Revealing the Atomic Origin of Heterogeneous Li-Ion Diffusion by Probing Na
Abstract
Tracing the dynamic process of Li-ion transport at the atomic scale has long been attempted in solid state ionics and is essential for battery material engineering. Approaches via phase change, strain, and valence states of redox species have been developed to circumvent the technical challenge of direct imaging Li; however, all are limited by poor spatial resolution and weak correlation with state-of-charge (SOC). An ion-exchange approach is adopted by sodiating the delithiated cathode and probing Na distribution to trace the Li deintercalation, which enables the visualization of heterogeneous Li-ion diffusion down to the atomic level. In a model LiNi1/3Mn1/3Co1/3O2 cathode, dislocation-mediated ion diffusion is kinetically favorable at low SOC and planar diffusion along (003) layers dominates at high SOC. These processes work synergistically to determine the overall ion-diffusion dynamics. Here, the heterogeneous nature of ion diffusion in battery materials is unveiled and the role of defect engineering in tailoring ion-transport kinetics is stressed.
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Beijing Univ. of Technology, Beijing (China)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States); Stanford Univ., Stanford, CA (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V). Battery Materials Research (BMR) Program; USDOE Office of Electricity (OE)
- OSTI Identifier:
- 1559944
- Alternate Identifier(s):
- OSTI ID: 1523674
- Grant/Contract Number:
- AC02-06CH11357; 70247A; AC02‐06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 29; Journal ID: ISSN 0935-9648
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; dislocation diffusion; ion-exchange; layer diffusion; layered cathode; lithium-ion batteries
Citation Formats
Xiao, Biwei, Wang, Kuan, Xu, Gui -Liang, Song, Junhua, Chen, Zonghai, Amine, Khalil, Reed, David, Sui, Manling, Sprenkle, Vincent L., Ren, Yang, Yan, Pengfei, and Li, Xiaolin. Revealing the Atomic Origin of Heterogeneous Li-Ion Diffusion by Probing Na. United States: N. p., 2019.
Web. doi:10.1002/adma.201805889.
Xiao, Biwei, Wang, Kuan, Xu, Gui -Liang, Song, Junhua, Chen, Zonghai, Amine, Khalil, Reed, David, Sui, Manling, Sprenkle, Vincent L., Ren, Yang, Yan, Pengfei, & Li, Xiaolin. Revealing the Atomic Origin of Heterogeneous Li-Ion Diffusion by Probing Na. United States. https://doi.org/10.1002/adma.201805889
Xiao, Biwei, Wang, Kuan, Xu, Gui -Liang, Song, Junhua, Chen, Zonghai, Amine, Khalil, Reed, David, Sui, Manling, Sprenkle, Vincent L., Ren, Yang, Yan, Pengfei, and Li, Xiaolin. Thu .
"Revealing the Atomic Origin of Heterogeneous Li-Ion Diffusion by Probing Na". United States. https://doi.org/10.1002/adma.201805889. https://www.osti.gov/servlets/purl/1559944.
@article{osti_1559944,
title = {Revealing the Atomic Origin of Heterogeneous Li-Ion Diffusion by Probing Na},
author = {Xiao, Biwei and Wang, Kuan and Xu, Gui -Liang and Song, Junhua and Chen, Zonghai and Amine, Khalil and Reed, David and Sui, Manling and Sprenkle, Vincent L. and Ren, Yang and Yan, Pengfei and Li, Xiaolin},
abstractNote = {Tracing the dynamic process of Li-ion transport at the atomic scale has long been attempted in solid state ionics and is essential for battery material engineering. Approaches via phase change, strain, and valence states of redox species have been developed to circumvent the technical challenge of direct imaging Li; however, all are limited by poor spatial resolution and weak correlation with state-of-charge (SOC). An ion-exchange approach is adopted by sodiating the delithiated cathode and probing Na distribution to trace the Li deintercalation, which enables the visualization of heterogeneous Li-ion diffusion down to the atomic level. In a model LiNi1/3Mn1/3Co1/3O2 cathode, dislocation-mediated ion diffusion is kinetically favorable at low SOC and planar diffusion along (003) layers dominates at high SOC. These processes work synergistically to determine the overall ion-diffusion dynamics. Here, the heterogeneous nature of ion diffusion in battery materials is unveiled and the role of defect engineering in tailoring ion-transport kinetics is stressed.},
doi = {10.1002/adma.201805889},
journal = {Advanced Materials},
number = 29,
volume = 31,
place = {United States},
year = {2019},
month = {5}
}
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Works referenced in this record:
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries
journal, March 2015
- Liu, Wen; Oh, Pilgun; Liu, Xien
- Angewandte Chemie International Edition, Vol. 54, Issue 15
Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries
journal, January 2017
- Xu, Gui-Liang; Amine, Rachid; Xu, Yue-Feng
- Energy & Environmental Science, Vol. 10, Issue 7
Probing three-dimensional sodiation–desodiation equilibrium in sodium-ion batteries by in situ hard X-ray nanotomography
journal, June 2015
- Wang, Jiajun; Eng, Christopher; Chen-Wiegart, Yu-chen Karen
- Nature Communications, Vol. 6, Issue 1
Numerical study of grain boundary effect on Li+ effective diffusivity and intercalation-induced stresses in Li-ion battery active materials
journal, October 2013
- Han, Sangwoo; Park, Jonghyun; Lu, Wei
- Journal of Power Sources, Vol. 240
Localized concentration reversal of lithium during intercalation into nanoparticles
journal, January 2018
- Zhang, Wei; Yu, Hui-Chia; Wu, Lijun
- Science Advances, Vol. 4, Issue 1
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials
journal, March 2018
- Tian, Chixia; Xu, Yahong; Nordlund, Dennis
- Joule, Vol. 2, Issue 3
Emerging In Situ and Operando Nanoscale X-Ray Imaging Techniques for Energy Storage Materials
journal, February 2015
- Nelson Weker, Johanna; Toney, Michael F.
