Kinetic phase evolution of spinel cobalt oxide during lithiation
Abstract
Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Harvard Univ., Cambridge, MA (United States)
- Univ. of Maryland, College Park, MD (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1328370
- Report Number(s):
- BNL-112671-2016-JA
Journal ID: ISSN 1936-0851; KC0403020
- Grant/Contract Number:
- SC0012704; SC0012673
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Name: ACS Nano; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 29 ENERGY PLANNING, POLICY, AND ECONOMY; Co3O4 nanoparticles; lithium ion battery; in situ TEM; Center for Functional Nanomaterials
Citation Formats
Li, Jing, He, Kai, Meng, Qingping, Li, Xin, Zhu, Yizhou, Hwang, Sooyeon, Sun, Ke, Gan, Hong, Zhu, Yimei, Mo, Yifei, Stach, Eric A., and Su, Dong. Kinetic phase evolution of spinel cobalt oxide during lithiation. United States: N. p., 2016.
Web. doi:10.1021/acsnano.6b04958.
Li, Jing, He, Kai, Meng, Qingping, Li, Xin, Zhu, Yizhou, Hwang, Sooyeon, Sun, Ke, Gan, Hong, Zhu, Yimei, Mo, Yifei, Stach, Eric A., & Su, Dong. Kinetic phase evolution of spinel cobalt oxide during lithiation. United States. https://doi.org/10.1021/acsnano.6b04958
Li, Jing, He, Kai, Meng, Qingping, Li, Xin, Zhu, Yizhou, Hwang, Sooyeon, Sun, Ke, Gan, Hong, Zhu, Yimei, Mo, Yifei, Stach, Eric A., and Su, Dong. Thu .
"Kinetic phase evolution of spinel cobalt oxide during lithiation". United States. https://doi.org/10.1021/acsnano.6b04958. https://www.osti.gov/servlets/purl/1328370.
@article{osti_1328370,
title = {Kinetic phase evolution of spinel cobalt oxide during lithiation},
author = {Li, Jing and He, Kai and Meng, Qingping and Li, Xin and Zhu, Yizhou and Hwang, Sooyeon and Sun, Ke and Gan, Hong and Zhu, Yimei and Mo, Yifei and Stach, Eric A. and Su, Dong},
abstractNote = {Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.},
doi = {10.1021/acsnano.6b04958},
journal = {ACS Nano},
number = ,
volume = ,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Li-ion battery materials: present and future
journal, June 2015
- Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae
- Materials Today, Vol. 18, Issue 5
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes
journal, September 2014
- Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R.
- Nature Materials, Vol. 13, Issue 12
Battery materials for ultrafast charging and discharging
journal, March 2009
- Kang, Byoungwoo; Ceder, Gerbrand
- Nature, Vol. 458, Issue 7235, p. 190-193
Ultimate Limits to Intercalation Reactions for Lithium Batteries
journal, October 2014
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 114, Issue 23
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
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
From the vanadates to 3d-metal oxides negative electrodes
journal, September 2000
- Poizot, P.; Laruelle, S.; Grugeon, S.
- Ionics, Vol. 6, Issue 5-6
Transitions from Near-Surface to Interior Redox upon Lithiation in Conversion Electrode Materials
journal, January 2015
- He, Kai; Xin, Huolin L.; Zhao, Kejie
- Nano Letters, Vol. 15, Issue 2
Lithium insertion into Co3O4: A preliminary investigation
journal, September 1985
- Thackeray, M.; Baker, S.; Adendorff, K.
- Solid State Ionics, Vol. 17, Issue 2
Co3O4 nanorods/graphene nanosheets nanocomposites for lithium ion batteries with improved reversible capacity and cycle stability
journal, March 2012
- Tao, Liqi; Zai, Jiantao; Wang, Kaixue
- Journal of Power Sources, Vol. 202
Electrochemical reaction of nanocrystalline Co3O4 thin film with Lithium
journal, May 2004
- Fu, Z.; Wang, Y.; Zhang, Y.
- Solid State Ionics, Vol. 170, Issue 1-2
The Electrochemical Reduction of Co[sub 3]O[sub 4] in a Lithium Cell
journal, January 2002
- Larcher, D.; Sudant, G.; Leriche, J-B.
