Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes
Abstract
Owing to the capacity boost from oxygen redox activities, Li-rich cation-disordered rocksalts (LRCDRS) represent a new class of promising high-energy Li-ion battery cathode materials. Redox-inactive transition-metal (TM) cations, typically d0 TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d0 TM (Nb5+ and Ti4+) is systematically compared on the redox chemistry of Mn-based model LRCDRS cathodes, namely Li1.3Nb0.3Mn0.4O2 (LNMO), Li1.25Nb0.15Ti0.2Mn0.4O2 (LNTMO), and Li1.2Ti0.4Mn0.4O2 (LTMO). Although electrochemically inactive, d0 TM serves as a modulator for oxygen redox, with Nb5+ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X-ray scattering reveal that Ti4+ is better in stabilizing the oxidized oxygen anions (On-, 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d0 TM on degradation mechanism further suggests that proper design of redox-inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.
- Authors:
-
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
- OSTI Identifier:
- 1635193
- Alternate Identifier(s):
- OSTI ID: 1617077
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Small
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 22; Journal ID: ISSN 1613-6810
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cation‐disordered rocksalt cathodes; lithium‐ion batteries; oxygen redox degradation mechanism; redox‐inactive transition metals
Citation Formats
Chen, Dongchang, Wu, Jinpeng, Papp, Joseph K., McCloskey, Bryan D., Yang, Wanli, and Chen, Guoying. Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes. United States: N. p., 2020.
Web. doi:10.1002/smll.202000656.
Chen, Dongchang, Wu, Jinpeng, Papp, Joseph K., McCloskey, Bryan D., Yang, Wanli, & Chen, Guoying. Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes. United States. https://doi.org/10.1002/smll.202000656
Chen, Dongchang, Wu, Jinpeng, Papp, Joseph K., McCloskey, Bryan D., Yang, Wanli, and Chen, Guoying. Mon .
"Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes". United States. https://doi.org/10.1002/smll.202000656. https://www.osti.gov/servlets/purl/1635193.
@article{osti_1635193,
title = {Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes},
author = {Chen, Dongchang and Wu, Jinpeng and Papp, Joseph K. and McCloskey, Bryan D. and Yang, Wanli and Chen, Guoying},
abstractNote = {Owing to the capacity boost from oxygen redox activities, Li-rich cation-disordered rocksalts (LRCDRS) represent a new class of promising high-energy Li-ion battery cathode materials. Redox-inactive transition-metal (TM) cations, typically d0 TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d0 TM (Nb5+ and Ti4+) is systematically compared on the redox chemistry of Mn-based model LRCDRS cathodes, namely Li1.3Nb0.3Mn0.4O2 (LNMO), Li1.25Nb0.15Ti0.2Mn0.4O2 (LNTMO), and Li1.2Ti0.4Mn0.4O2 (LTMO). Although electrochemically inactive, d0 TM serves as a modulator for oxygen redox, with Nb5+ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X-ray scattering reveal that Ti4+ is better in stabilizing the oxidized oxygen anions (On-, 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d0 TM on degradation mechanism further suggests that proper design of redox-inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.},
doi = {10.1002/smll.202000656},
journal = {Small},
number = 22,
volume = 16,
place = {United States},
year = {Mon May 04 00:00:00 EDT 2020},
month = {Mon May 04 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 29 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
In Situ L-Edge XAS Study of a Manganese Oxide Water Oxidation Catalyst
journal, May 2017
- Xi, Lifei; Schwanke, Christoph; Xiao, Jie
- The Journal of Physical Chemistry C, Vol. 121, Issue 22
Spectroscopic Signature of Oxidized Oxygen States in Peroxides
journal, October 2018
- Zhuo, Zengqing; Pemmaraju, Chaitanya Das; Vinson, John
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 21
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering
journal, January 2019
- Wu, Jinpeng; Li, Qinghao; Sallis, Shawn
- Condensed Matter, Vol. 4, Issue 1
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
journal, May 2013
- Qiao, Ruimin; Chin, Timothy; Harris, Stephen J.
- Current Applied Physics, Vol. 13, Issue 3
Theoretical Fingerprints of Transition Metal L 2,3 XANES and ELNES for Lithium Transition Metal Oxides by ab Initio Multiplet Calculations
journal, May 2011
- Ikeno, Hidekazu; Mizoguchi, Teruyasu; Koyama, Yukinori
- The Journal of Physical Chemistry C, Vol. 115, Issue 23
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials
journal, April 2018
- Lee, Jinhyuk; Kitchaev, Daniil A.; Kwon, Deok-Hwang
- Nature, Vol. 556, Issue 7700
Stabilizing the Oxygen Lattice and Reversible Oxygen Redox Chemistry through Structural Dimensionality in Lithium-Rich Cathode Oxides
journal, February 2019
- Zhao, Enyue; Li, Qinghao; Meng, Fanqi
- Angewandte Chemie International Edition, Vol. 58, Issue 13
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox
journal, January 2018
- House, Robert A.; Jin, Liyu; Maitra, Urmimala
- Energy & Environmental Science, Vol. 11, Issue 4
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016
- Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
- Nature Chemistry, Vol. 8, Issue 7
Unravelling Solid-State Redox Chemistry in Li 1.3 Nb 0.3 Mn 0.4 O 2 Single-Crystal Cathode Material
journal, February 2018
- Kan, Wang Hay; Chen, Dongchang; Papp, Joseph K.
