High capacity Li/Ni rich Ni-Ti-Mo oxide cathode for Li-ion batteries
Abstract
With the rising cost and insufficient supply of cobalt, the thrust for cobalt-free cathode materials with the high specific capacity to build Li-ion batteries has increased significantly. Using nickel as the prime electrochemical active species, we have synthesized a new-class of materials with the combination of ordered and disordered phases. To obtain high capacity and electrical charge neutrality, stoichiometry of cations designed in a way that it forms Li/Ni rich Ni-Ti-Mo oxide materials. In addition to conventional capacity from redox activity of transition metals, partially reversible oxygen redox reaction also contributes to electrochemical activity and thus results in unusual high capacity. The resultant cathode materials of LiNi0.5Ti0.5O2-(Li4MoO5)0.8 and LiNiO2 mixture phases reach the specific capacity of 240 mAh/g. Detailed soft X-ray absorption spectroscopy and electron microscopy are used to reveal the crystal phases in this system and trace changes in the Ni2+/Ni4+ redox couple during charge-discharge processes. Finally, such comprehensive analysis of ordered-disordered oxides suggesting potentiality to develop high-capacity cobalt-free cathodes.
- Authors:
-
- Rice Univ., Houston, TX (United States)
- Rice Univ., Houston, TX (United States); Univ. of Houston, TX (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1608945
- Alternate Identifier(s):
- OSTI ID: 1594221
- Grant/Contract Number:
- AC02-76SF00515; SC00014607
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Solid State Ionics
- Additional Journal Information:
- Journal Volume: 345; Journal Issue: C; Journal ID: ISSN 0167-2738
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Li-ion battery; Li excess cathodes; order-disorder materials; oxygen redox activity; x-ray absorption spectroscopy
Citation Formats
Xu, Jianan, Babu, Ganguli, Kato, Keiko, Robles Hernández, Francisco C., Puthirath, Anand B., Britz, Alexander, Nordlund, Dennis, Sainio, Sami, Bergmann, Uwe, and Ajayan, Pulickel M. High capacity Li/Ni rich Ni-Ti-Mo oxide cathode for Li-ion batteries. United States: N. p., 2019.
Web. doi:10.1016/j.ssi.2019.115172.
Xu, Jianan, Babu, Ganguli, Kato, Keiko, Robles Hernández, Francisco C., Puthirath, Anand B., Britz, Alexander, Nordlund, Dennis, Sainio, Sami, Bergmann, Uwe, & Ajayan, Pulickel M. High capacity Li/Ni rich Ni-Ti-Mo oxide cathode for Li-ion batteries. United States. https://doi.org/10.1016/j.ssi.2019.115172
Xu, Jianan, Babu, Ganguli, Kato, Keiko, Robles Hernández, Francisco C., Puthirath, Anand B., Britz, Alexander, Nordlund, Dennis, Sainio, Sami, Bergmann, Uwe, and Ajayan, Pulickel M. Fri .
"High capacity Li/Ni rich Ni-Ti-Mo oxide cathode for Li-ion batteries". United States. https://doi.org/10.1016/j.ssi.2019.115172. https://www.osti.gov/servlets/purl/1608945.