- Journal of The Electrochemical Society, Vol. 149, Issue 3
Mesoporous Co 3 O 4 Nanowire Arrays for Lithium Ion Batteries with High Capacity and Rate Capability
journal, January 2008
- Li, Yanguang; Tan, Bing; Wu, Yiying
- Nano Letters, Vol. 8, Issue 1
Nanorod-assembled Co3O4 hexapods with enhanced electrochemical performance for lithium-ion batteries
journal, January 2012
- Wang, Liming; Liu, Bin; Ran, Sihan
- Journal of Materials Chemistry, Vol. 22, Issue 44
High-performance anode based on porous Co3O4 nanodiscs
journal, June 2014
- Pan, Anqiang; Wang, Yaping; Xu, Wu
- Journal of Power Sources, Vol. 255
Molten hydroxides synthesis of hierarchical cobalt oxide nanostructure and its application as anode material for lithium ion batteries
journal, May 2011
- Xu, Minwei; Wang, Fei; Zhao, Mingshu
- Electrochimica Acta, Vol. 56, Issue 13
Micro-/Nanostructured Co 3 O 4 Anode with Enhanced Rate Capability for Lithium-Ion Batteries
journal, May 2014
- Huang, Guoyong; Xu, Shengming; Lu, Shasha
- ACS Applied Materials & Interfaces, Vol. 6, Issue 10
Mesoporous and nanowire Co 3 O 4 as negative electrodes for rechargeable lithium batteries
journal, January 2007
- Shaju, Kuthanapillil M.; Jiao, Feng; Débart, Aurélie
- Phys. Chem. Chem. Phys., Vol. 9, Issue 15
Graphene Anchored with Co3O4 Nanoparticles as Anode of Lithium Ion Batteries with Enhanced Reversible Capacity and Cyclic Performance
journal, June 2010
- Wu, Zhong-Shuai; Ren, Wencai; Wen, Lei
- ACS Nano, Vol. 4, Issue 6, p. 3187-3194
Co3O4 Nanocages for High-Performance Anode Material in Lithium-Ion Batteries
journal, March 2012
- Yan, Nan; Hu, Lin; Li, Yan
- The Journal of Physical Chemistry C, Vol. 116, Issue 12, p. 7227-7235
In situ TEM electrochemistry of anode materials in lithium ion batteries
journal, January 2011
- Liu, Xiao Hua; Huang, Jian Yu
- Energy & Environmental Science, Vol. 4, Issue 10
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014
- Liu, H.; Strobridge, F. C.; Borkiewicz, O. J.
- Science, Vol. 344, Issue 6191
Overpotential-Dependent Phase Transformation Pathways in Lithium Iron Phosphate Battery Electrodes
journal, November 2010
- Kao, Yu-Hua; Tang, Ming; Meethong, Nonglak
- Chemistry of Materials, Vol. 22, Issue 21
Intercalation Pathway in Many-Particle LiFePO 4 Electrode Revealed by Nanoscale State-of-Charge Mapping
journal, February 2013
- Chueh, William C.; El Gabaly, Farid; Sugar, Joshua D.
- Nano Letters, Vol. 13, Issue 3
In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
journal, December 2010
- Huang, J. Y.; Zhong, L.; Wang, C. M.
- Science, Vol. 330, Issue 6010, p. 1515-1520
In Situ TEM Study of Lithiation Behavior of Silicon Nanoparticles Attached to and Embedded in a Carbon Matrix
journal, August 2012
- Gu, Meng; Li, Ying; Li, Xiaolin
- ACS Nano, Vol. 6, Issue 9
In Situ Transmission Electron Microscopy Observation of Microstructure and Phase Evolution in a SnO 2 Nanowire during Lithium Intercalation
journal, May 2011
- Wang, Chong-Min; Xu, Wu; Liu, Jun
- Nano Letters, Vol. 11, Issue 5
Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy
journal, September 2012
- McDowell, Matthew T.; Ryu, Ill; Lee, Seok Woo
- Advanced Materials, Vol. 24, Issue 45
In Situ Observation of Divergent Phase Transformations in Individual Sulfide Nanocrystals
journal, January 2015
- McDowell, Matthew T.; Lu, Zhenda; Koski, Kristie J.
- Nano Letters, Vol. 15, Issue 2
Sodiation via Heterogeneous Disproportionation in FeF 2 Electrodes for Sodium-Ion Batteries
journal, June 2014
- He, Kai; Zhou, Yongning; Gao, Peng
- ACS Nano, Vol. 8, Issue 7
Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy
journal, May 2016
- He, Kai; Zhang, Sen; Li, Jing
- Nature Communications, Vol. 7, Issue 1
Atomic-Scale Observation of Lithiation Reaction Front in Nanoscale SnO 2 Materials
journal, June 2013
- Nie, Anmin; Gan, Li-Yong; Cheng, Yingchun
- ACS Nano, Vol. 7, Issue 7
In Situ Transmission Electron Microscopy Observation of Pulverization of Aluminum Nanowires and Evolution of the Thin Surface Al 2 O 3 Layers during Lithiation–Delithiation Cycles
journal, October 2011
- Liu, Yang; Hudak, Nicholas S.; Huber, Dale L.
