Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes
Abstract
Silicon demonstrates great potential as a next-generation lithium ion battery anode because of high capacity and elemental abundance. However, the issue of low initial Coulombic efficiency needs to be addressed to enable large-scale applications. There are mainly two mechanisms for this lithium loss in the first cycle: the formation of the solid electrolyte interphase and lithium trapping in the electrode. The former has been heavily investigated while the latter has been largely neglected. Here, through both theoretical calculation and experimental study, we demonstrate that by introducing Ge substitution in Si with fine compositional control, the energy barrier of lithium diffusion will be greatly reduced because of the lattice expansion. This effect of isovalent isomorphism significantly reduces the Li trapping by ~70% and improves the initial Coulombic efficiency to over 90%. We expect that various systems of battery materials can benefit from this mechanism for fine-tuning their electrochemical behaviors.
- Authors:
-
- Nanjing Univ. (China). National Lab. of Solid State Microstructures, College of Engineering and Applied Sciences, Jiangsu Key Lab. of Artificial Functional Materials
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1597487
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Science Advances
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 11; Journal ID: ISSN 2375-2548
- Publisher:
- AAAS
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Zhu, Bin, Liu, Guoliang, Lv, Guangxin, Mu, Yu, Zhao, Yunlei, Wang, Yuxi, Li, Xiuqiang, Yao, Pengcheng, Deng, Yu, Cui, Yi, and Zhu, Jia. Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes. United States: N. p., 2019.
Web. doi:10.1126/sciadv.aax0651.
Zhu, Bin, Liu, Guoliang, Lv, Guangxin, Mu, Yu, Zhao, Yunlei, Wang, Yuxi, Li, Xiuqiang, Yao, Pengcheng, Deng, Yu, Cui, Yi, & Zhu, Jia. Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes. United States. https://doi.org/10.1126/sciadv.aax0651
Zhu, Bin, Liu, Guoliang, Lv, Guangxin, Mu, Yu, Zhao, Yunlei, Wang, Yuxi, Li, Xiuqiang, Yao, Pengcheng, Deng, Yu, Cui, Yi, and Zhu, Jia. Fri .
"Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes". United States. https://doi.org/10.1126/sciadv.aax0651. https://www.osti.gov/servlets/purl/1597487.
@article{osti_1597487,
title = {Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes},
author = {Zhu, Bin and Liu, Guoliang and Lv, Guangxin and Mu, Yu and Zhao, Yunlei and Wang, Yuxi and Li, Xiuqiang and Yao, Pengcheng and Deng, Yu and Cui, Yi and Zhu, Jia},
abstractNote = {Silicon demonstrates great potential as a next-generation lithium ion battery anode because of high capacity and elemental abundance. However, the issue of low initial Coulombic efficiency needs to be addressed to enable large-scale applications. There are mainly two mechanisms for this lithium loss in the first cycle: the formation of the solid electrolyte interphase and lithium trapping in the electrode. The former has been heavily investigated while the latter has been largely neglected. Here, through both theoretical calculation and experimental study, we demonstrate that by introducing Ge substitution in Si with fine compositional control, the energy barrier of lithium diffusion will be greatly reduced because of the lattice expansion. This effect of isovalent isomorphism significantly reduces the Li trapping by ~70% and improves the initial Coulombic efficiency to over 90%. We expect that various systems of battery materials can benefit from this mechanism for fine-tuning their electrochemical behaviors.},
doi = {10.1126/sciadv.aax0651},
journal = {Science Advances},
number = 11,
volume = 5,
place = {United States},
year = {2019},
month = {11}
}
Web of Science
Works referenced in this record:
High performance silicon nanoparticle anode in fluoroethylene carbonate-based electrolyte for Li-ion batteries
journal, January 2012
- Lin, Yong-Mao; Klavetter, Kyle C.; Abel, Paul R.
- Chemical Communications, Vol. 48, Issue 58
Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes
journal, June 2016
- Michan, Alison L.; Divitini, Giorgio; Pell, Andrew J.