- Chemistry of Materials, Vol. 30, Issue 5
Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering
journal, June 2018
- Yang, Wanli; Devereaux, Thomas P.
- Journal of Power Sources, Vol. 389
The first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V
journal, March 2004
- Kim, Jung-Min; Chung, Hoon-Taek
- Electrochimica Acta, Vol. 49, Issue 6
Operando X-ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2 in Li Ion Batteries
journal, March 2014
- Koga, H.; Croguennec, L.; Ménétrier, M.
- The Journal of Physical Chemistry C, Vol. 118, Issue 11
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014
- Lee, J.; Urban, A.; Li, X.
- Science, Vol. 343, Issue 6170
Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries
journal, September 2015
- Qiao, Ruimin; Dai, Kehua; Mao, Jing
- Nano Energy, Vol. 16
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
journal, April 2018
- Assat, Gaurav; Tarascon, Jean-Marie
- Nature Energy, Vol. 3, Issue 5
Computational Design and Preparation of Cation-Disordered Oxides for High-Energy-Density Li-Ion Batteries
journal, May 2016
- Urban, Alexander; Matts, Ian; Abdellahi, Aziz
- Advanced Energy Materials, Vol. 6, Issue 15
Modular soft x-ray spectrometer for applications in energy sciences and quantum materials
journal, January 2017
- Chuang, Yi-De; Shao, Yu-Cheng; Cruz, Alejandro
- Review of Scientific Instruments, Vol. 88, Issue 1
Positive Electrode Materials for Li-Ion and Li-Batteries †
journal, February 2010
- Ellis, Brian L.; Lee, Kyu Tae; Nazar, Linda F.
- Chemistry of Materials, Vol. 22, Issue 3
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions
journal, February 2019
- Dai, Kehua; Wu, Jinpeng; Zhuo, Zengqing
- Joule, Vol. 3, Issue 2
Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes
journal, January 2018
- Kitchaev, Daniil A.; Lun, Zhengyan; Richards, William D.
- Energy & Environmental Science, Vol. 11, Issue 8
Quantification of Surface Oxygen Depletion and Solid Carbonate Evolution on the First Cycle of LiNi 0.6 Mn 0.2 Co 0.2 O 2 Electrodes
journal, April 2019
- Renfrew, Sara E.; McCloskey, Bryan D.
- ACS Applied Energy Materials, Vol. 2, Issue 5
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Materials Challenges Facing Electrical Energy Storage
journal, April 2008
- Whittingham, M. Stanley
- MRS Bulletin, Vol. 33, Issue 4
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries
journal, December 2016
- Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue
- Nature Communications, Vol. 7, Issue 1
Electronic-Structure Origin of Cation Disorder in Transition-Metal Oxides
journal, October 2017
- Urban, Alexander; Abdellahi, Aziz; Dacek, Stephen
- Physical Review Letters, Vol. 119, Issue 17
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017
- Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing
- Review of Scientific Instruments, Vol. 88, Issue 3
High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure
journal, June 2015
- Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
Phase Transformation and Lithiation Effect on Electronic Structure of Li x FePO 4 : An In-Depth Study by Soft X-ray and Simulations
journal, August 2012
- Liu, Xiaosong; Liu, Jun; Qiao, Ruimin
- Journal of the American Chemical Society, Vol. 134, Issue 33
Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries
journal, February 2019
- Ji, Huiwen; Urban, Alexander; Kitchaev, Daniil A.
- Nature Communications, Vol. 10, Issue 1
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
A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides
journal, January 2015
- Lee, Jinhyuk; Seo, Dong-Hwa; Balasubramanian, Mahalingam
- Energy & Environmental Science, Vol. 8, Issue 11
In situ X-ray absorption spectroscopic study of Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2
journal, August 2011
- Ito, Atsushi; Sato, Yuichi; Sanada, Takashi
- Journal of Power Sources, Vol. 196, Issue 16
Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry
journal, May 2011
- McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166
Combining Accurate O 2 and Li 2 O 2 Assays to Separate Discharge and Charge Stability Limitations in Nonaqueous Li–O 2 Batteries
journal, August 2013
- McCloskey, Bryan D.; Valery, Alexia; Luntz, Alan C.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 17