- Nano Letters, Vol. 11, Issue 10
In Situ Transmission Electron Microscopy Investigation of the Electrochemical Lithiation–Delithiation of Individual Co 9 S 8 /Co-Filled Carbon Nanotubes
journal, November 2013
- Su, Qingmei; Du, Gaohui; Zhang, Jun
- ACS Nano, Vol. 7, Issue 12
Atomic Resolution Study of Reversible Conversion Reaction in Metal Oxide Electrodes for Lithium-Ion Battery
journal, October 2014
- Luo, Langli; Wu, Jinsong; Xu, Junming
- ACS Nano, Vol. 8, Issue 11
Reactions of graphene supported Co 3 O 4 nanocubes with lithium and magnesium studied by in situ transmission electron microscopy
journal, January 2016
- Luo, Langli; Wu, Jinsong; Li, Qianqian
- Nanotechnology, Vol. 27, Issue 8
Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3
journal, August 2004
- Muller, David A.; Nakagawa, Naoyuki; Ohtomo, Akira
- Nature, Vol. 430, Issue 7000
Sodiation Kinetics of Metal Oxide Conversion Electrodes: A Comparative Study with Lithiation
journal, August 2015
- He, Kai; Lin, Feng; Zhu, Yizhou
- Nano Letters, Vol. 15, Issue 9
Revealing the electrochemical conversion mechanism of porous Co 3 O 4 nanoplates in lithium ion battery by in situ transmission electron microscopy
journal, October 2014
- Su, Qingmei; Zhang, Jun; Wu, Yishan
- Nano Energy, Vol. 9
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013
- Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav
- Computational Materials Science, Vol. 68
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013
- Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
- APL Materials, Vol. 1, Issue 1
Formation enthalpies by mixing GGA and GGA calculations
journal, July 2011
- Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping
- Physical Review B, Vol. 84, Issue 4
Oxidation energies of transition metal oxides within the framework
journal, May 2006
- Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand
- Physical Review B, Vol. 73, Issue 19
Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
journal, June 2012
- Bazant, Martin Z.
- Accounts of Chemical Research, Vol. 46, Issue 5
Suppression of Phase Separation in LiFePO 4 Nanoparticles During Battery Discharge
journal, November 2011
- Bai, Peng; Cogswell, Daniel A.; Bazant, Martin Z.
- Nano Letters, Vol. 11, Issue 11
Free Energy of a Nonuniform System. I. Interfacial Free Energy
journal, February 1958
- Cahn, John W.; Hilliard, John E.
- The Journal of Chemical Physics, Vol. 28, Issue 2
Works referencing / citing this record:
In‐situ structural characterizations of electrochemical intercalation of graphite compounds
journal, October 2019
- Li, Na; Su, Dong
- Carbon Energy, Vol. 1, Issue 2
Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research
journal, May 2019
- Liu, Dongqing; Shadike, Zulipiya; Lin, Ruoqian
- Advanced Materials, Vol. 31, Issue 28
A critical review-promises and barriers of conversion electrodes for Li-ion batteries
journal, April 2017
- Kraytsberg, Alexander; Ein-Eli, Yair
- Journal of Solid State Electrochemistry, Vol. 21, Issue 7
Atomic visualization of a non-equilibrium sodiation pathway in copper sulfide
journal, March 2018
- Park, Jae Yeol; Kim, Sung Joo; Chang, Joon Ha
- Nature Communications, Vol. 9, Issue 1
Phase evolution of conversion-type electrode for lithium ion batteries
journal, May 2019
- Li, Jing; Hwang, Sooyeon; Guo, Fangming
- Nature Communications, Vol. 10, Issue 1
Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite
journal, January 2019
- Li, Jing; Meng, Qingping; Zhang, Yiman
- Nature Communications, Vol. 10, Issue 1
Recent Advances in Designing High-Capacity Anode Nanomaterials for Li-Ion Batteries and Their Atomic-Scale Storage Mechanism Studies
journal, April 2018
- Cui, Qiuhong; Zhong, Yeteng; Pan, Lu
- Advanced Science, Vol. 5, Issue 7
Defects‐Induced In‐Plane Heterophase in Cobalt Oxide Nanosheets for Oxygen Evolution Reaction
journal, October 2019
- Liu, Zhijuan; Xiao, Zhaohui; Luo, Gan
- Small, Vol. 15, Issue 50
Atomic visualization of a non-equilibrium sodiation pathway in copper sulfide
journal, March 2018
- Park, Jae Yeol; Kim, Sung Joo; Chang, Joon Ha
- Nature Communications, Vol. 9, Issue 1
Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite
journal, January 2019
- Li, Jing; Meng, Qingping; Zhang, Yiman
- Nature Communications, Vol. 10, Issue 1
Phase evolution of conversion-type electrode for lithium ion batteries
journal, May 2019
- Li, Jing; Hwang, Sooyeon; Guo, Fangming
- Nature Communications, Vol. 10, Issue 1