- Journal of the American Chemical Society, Vol. 138, Issue 25
Correlating Structure and Function of Battery Interphases at Atomic Resolution Using Cryoelectron Microscopy
journal, October 2018
- Li, Yuzhang; Huang, William; Li, Yanbin
- Joule, Vol. 2, Issue 10
Hierarchical Carbon-Coated Ball-Milled Silicon: Synthesis and Applications in Free-Standing Electrodes and High-Voltage Full Lithium-Ion Batteries
journal, May 2018
- Shen, Chenfei; Fang, Xin; Ge, Mingyuan
- ACS Nano, Vol. 12, Issue 6
Superionic Conductors: Li 10+δ [Sn y Si 1– y ] 1+δ P 2−δ S 12 with a Li 10 GeP 2 S 12 -type Structure in the Li 3 PS 4 –Li 4 SnS 4 –Li 4 SiS 4 Quasi-ternary System
journal, July 2017
- Sun, Yulong; Suzuki, Kota; Hori, Satoshi
- Chemistry of Materials, Vol. 29, Issue 14
High-performance lithium-ion anodes using a hierarchical bottom-up approach
journal, March 2010
- Magasinski, A.; Dixon, P.; Hertzberg, B.
- Nature Materials, Vol. 9, Issue 4, p. 353-358
Sodium Carboxymethyl Cellulose
journal, January 2007
- Li, Jing; Lewis, R. B.; Dahn, J. R.
- Electrochemical and Solid-State Letters, Vol. 10, Issue 2
Sn 78 Ge 22 @Carbon Core−Shell Nanowires as Fast and High-Capacity Lithium Storage Media
journal, September 2007
- Lee, Hyojin; Cho, Jaephil
- Nano Letters, Vol. 7, Issue 9
High-capacity battery cathode prelithiation to offset initial lithium loss
journal, January 2016
- Sun, Yongming; Lee, Hyun-Wook; Seh, Zhi Wei
- Nature Energy, Vol. 1, Issue 1
Bottleneck of Diffusion and Inductive Effects in Li 10 Ge 1– x Sn x P 2 S 12
journal, February 2018
- Krauskopf, Thorben; Culver, Sean P.; Zeier, Wolfgang G.
- Chemistry of Materials, Vol. 30, Issue 5
High-performance lithium battery anodes using silicon nanowires
journal, December 2007
- Chan, Candace K.; Peng, Hailin; Liu, Gao
- Nature Nanotechnology, Vol. 3, Issue 1, p. 31-35
Nanostructured Si (1- x ) Ge x for Tunable Thin Film Lithium-Ion Battery Anodes
journal, March 2013
- Abel, Paul R.; Chockla, Aaron M.; Lin, Yong-Mao
- ACS Nano, Vol. 7, Issue 3
From molecules to solids with the DMol3 approach
journal, November 2000
- Delley, B.
- The Journal of Chemical Physics, Vol. 113, Issue 18
Scalable Production of Si Nanoparticles Directly from Low Grade Sources for Lithium-Ion Battery Anode
journal, August 2015
- Zhu, Bin; Jin, Yan; Tan, Yingling
- Nano Letters, Vol. 15, Issue 9
An all‐electron numerical method for solving the local density functional for polyatomic molecules
journal, January 1990
- Delley, B.
- The Journal of Chemical Physics, Vol. 92, Issue 1
Promises and challenges of nanomaterials for lithium-based rechargeable batteries
journal, June 2016
- Sun, Yongming; Liu, Nian; Cui, Yi
- Nature Energy, Vol. 1, Issue 7
Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes
journal, January 2016
- Li, Yuzhang; Yan, Kai; Lee, Hyun-Wook
- Nature Energy, Vol. 1, Issue 2
Silicon Nanotube Battery Anodes
journal, November 2009
- Park, Mi-Hee; Kim, Min Gyu; Joo, Jaebum
- Nano Letters, Vol. 9, Issue 11, p. 3844-3847
Mesoporous Silicon Hollow Nanocubes Derived from Metal–Organic Framework Template for Advanced Lithium-Ion Battery Anode
journal, April 2017
- Yoon, Taeseung; Bok, Taesoo; Kim, Chulhyun
- ACS Nano, Vol. 11, Issue 5
Stable cycling of double-walled silicon nanotube battery anodes through solid–electrolyte interphase control
journal, March 2012
- Wu, Hui; Chan, Gerentt; Choi, Jang Wook
- Nature Nanotechnology, Vol. 7, Issue 5
Lithium trapping in alloy forming electrodes and current collectors for lithium based batteries
journal, January 2017
- Rehnlund, David; Lindgren, Fredrik; Böhme, Solveig
- Energy & Environmental Science, Vol. 10, Issue 6
Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955
- Mulliken, R. S.