- Advanced Functional Materials, Vol. 25, Issue 11
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
Dichotomy in the Lithiation Pathway of Ellipsoidal and Platelet LiFePO 4 Particles Revealed through Nanoscale Operando State-of-Charge Imaging
journal, May 2015
- Li, Yiyang; Weker, Johanna Nelson; Gent, William E.
- Advanced Functional Materials, Vol. 25, Issue 24
Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films
journal, January 2011
- Chung, Ding-Wen; Balke, Nina; Kalinin, Sergei V.
- Journal of The Electrochemical Society, Vol. 158, Issue 10
Topological defect dynamics in operando battery nanoparticles
journal, June 2015
- Ulvestad, A.; Singer, A.; Clark, J. N.
- Science, Vol. 348, Issue 6241
Nanoscale Measurements of Lithium-Ion-Battery Materials using Scanning Probe Techniques
journal, November 2016
- Danis, Laurence; Gateman, Samantha M.; Kuss, Christian
- ChemElectroChem, Vol. 4, Issue 1
Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles
journal, August 2016
- Wang, Jiajun; Karen Chen-Wiegart, Yu-chen; Eng, Christopher
- Nature Communications, Vol. 7, Issue 1
High Capacity O3-Type Na[Li 0.05 (Ni 0.25 Fe 0.25 Mn 0.5 ) 0.95 ]O 2 Cathode for Sodium Ion Batteries
journal, October 2014
- Oh, Seung-Min; Myung, Seung-Taek; Hwang, Jang-Yeon
- Chemistry of Materials, Vol. 26, Issue 21
In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO 2 Cathode in a Working All-Solid-State Battery
journal, March 2017
- Gong, Yue; Zhang, Jienan; Jiang, Liwei
- Journal of the American Chemical Society, Vol. 139, Issue 12
Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles
journal, August 2016
- Lim, Jongwoo; Li, Yiyang; Alsem, Daan Hein
- Science, Vol. 353, Issue 6299
Na-Ion Battery Anodes: Materials and Electrochemistry
journal, January 2016
- Luo, Wei; Shen, Fei; Bommier, Clement
- Accounts of Chemical Research, Vol. 49, Issue 2
Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries
journal, October 2013
- Ebner, M.; Marone, F.; Stampanoni, M.
- Science, Vol. 342, Issue 6159
Functioning Mechanism of AlF 3 Coating on the Li- and Mn-Rich Cathode Materials
journal, November 2014
- Zheng, Jianming; Gu, Meng; Xiao, Jie
- Chemistry of Materials, Vol. 26, Issue 22
In operando tracking phase transformation evolution of lithium iron phosphate with hard X-ray microscopy
journal, August 2014
- Wang, Jiajun; Chen-Wiegart, Yu-chen Karen; Wang, Jun
- Nature Communications, Vol. 5, Issue 1
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
Structural and Chemical Evolution of Li- and Mn-Rich Layered Cathode Material
journal, February 2015
- Zheng, Jianming; Xu, Pinghong; Gu, Meng
- Chemistry of Materials, Vol. 27, Issue 4
Routes to High Energy Cathodes of Sodium-Ion Batteries
journal, December 2015
- Fang, Chun; Huang, Yunhui; Zhang, Wuxing
- Advanced Energy Materials, Vol. 6, Issue 5
Nanoscale optical imaging of lithium-ion distribution on a LiCoO 2 cathode surface
journal, April 2017
- Hara, Kosuke; Yano, Taka-aki; Hata, Junichi
- Applied Physics Express, Vol. 10, Issue 5
Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles
journal, May 2016
- Gent, William E.; Li, Yiyang; Ahn, Sungjin
- Advanced Materials, Vol. 28, Issue 31
Reversible NaFePO4 electrode for sodium secondary batteries
journal, August 2012
- Oh, Seung-Min; Myung, Seung-Taek; Hassoun, Jusef
- Electrochemistry Communications, Vol. 22
Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High-Performance Cathode
journal, October 2017
- Xiao, Biwei; Liu, Hanshuo; Liu, Jian
- Advanced Materials, Vol. 29, Issue 47
Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries
journal, January 2017
- Yan, Pengfei; Zheng, Jianming; Gu, Meng
- Nature Communications, Vol. 8, Issue 1
Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon
journal, March 2017
- Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.