@article{osti_1608945,
title = {High capacity Li/Ni rich Ni-Ti-Mo oxide cathode for Li-ion batteries},
author = {Xu, Jianan and Babu, Ganguli and Kato, Keiko and Robles Hernández, Francisco C. and Puthirath, Anand B. and Britz, Alexander and Nordlund, Dennis and Sainio, Sami and Bergmann, Uwe and Ajayan, Pulickel M.},
abstractNote = {With the rising cost and insufficient supply of cobalt, the thrust for cobalt-free cathode materials with the high specific capacity to build Li-ion batteries has increased significantly. Using nickel as the prime electrochemical active species, we have synthesized a new-class of materials with the combination of ordered and disordered phases. To obtain high capacity and electrical charge neutrality, stoichiometry of cations designed in a way that it forms Li/Ni rich Ni-Ti-Mo oxide materials. In addition to conventional capacity from redox activity of transition metals, partially reversible oxygen redox reaction also contributes to electrochemical activity and thus results in unusual high capacity. The resultant cathode materials of LiNi0.5Ti0.5O2-(Li4MoO5)0.8 and LiNiO2 mixture phases reach the specific capacity of 240 mAh/g. Detailed soft X-ray absorption spectroscopy and electron microscopy are used to reveal the crystal phases in this system and trace changes in the Ni2+/Ni4+ redox couple during charge-discharge processes. Finally, such comprehensive analysis of ordered-disordered oxides suggesting potentiality to develop high-capacity cobalt-free cathodes.},
doi = {10.1016/j.ssi.2019.115172},
journal = {Solid State Ionics},
number = C,
volume = 345,
place = {United States},
year = {Fri Dec 06 00:00:00 EST 2019},
month = {Fri Dec 06 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Synthesis and Surface Modification of LiCo1/3Ni1/3Mn1/3O2 for Lithium Battery Applications
journal, January 2014
- Babu, Ganguli; Kalaiselvi, N.; Bhuvaneswari, D.
- Journal of Electronic Materials, Vol. 43, Issue 4
Optimized LiFePO[sub 4] for Lithium Battery Cathodes
journal, January 2001
- Yamada, A.; Chung, S. C.; Hinokuma, K.
- Journal of The Electrochemical Society, Vol. 148, Issue 3
A disordered rock-salt Li-excess cathode material with high capacity and substantial oxygen redox activity: Li 1.25 Nb 0.25 Mn 0.5 O 2
journal, November 2015
- Wang, Rui; Li, Xin; Liu, Lei
- Electrochemistry Communications, Vol. 60
Attainable high capacity in Li-excess Li-Ni-Ru-O rock-salt cathode for lithium ion battery
journal, August 2017
- Wang, Xingbo; Huang, Weifeng; Tao, Shi
- Journal of Power Sources, Vol. 359
Reversible Three-Electron Redox Reaction of Mo 3+ /Mo 6+ for Rechargeable Lithium Batteries
journal, March 2017
- Hoshino, Satoshi; Glushenkov, Alexey M.; Ichikawa, Shinnosuke
- ACS Energy Letters, Vol. 2, Issue 4
The Li 3 Ru y Nb 1– y O 4 (0 ≤ y ≤ 1) System: Structural Diversity and Li Insertion and Extraction Capabilities
journal, May 2017
- Jacquet, Quentin; Perez, Arnaud; Batuk, Dmitry
- Chemistry of Materials, Vol. 29, Issue 12
Anionic Redox in Rechargeable Lithium Batteries
journal, June 2017
- Li, Biao; Xia, Dingguo
- Advanced Materials, Vol. 29, Issue 48
Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li 4 FeSbO 6
journal, April 2015
- McCalla, Eric; Sougrati, Moulay Tahar; Rousse, Gwenaelle
- Journal of the American Chemical Society, Vol. 137, Issue 14
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016
- Luo, Kun; Roberts, Matthew R.; Hao, Rong
- Nature Chemistry, Vol. 8, Issue 7
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
Decoupling Cationic–Anionic Redox Processes in a Model Li-Rich Cathode via Operando X-ray Absorption Spectroscopy
journal, November 2017
- Assat, Gaurav; Iadecola, Antonella; Delacourt, Charles
- Chemistry of Materials, Vol. 29, Issue 22
Operando EPR for Simultaneous Monitoring of Anionic and Cationic Redox Processes in Li-Rich Metal Oxide Cathodes
journal, August 2017
- Tang, Mingxue; Dalzini, Annalisa; Li, Xiang
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries
journal, January 2016
- Saubanère, M.; McCalla, E.; Tarascon, J. -M.