- The Journal of Chemical Physics, Vol. 23, Issue 10
Artificial Solid Electrolyte Interphase-Protected Li x Si Nanoparticles: An Efficient and Stable Prelithiation Reagent for Lithium-Ion Batteries
journal, June 2015
- Zhao, Jie; Lu, Zhenda; Wang, Haotian
- Journal of the American Chemical Society, Vol. 137, Issue 26
Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density
journal, June 2015
- Son, In Hyuk; Hwan Park, Jong; Kwon, Soonchul
- Nature Communications, Vol. 6, Issue 1
The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes
journal, August 2015
- Schroder, Kjell; Alvarado, Judith; Yersak, Thomas A.
- Chemistry of Materials, Vol. 27, Issue 16
Improved Performance of the Silicon Anode for Li-Ion Batteries: Understanding the Surface Modification Mechanism of Fluoroethylene Carbonate as an Effective Electrolyte Additive
journal, March 2015
- Xu, Chao; Lindgren, Fredrik; Philippe, Bertrand
- Chemistry of Materials, Vol. 27, Issue 7
Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries
journal, July 2017
- Choi, Sunghun; Kwon, Tae-woo; Coskun, Ali
- Science, Vol. 357, Issue 6348
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries
journal, September 2000
- Poizot, P.; Laruelle, S.; Grugeon, S.
- Nature, Vol. 407, Issue 6803, p. 496-499
Ab initio and kinetic Monte Carlo study of lithium diffusion in LiSi, Li12Si7, Li13Si5 and Li15Si4
journal, October 2016
- Moon, Janghyuk; Lee, Byeongchan; Cho, Maenghyo
- Journal of Power Sources, Vol. 328
The synchronous-transit method for determining reaction pathways and locating molecular transition states
journal, July 1977
- Halgren, Thomas A.; Lipscomb, William N.
- Chemical Physics Letters, Vol. 49, Issue 2
Effect of vinylene carbonate (VC) as electrolyte additive on electrochemical performance of Si film anode for lithium ion batteries
journal, December 2007
- Chen, Libao; Wang, Ke; Xie, Xiaohua
- Journal of Power Sources, Vol. 174, Issue 2
Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes
journal, January 1997
- Peled, E.
- Journal of The Electrochemical Society, Vol. 144, Issue 8
Controlled Prelithiation of Silicon Monoxide for High Performance Lithium-Ion Rechargeable Full Cells
journal, December 2015
- Kim, Hye Jin; Choi, Sunghun; Lee, Seung Jong
- Nano Letters, Vol. 16, Issue 1
Effect of Fluoroethylene Carbonate (FEC) on the Performance and Surface Chemistry of Si-Nanowire Li-Ion Battery Anodes
journal, December 2011
- Etacheri, Vinodkumar; Haik, Ortal; Goffer, Yossi
- Langmuir, Vol. 28, Issue 1
Cycling Behavior of Thin Film LiAl Electrodes with Liquid and Solid Electrolytes
journal, January 1985
- Maskell, W. C.
- Journal of The Electrochemical Society, Vol. 132, Issue 7
First-principles simulation: ideas, illustrations and the CASTEP code
journal, March 2002
- Segall, M. D.; Lindan, Philip J. D.; Probert, M. J.
- Journal of Physics: Condensed Matter, Vol. 14, Issue 11
Dry-air-stable lithium silicide–lithium oxide core–shell nanoparticles as high-capacity prelithiation reagents
journal, October 2014
- Zhao, Jie; Lu, Zhenda; Liu, Nian
- Nature Communications, Vol. 5, Article No. 5088
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992
- Perdew, John P.; Chevary, J. A.; Vosko, S. H.
- Physical Review B, Vol. 46, Issue 11
Size-Dependent Fracture of Silicon Nanoparticles During Lithiation
journal, January 2012
- Liu, Xiao Hua; Zhong, Li; Huang, Shan
- ACS Nano, Vol. 6, Issue 2
The Surface Chemistry of Lithium Electrodes in Alkyl Carbonate Solutions
journal, January 1994
- Aurbach, Doron
- Journal of The Electrochemical Society, Vol. 141, Issue 1
Building better batteries
journal, February 2008
- Armand, M.; Tarascon, J.-M.
- Nature, Vol. 451, Issue 7179, p. 652-657
A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries
journal, September 2011
- Kovalenko, I.; Zdyrko, B.; Magasinski, A.