- Advanced Materials, Vol. 29, Issue 18
Atomic-Scale Monitoring of Electrode Materials in Lithium-Ion Batteries using In Situ Transmission Electron Microscopy
journal, October 2017
- Shang, Tongtong; Wen, Yuren; Xiao, Dongdong
- Advanced Energy Materials, Vol. 7, Issue 23
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
journal, July 2018
- Singer, A.; Zhang, M.; Hy, S.
- Nature Energy, Vol. 3, Issue 8
Layered P2/O3 Intergrowth Cathode: Toward High Power Na-Ion Batteries
journal, July 2014
- Lee, Eungje; Lu, Jun; Ren, Yang
- Advanced Energy Materials, Vol. 4, Issue 17
Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode
journal, May 2017
- Yan, Pengfei; Zheng, Jianming; Zhang, Ji-Guang
- Nano Letters, Vol. 17, Issue 6
Construction of ground-state preserving sparse lattice models for predictive materials simulations
journal, August 2017
- Huang, Wenxuan; Urban, Alexander; Rong, Ziqin
- npj Computational Materials, Vol. 3, Issue 1
Batteries: Imaging degradation
journal, November 2016
- Shearing, Paul R.
- Nature Energy, Vol. 1, Issue 11
Development of High Capacity Cathode Material for Sodium Ion Batteries Na 0.95 Li 0.15 (Ni 0.15 Mn 0.55 Co 0.1 )O 2
journal, January 2013
- Kataoka, Riki; Mukai, Takashi; Yoshizawa, Akihiro
- Journal of The Electrochemical Society, Vol. 160, Issue 6
Synthesis, Structure, and Electrochemical Properties of the Layered Sodium Insertion Cathode Material: NaNi 1 / 3 Mn 1 / 3 Co 1 / 3 O 2
journal, April 2012
- Sathiya, M.; Hemalatha, K.; Ramesha, K.
- Chemistry of Materials, Vol. 24, Issue 10
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy
journal, October 2017
- Li, Yuzhang; Li, Yanbin; Pei, Allen
- Science, Vol. 358, Issue 6362
Sodium-ion batteries: present and future
journal, January 2017
- Hwang, Jang-Yeon; Myung, Seung-Taek; Sun, Yang-Kook
- Chemical Society Reviews, Vol. 46, Issue 12
From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises
journal, November 2017
- Nayak, Prasant Kumar; Yang, Liangtao; Brehm, Wolfgang
- Angewandte Chemie International Edition, Vol. 57, Issue 1
Identifying the Critical Role of Li Substitution in P2–Na x [Li y Ni z Mn 1– y – z ]O 2 (0 < x , y , z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries
journal, December 2013
- Xu, Jing; Lee, Dae Hoe; Clément, Raphaële J.
- Chemistry of Materials, Vol. 26, Issue 2
Is there a Stobbs factor in atomic-resolution STEM-EELS mapping?
journal, April 2014
- Xin, Huolin L.; Dwyer, Christian; Muller, David A.
- Ultramicroscopy, Vol. 139
Visualization of electrochemically driven solid-state phase transformations using operando hard X-ray spectro-imaging
journal, April 2015
- Li, Linsen; Chen-Wiegart, Yu-chen Karen; Wang, Jiajun
- Nature Communications, Vol. 6, Issue 1
Nanoscale mapping of ion diffusion in a lithium-ion battery cathode
journal, August 2010
- Balke, N.; Jesse, S.; Morozovska, A. N.
- Nature Nanotechnology, Vol. 5, Issue 10
Lithium Batteries and Cathode Materials
journal, December 2004
- Whittingham, M. Stanley
- ChemInform, Vol. 35, Issue 50
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
text, January 2018
- Singer, A.; Zhang, M.; Hy, S.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Localized concentration reversal of lithium during intercalation into nanoparticles.
text, January 2018
- Zhang, Wei; Yu, Hui-Chia; Wu, Lijun
- Apollo - University of Cambridge Repository
Is There a Stobbs Factor in Atomic-Resolution STEM-EELS Mapping?
journal, July 2011
- Xin, H.; Dwyer, C.; Muller, D.
- Microscopy and Microanalysis, Vol. 17, Issue S2
Works referencing / citing this record:
Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials
journal, January 2020
- Xu, Zhengrui; Jiang, Zhisen; Kuai, Chunguang
- Nature Communications, Vol. 11, Issue 1