- Energy & Environmental Science, Vol. 9, Issue 3
Molecular Orbital Principles of Oxygen-Redox Battery Electrodes
journal, October 2017
- Okubo, Masashi; Yamada, Atsuo
- ACS Applied Materials & Interfaces, Vol. 9, Issue 42
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
A High-Capacity O2-Type Li-Rich Cathode Material with a Single-Layer Li 2 MnO 3 Superstructure
journal, March 2018
- Zuo, Yuxuan; Li, Biao; Jiang, Ning
- Advanced Materials, Vol. 30, Issue 16
Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4
journal, December 2017
- Perez, Arnaud J.; Jacquet, Quentin; Batuk, Dmitry
- Nature Energy, Vol. 2, Issue 12
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
Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials
journal, October 2017
- Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.
- Nature Communications, Vol. 8, Issue 1
Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014
- Sathiya, M.; Abakumov, A. M.; Foix, D.
- Nature Materials, Vol. 14, Issue 2
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
Facile Synthesis of The Li-Rich Layered Oxide Li 1.23 Ni 0.09 Co 0.12 Mn 0.56 O 2 with Superior Lithium Storage Performance and New Insights into Structural Transformation of the Layered Oxide Material during Charge–Discharge Cycle: In Situ XRD Characterization
journal, April 2014
- Shen, Chong-Heng; Wang, Qin; Fu, Fang
- ACS Applied Materials & Interfaces, Vol. 6, Issue 8
Synthesis and electrochemistry of cubic rocksalt Li–Ni–Ti–O compounds in the phase diagram of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2
journal, October 2008
- Zhang, Lianqi; Noguchi, Hideyuki; Li, Decheng
- Journal of Power Sources, Vol. 185, Issue 1
Characterization of NiO by XPS
journal, July 1994
- Mansour, A. N.
- Surface Science Spectra, Vol. 3, Issue 3
Characterization of LiNiO 2 by XPS
journal, July 1994
- Mansour, A. N.
- Surface Science Spectra, Vol. 3, Issue 3
Probing the electrode/electrolyte interface in the lithium excess layered oxide Li1.2Ni0.2Mn0.6O2
journal, January 2013
- Carroll, Kyler J.; Qian, Danna; Fell, Chris
- Physical Chemistry Chemical Physics, Vol. 15, Issue 26
Spectroscopic characterization of the interaction of lithium with thin films of the ionic liquid 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide
journal, January 2014
- Olschewski, Mark; Gustus, René; Marschewski, Marcel
- Phys. Chem. Chem. Phys., Vol. 16, Issue 47
X-ray Photoemission Spectroscopy Study of Cationic and Anionic Redox Processes in High-Capacity Li-Ion Battery Layered-Oxide Electrodes
journal, January 2016
- Foix, Dominique; Sathiya, Mariyappan; McCalla, Eric
- The Journal of Physical Chemistry C, Vol. 120, Issue 2
Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes
journal, November 2015
- Qiao, Ruimin; Wray, L. Andrew; Kim, Jung-Hyun
- The Journal of Physical Chemistry C, Vol. 119, Issue 49
Chemometrics applied to unravel multicomponent processes and mixtures
journal, December 2003
- de Juan, A.; Tauler, R.
- Analytica Chimica Acta, Vol. 500, Issue 1-2
V IV Disproportionation Upon Sodium Extraction From Na 3 V 2 (PO 4 ) 2 F 3 Observed by Operando X-ray Absorption Spectroscopy and Solid-State NMR
journal, February 2017
- Broux, Thibault; Bamine, Tahya; Simonelli, Laura
- The Journal of Physical Chemistry C, Vol. 121, Issue 8
Li deinsertion mechanism and Jahn–Teller distortion in LiFe 0.75 Mn 0.25 PO 4 : an operando x-ray absorption spectroscopy investigation
journal, March 2017
- Iadecola, Antonella; Perea, Alexis; Aldon, Laurent
- Journal of Physics D: Applied Physics, Vol. 50, Issue 14
Understanding the lithiation/delithiation mechanism of Si 1−x Ge x alloys
journal, January 2017
- Loaiza, Laura C.; Salager, Elodie; Louvain, Nicolas
- Journal of Materials Chemistry A, Vol. 5, Issue 24
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2
journal, August 2016
- Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló
- Journal of the American Chemical Society, Vol. 138, Issue 35