Synthesis and Electrochemical and Structural Investigations of Oxidatively Stable Li2MoO3 and xLi2MoO3·(1 – x)LiMO2 Composite Cathodes

Self, Ethan C.; Zou, Lianfeng; Zhang, Ming-Jian; Opfer, Richard; Ruther, Rose E.; Veith, Gabriel M.; Song, Bohang; Wang, Chongmin; Wang, Feng; Huq, Ashfia; Nanda, Jagjit

doi:10.1021/acs.chemmater.8b01408

Title: Synthesis and Electrochemical and Structural Investigations of Oxidatively Stable Li₂MoO₃ and xLi₂MoO₃·(1 – x)LiMO₂ Composite Cathodes

Journal Article · Fri Jun 29 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b01408· OSTI ID:1843412

Self, Ethan C. ^[1]; Zou, Lianfeng ^[2]; Zhang, Ming-Jian ^[3]; Opfer, Richard ^[1]; Ruther, Rose E. ^[1];

^[1]; Song, Bohang ^[1];

^[2];

^[3]; Huq, Ashfia ^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

We report the structural evolution of Li₂MoO₃ during electrochemical delithiation/lithiation is reported. Li₂MoO₃ undergoes an irreversible crystalline to amorphous transformation which starts during the first delithiation step and gradually proceeds throughout subsequent cycles. This observation is supported by complementary data obtained from X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The amorphization does not prevent reversible Li storage, and the Li₂MoO₃ cathodes exhibit initial capacities of 147 mAh/g (corresponding to 0.87 Li cycled per formula unit) at an average operating potential ~2.5 V vs Li/Li⁺ with reasonably good cycling stability (81% capacity retention after 50 cycles). In-situ mass spectrometry studies reveal the amorphization of Li₂MoO₃ does not involve the release of oxygen gas even when charged to very positive potentials (i.e., 4.8 V vs Li/Li⁺). The Li storage properties and excellent oxidative stability of Li₂MoO₃ make it a promising candidate to improve the performance of traditional LiMO₂ compounds in layered–layered composite cathodes with the general formula xLi₂MoO₃·(1 – x)LiMO₂. Multiple synthesis routes were explored to prepare composites with x = 0.10–0.15, and their structure was characterized using XRD and time-of-flight neutron diffraction. Lastly, preliminary characterization of these materials shows that Li₂MoO₃ improves the cycling stability of an NMC cathode, presumably by mitigating detrimental structural rearrangement at high states of charge.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; AC05-00OR22725; DMR-1332208

OSTI ID:: 1843412

Alternate ID(s):: OSTI ID: 1474654

Report Number(s):: PNNL-SA-138456

Journal Information:: Chemistry of Materials, Vol. 30, Issue 15; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 19 works

Citation information provided by
Web of Science

References (32)