- Science, Vol. 334, Issue 6052
A Laser Ablation Method for the Synthesis of Crystalline Semiconductor Nanowires
journal, January 1998
- Morales, Alfredo M.; Lieber, Charles M.
- Science, Vol. 279, Issue 5348, p. 208-211
On the origin of the capacity fading for aluminium negative electrodes in Li-ion batteries
journal, December 2014
- Oltean, Gabriel; Tai, Cheuk-Wai; Edström, Kristina
- Journal of Power Sources, Vol. 269
Nonfilling Carbon Coating of Porous Silicon Micrometer-Sized Particles for High-Performance Lithium Battery Anodes
journal, February 2015
- Lu, Zhenda; Liu, Nian; Lee, Hyun-Wook
- ACS Nano, Vol. 9, Issue 3
Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014
- Larcher, D.; Tarascon, J-M.
- Nature Chemistry, Vol. 7, Issue 1
Dual-Functionalized Double Carbon Shells Coated Silicon Nanoparticles for High Performance Lithium-Ion Batteries
journal, March 2017
- Chen, Shuangqiang; Shen, Laifa; van Aken, Peter A.
- Advanced Materials, Vol. 29, Issue 21
A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes
journal, February 2014
- Liu, Nian; Lu, Zhenda; Zhao, Jie
- Nature Nanotechnology, Vol. 9, Issue 3
First principles methods using CASTEP
journal, January 2005
- Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J.
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6
Revealing lithium–silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy
journal, February 2014
- Ogata, K.; Salager, E.; Kerr, C. J.
- Nature Communications, Vol. 5, Issue 1
Li–O2 and Li–S batteries with high energy storage
journal, January 2012
- Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
- Nature Materials, Vol. 11, Issue 1, p. 19-29
Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy lithium-ion batteries
journal, August 2016
- Ko, Minseong; Chae, Sujong; Ma, Jiyoung
- Nature Energy, Vol. 1, Issue 9
Mesoporous silicon sponge as an anti-pulverization structure for high-performance lithium-ion battery anodes
journal, July 2014
- Li, Xiaolin; Gu, Meng; Hu, Shenyang
- Nature Communications, Vol. 5, Issue 1
Porous Doped Silicon Nanowires for Lithium Ion Battery Anode with Long Cycle Life
journal, April 2012
- Ge, Mingyuan; Rong, Jiepeng; Fang, Xin
- Nano Letters, Vol. 12, Issue 5
Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−M )P2S12 (M = Si, Sn)
journal, December 2014
- Kato, Yuki; Saito, Ryoko; Sakano, Mitsuru
- Journal of Power Sources, Vol. 271
Micro-sized nano-porous Si/C anodes for lithium ion batteries
journal, January 2015
- Tian, Huajun; Tan, Xiaojian; Xin, Fengxia
- Nano Energy, Vol. 11
Preparation, Structural Characterization, and Electrical Conductivity of Highly Ion-Conducting Glasses and Glass Ceramics in the System Li 1+ x Al x Sn y Ge 2-(x+y) (PO 4 ) 3
journal, June 2016
- Santagneli, Silvia H.; Baldacim, Helio V. A.; Ribeiro, Sidney J. L.
- The Journal of Physical Chemistry C, Vol. 120, Issue 27
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model
journal, January 1979
- Peled, E.
- Journal of The Electrochemical Society, Vol. 126, Issue 12
Alloy Design for Lithium-Ion Battery Anodes
journal, January 2007
- Obrovac, M. N.; Christensen, Leif; Le, Dinh Ba
- Journal of The Electrochemical Society, Vol. 154, Issue 9, p. A849-A855
Promise and reality of post-lithium-ion batteries with high energy densities
journal, March 2016
- Choi, Jang Wook; Aurbach, Doron
- Nature Reviews Materials, Vol. 1, Issue 4
High-performance lithium battery anodes using silicon nanowires
book, October 2010
- Chan, Candace K.; Peng, Hailin; Liu, Gao
- Materials for Sustainable Energy: A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group, p. 187-191
Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes
text, January 2016
- Michan, Alison L.; Divitini, Giorgio; Pell, Andrew J.
- Apollo - University of Cambridge Repository
Sodium Carboxymethyl Cellulose
journal, January 1985
- Senda, Hisakazu
- Journal of Synthetic Organic Chemistry, Japan, Vol. 43, Issue 4