. W.
- Journal of Power Sources, Vol. 364
Monolayered Silicon and Germanium Monopnictide Semiconductors: Excellent Stability, High Absorbance, and Strain Engineering of Electronic Properties
journal, January 2018
- Cheng, Ai-Qiang; He, Zi; Zhao, Jun
- ACS Applied Materials & Interfaces, Vol. 10, Issue 6
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Cu 3 P Binary Phosphide: Synthesis via a Wet Mechanochemical Method and Electrochemical Behavior as Negative Electrode Material for Lithium-Ion Batteries
journal, September 2012
- Stan, Marian Cristian; Klöpsch, Richard; Bhaskar, Aiswarya
- Advanced Energy Materials, Vol. 3, Issue 2
The crystal structures of the germanium–arsenic compounds: I. Germanium diarsenide, GeAs 2
journal, February 1962
- Bryden, J. H.
- Acta Crystallographica, Vol. 15, Issue 2
Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li 1– x Sn 2+ x As 2
journal, March 2015
- Lee, Kathleen; Kaseman, Derrick; Sen, Sabyasachi
- Journal of the American Chemical Society, Vol. 137, Issue 10
Synthesis of hollow spherical tin phosphides (Sn4P3) and their high adsorptive and electrochemical performance
journal, March 2016
- Liu, Shuling; Zhang, Hongzhe; Xu, Liqiang
- Journal of Crystal Growth, Vol. 438
Emerging nanostructured electrode materials for water electrolysis and rechargeable beyond Li-ion batteries
journal, January 2017
- Pomerantseva, Ekaterina; Resini, Carlo; Kovnir, Kirill
- Advances in Physics: X, Vol. 2, Issue 2
Electronic structure of the germanium phosphide monolayer and Li-diffusion in its bilayer
journal, January 2016
- Shojaei, Fazel; Kang, Hong Seok
- Physical Chemistry Chemical Physics, Vol. 18, Issue 47
Über Siliciumarsenide
journal, August 1941
- Klemm, Wilhelm; Pirscher, Peter
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 247, Issue 3
Adsorption and Diffusion of Lithium on Layered Silicon for Li-Ion Storage
journal, April 2013
- Tritsaris, Georgios A.; Kaxiras, Efthimios; Meng, Sheng
- Nano Letters, Vol. 13, Issue 5
GeAs 2 : A IV–V Group Two-Dimensional Semiconductor with Ultralow Thermal Conductivity and High Thermoelectric Efficiency
journal, July 2017
- Zhao, Tianqi; Sun, Yajing; Shuai, Zhigang
- Chemistry of Materials, Vol. 29, Issue 15
Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994
- Blöchl, Peter E.; Jepsen, O.; Andersen, O. K.
- Physical Review B, Vol. 49, Issue 23
Cu3P as anode material for lithium ion battery: powder morphology and electrochemical performances
journal, September 2004
- Bichat, Marie-Pierre; Politova, Tatiana; Pfeiffer, Heriberto
- Journal of Power Sources, Vol. 136, Issue 1
Air stable copper phosphide (Cu3P): a possible negative electrode material for lithium batteries
journal, March 2004
- Pfeiffer, Heriberto; Tancret, Franck; Bichat, Marie-Pierre
- Electrochemistry Communications, Vol. 6, Issue 3
The Crystal Structure of SiAs.
journal, January 1965
- Wadsten, Tommy; Burmester, S.; Cederberg, G.
- Acta Chemica Scandinavica, Vol. 19
Amorphous silicon anode for lithium-ion rechargeable batteries
journal, April 2003
- Jung, H.
- Journal of Power Sources, Vol. 115, Issue 2
Konstitution von Phosphiden, Arseniden, Antimoniden und Wismutiden des Lithiums, Natriums und Kaliums
journal, August 1937
- Brauer, G.; Zintl, E.
- Zeitschrift für Physikalische Chemie, Vol. 37B, Issue 1
Crystal structure of the low-temperature modification of trilithium heptaarsenide, LT-Li3As7
journal, December 2002
- Hönle, W.; Buresch, J.; Peters, K.
- Zeitschrift für Kristallographie - New Crystal Structures, Vol. 217, Issue JG
A Facile High-Yield Solvothermal Route to Tin Phosphide Sn4P3.
journal, March 2007
- Kovnir, Kirill A.; Kolen'ko, Yury V.; Ray, Sugata
- ChemInform, Vol. 38, Issue 11
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
Application of silicene, germanene and stanene for Na or Li ion storage: A theoretical investigation
text, January 2017
- Mortazavi, B.; Dianat, A.; Cuniberti, G.
- arXiv
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journal, November 2019
- Eickhoff, Henrik; Sedlmeier, Christian; Klein, Wilhelm
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 646, Issue 3
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journal, January 2020
- Zeng, Hui; Chen, Ru‐Shan; Yao, Ge
- Advanced Electronic Materials, Vol. 6, Issue 3