Synthesis, Structure, and Electrochemical Performance of High Capacity Li ₂ Cu _0.5 Ni _0.5 O ₂ Cathodes Ruther, Rose E.; Zhou, Hui; Dhital, Chetan Chemistry of Materials, Vol. 27, Issue 19 https://doi.org/10.1021/acs.chemmater.5b02843	journal	September 2015
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes Sathiya, M.; Rousse, G.; Ramesha, K. Nature Materials, Vol. 12, Issue 9 https://doi.org/10.1038/nmat3699	journal	July 2013
High Capacity, Surface-Modified Layered Li [Li _(1−x) ∕ ₃Mn _(2−x) ∕ ₃Ni_x ∕ ₃Co_{x ∕ 3} ] O₂ Cathodes with Low Irreversible Capacity Loss Wu, Y.; Manthiram, A. Electrochemical and Solid-State Letters, Vol. 9, Issue 5, p. A221-A224 https://doi.org/10.1149/1.2180528	journal	March 2006
Surface Structures of Supported Molybdenum Oxide Catalysts: Characterization by Raman and Mo L3-Edge XANES Hu, Hangchun; Wachs, Israel E.; Bare, Simon R. The Journal of Physical Chemistry, Vol. 99, Issue 27 https://doi.org/10.1021/j100027a034	journal	July 1995
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Structural and electrochemical stability of Li-rich layer structured Li2MoO3 in air Ma, Jun; Gao, Yurui; Wang, Zhaoxiang Journal of Power Sources, Vol. 258 https://doi.org/10.1016/j.jpowsour.2014.02.056	journal	July 2014
Material design of high-capacity Li-rich layered-oxide electrodes: Li ₂ MnO ₃ and beyond Kim, Soo; Aykol, Muratahan; Hegde, Vinay I. Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/C7EE01782K	journal	January 2017
Preparation and electrochemical properties of Li ₂ MoO ₃ /C composites for rechargeable Li-ion batteries Kumakura, Shinichi; Shirao, Yotaro; Kubota, Kei Physical Chemistry Chemical Physics, Vol. 18, Issue 41 https://doi.org/10.1039/C6CP05162F	journal	January 2016
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes Gallagher, Kevin G.; Croy, Jason R.; Balasubramanian, Mahalingam Electrochemistry Communications, Vol. 33 https://doi.org/10.1016/j.elecom.2013.04.022	journal	August 2013
Raman and ultraviolet spectroscopic characterization of molybdena on alumina catalysts Jeziorowski, Helge.; Knoezinger, Helmut. The Journal of Physical Chemistry, Vol. 83, Issue 9 https://doi.org/10.1021/j100472a012	journal	May 1979
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2524	journal	May 2016
The effect of different binders on electrochemical properties of LiNi1/3Mn1/3Co1/3O2 cathode material in lithium ion batteries Xu, Jiantie; Chou, Shu-Lei; Gu, Qin-fen Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.10.033	journal	March 2013
Structural Transformations in High-Capacity Li ₂ Cu _0.5 Ni _0.5 O ₂ Cathodes Ruther, Rose E.; Samuthira Pandian, Amaresh; Yan, Pengfei Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.6b05442	journal	March 2017
Challenges in the development of advanced Li-ion batteries: a review Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c1ee01598b	journal	January 2011
Examining Hysteresis in Composite x Li ₂ MnO ₃ ·(1– x )LiMO ₂ Cathode Structures Croy, Jason R.; Gallagher, Kevin G.; Balasubramanian, Mahalingam The Journal of Physical Chemistry C, Vol. 117, Issue 13 https://doi.org/10.1021/jp312658q	journal	March 2013
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
Structural changes in vanadium oxide-based cathodes during cycling in a lithium polymer electrolyte cell Macklin, W. J.; Neat, R. J.; Sandhu, S. S. Electrochimica Acta, Vol. 37, Issue 9 https://doi.org/10.1016/0013-4686(92)80145-C	journal	January 1992
Electrochemical behavior of submicron Li2MoO3 as anodes in lithium-ion batteries Li, Dan; He, Hongyan; Wu, Ximin Journal of Alloys and Compounds, Vol. 682 https://doi.org/10.1016/j.jallcom.2016.05.055	journal	October 2016
Structure and bonding in Li2MoO3 and Li2−xMoO3 (0 ≤ x ≤ 1.7) James, A. C. W. P.; Goodenough, J. B. Journal of Solid State Chemistry, Vol. 76, Issue 1 https://doi.org/10.1016/0022-4596(88)90194-6	journal	September 1988
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 Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló Journal of the American Chemical Society, Vol. 138, Issue 35 https://doi.org/10.1021/jacs.6b05111	journal	August 2016
Beyond One-Electron Reaction in Li Cathode Materials: Designing Li ₂ Mn _x Fe ₁ _- _x SiO ₄ Kokalj, Anton; Dominko, Robert; Mali, Gregor Chemistry of Materials, Vol. 19, Issue 15 https://doi.org/10.1021/cm063011l	journal	July 2007
Unexpected Voltage Fade in LMR-NMC Oxides Cycled below the “Activation” Plateau Li, Yan; Bareño, Javier; Bettge, Martin Journal of The Electrochemical Society, Vol. 162, Issue 1 https://doi.org/10.1149/2.0741501jes	journal	November 2014
Finite size effects on the structural progression induced by lithiation of V2O5: a combined diffraction and Raman spectroscopy study Horrocks, Gregory A.; Likely, Maliek F.; Velazquez, Jesus M. Journal of Materials Chemistry A, Vol. 1, Issue 48 https://doi.org/10.1039/c3ta13690f	journal	January 2013
Narrowing the Gap between Theoretical and Practical Capacities in Li-Ion Layered Oxide Cathode Materials Radin, Maxwell D.; Hy, Sunny; Sina, Mahsa Advanced Energy Materials, Vol. 7, Issue 20 https://doi.org/10.1002/aenm.201602888	journal	July 2017
Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6381	journal	November 2014
LiFeO ₂ -Incorporated Li ₂ MoO ₃ as a Cathode Additive for Lithium-Ion Battery Safety Park, Kyu-Sung; Im, Dongmin; Benayad, Anass Chemistry of Materials, Vol. 24, Issue 14 https://doi.org/10.1021/cm300505y	journal	July 2012
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/b702425h	journal	January 2007
Structural and Chemical Evolution of the Layered Li-Excess Li _x MnO ₃ as a Function of Li Content from First-Principles Calculations Lee, Eunseok; Persson, Kristin A. Advanced Energy Materials, Vol. 4, Issue 15 https://doi.org/10.1002/aenm.201400498	journal	June 2014
Li-ion battery materials: present and future Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae Materials Today, Vol. 18, Issue 5 https://doi.org/10.1016/j.mattod.2014.10.040	journal	June 2015
Optimization of Layered Cathode Materials for Lithium-Ion Batteries Julien, Christian; Mauger, Alain; Zaghib, Karim Materials, Vol. 9, Issue 7 https://doi.org/10.3390/ma9070595	journal	July 2016
Feasibility of Using Li ₂ MoO ₃ in Constructing Li-Rich High Energy Density Cathode Materials Ma, Jun; Zhou, Yong-Ning; Gao, Yurui Chemistry of Materials, Vol. 26, Issue 10 https://doi.org/10.1021/cm501025r	journal	May 2014
Synthesis and electrochemical properties of lithium molybdenum oxides Kobayashi, Hironori; Tabuchi, Mitsuharu; Shikano, Masahiro Journal of Power Sources, Vol. 81-82 https://doi.org/10.1016/S0378-7753(98)00227-4	journal	September 1999

Cited By (3)

Structural and Electrochemical Characterization of Thin Film Li ₂ MoO ₃ Electrodes Self, Ethan C.; Zhang, Yiman; Kercher, Andrew K. Journal of The Electrochemical Society, Vol. 166, Issue 6 https://doi.org/10.1149/2.1161904jes	journal	January 2019
Trace molybdenum doped Li ₂ RuO ₃ as a cathode material with enhanced performance for lithium ion batteries Wang, Jiali; Zhao, Yu; Zhang, Xiaoqiang Sustainable Energy & Fuels, Vol. 3, Issue 10 https://doi.org/10.1039/c9se00370c	journal	January 2019
Enhanced Electrochemical Performances of Cobalt-Doped Li2MoO3 Cathode Materials Yu, Zhiyong; Hao, Jishen; Li, Wenji Materials, Vol. 12, Issue 6 https://doi.org/10.3390/ma12060843	journal	March 2019