Conformal LiF Stabilized Interfaces via Electrochemical Fluorination on High Voltage Spinel Cathodes (≈4.9 V) for Lithium-Ion Batteries

Thapaliya, Bishnu Prasad; Borisevich, Albina Y.; Meyer III, Harry M.; Sun, Xiao‐Guang; Bridges, Craig A.; Dai, Sheng

doi:10.1002/admi.202201600

Title: Conformal LiF Stabilized Interfaces via Electrochemical Fluorination on High Voltage Spinel Cathodes (≈4.9 V) for Lithium-Ion Batteries

Journal Article · Mon Oct 03 00:00:00 EDT 2022 · Advanced Materials Interfaces

DOI:https://doi.org/10.1002/admi.202201600· OSTI ID:1908083

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States)

Abstract The high voltage LiNi _0.5 Mn _1.5 O ₄ (LNMO) spinel is one of the promising cathodes for the lithium‐ion batteries due to its high energy densities, good rate performance. However, its high operating potential (≈4.75 V) causes extensive oxidation of conventional carbonate electrolytes, resulting an unstable and thick cathode electrolyte interphase (CEI) layer with a large irreversible capacity and low coulombic efficiency. Herein, this work reports the formation of thin LiF stabilized interfaces on LNMO via electrochemical fluorination that significantly improves the cycling stability and enhanced the capacity. An electrochemically induced conformal LiF layer acts as a part of a robust CEI by reducing the leakage of electrons and allowing the conduction of Li ions through it. Because of the robust LiF stabilized CEI, LNMO delivers a discharge capacity of ≈148.5 and ≈117.1 mAh g ⁻¹ at 0.1 and 1 C rate, respectively. It exhibits excellent cyclability with 80% capacity retention (CR) after 600 cycles in lithium‐half cell and ≈90% CR after 200 cycles in full cell with only 0.03% and 0.05% capacity decay per cycle in conventional carbonate electrolytes without additives. Such an excellent electrochemical performance could lead to the potential development of high energy density batteries with high voltage cathodes for grid‐based applications.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1908083

Alternate ID(s):: OSTI ID: 1890774

Journal Information:: Advanced Materials Interfaces, Vol. 9, Issue 32; ISSN 2196-7350

Publisher:: Wiley-VCHCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries Thackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21892e	journal	January 2012
An Artificial Solid Electrolyte Interphase Enables the Use of a LiNi _0.5 Mn _1.5 O ₄ 5 V Cathode with Conventional Electrolytes Li, Juchuan; Baggetto, Loïc; Martha, Surendra K. Advanced Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aenm201300378	journal	August 2013
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
A Novel Electrolyte Salt Additive for Lithium-Ion Batteries with Voltages Greater than 4.7 V Li, Yunchao; Wan, Shun; Veith, Gabriel M. Advanced Energy Materials, Vol. 7, Issue 4 https://doi.org/10.1002/aenm.201601397	journal	November 2016
Understanding the Improvement in the Electrochemical Properties of Surface Modified 5 V LiMn _1.42 Ni _0.42 Co _0.16 O ₄ Spinel Cathodes in Lithium-ion Cells Liu, Jun; Manthiram, Arumugam Chemistry of Materials, Vol. 21, Issue 8 https://doi.org/10.1021/cm9000043	journal	April 2009
Microwave-Assisted Synthesis of High-Voltage Nanostructured LiMn_1.5Ni_0.5O₄ Spinel: Tuning the Mn³⁺ Content and Electrochemical Performance Jafta, Charl J.; Mathe, Mkhulu K.; Manyala, Ncholu ACS Applied Materials & Interfaces, Vol. 5, Issue 15, p. 7592-7598 https://doi.org/10.1021/am401894t	journal	July 2013
Higher, Stronger, Better…︁ A Review of 5 Volt Cathode Materials for Advanced Lithium-Ion Batteries Kraytsberg, Alexander; Ein-Eli, Yair Advanced Energy Materials, Vol. 2, Issue 8 https://doi.org/10.1002/aenm.201200068	journal	June 2012
Spinel materials for high-voltage cathodes in Li-ion batteries Liu, D.; Zhu, W.; Trottier, J. RSC Adv., Vol. 4, Issue 1 https://doi.org/10.1039/C3RA45706K	journal	January 2014
Influence of Cation Ordering and Lattice Distortion on the Charge–Discharge Behavior of LiMn _1.5 Ni _0.5 O ₄ Spinel between 5.0 and 2.0 V Lee, Eun-Sung; Nam, Kyung-Wan; Hu, Enyuan Chemistry of Materials, Vol. 24, Issue 18 https://doi.org/10.1021/cm3020836	journal	September 2012
Composition-Structure Relationships in the Li-Ion Battery Electrode Material LiNi _0.5 Mn _1.5 O ₄ Cabana, Jordi; Casas-Cabanas, Montserrat; Omenya, Fredrick O. Chemistry of Materials, Vol. 24, Issue 15 https://doi.org/10.1021/cm301148d	journal	August 2012
Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries Yang, Li; Ravdel, Boris; Lucht, Brett L. Electrochemical and Solid-State Letters, Vol. 13, Issue 8 https://doi.org/10.1149/1.3428515	journal	January 2010
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries Aurbach, Doron Journal of Power Sources, Vol. 89, Issue 2 https://doi.org/10.1016/S0378-7753(00)00431-6	journal	August 2000
Recent progress in high-voltage lithium ion batteries Hu, Meng; Pang, Xiaoli; Zhou, Zhen Journal of Power Sources, Vol. 237 https://doi.org/10.1016/j.jpowsour.2013.03.024	journal	September 2013
Understanding Transition-Metal Dissolution Behavior in LiNi _0.5 Mn _1.5 O ₄ High-Voltage Spinel for Lithium Ion Batteries Pieczonka, Nicholas P. W.; Liu, Zhongyi; Lu, Peng The Journal of Physical Chemistry C, Vol. 117, Issue 31 https://doi.org/10.1021/jp405158m	journal	July 2013
The Solid Electrolyte Interphase – The Most Important and the Least Understood Solid Electrolyte in Rechargeable Li Batteries Winter, Martin Zeitschrift für Physikalische Chemie, Vol. 223, Issue 10-11 https://doi.org/10.1524/zpch.2009.6086	journal	December 2009
Fabrication and characterization of Li–Mn–Ni–O sputtered thin film high voltage cathodes for Li-ion batteries Baggetto, Loïc; Unocic, Raymond R.; Dudney, Nancy J. Journal of Power Sources, Vol. 211 https://doi.org/10.1016/j.jpowsour.2012.03.076	journal	August 2012
Publisher's Note: Kinetics Study of the 5 V Spinel Cathode LiMn[sub 1.5]Ni[sub 0.5]O[sub 4] Before and After Surface Modifications [J. Electrochem. Soc., 156, A833 (2009)] Liu, J.; Manthiram, A. Journal of The Electrochemical Society, Vol. 156, Issue 12 https://doi.org/10.1149/1.3240895	journal	January 2009
Improved cycling performance of 5 V spinel LiMn1.5Ni0.5O4 by amorphous FePO4 coating Liu, Dilong; Bai, Ying; Zhao, Sen Journal of Power Sources, Vol. 219 https://doi.org/10.1016/j.jpowsour.2012.07.058	journal	December 2012
Graphene-oxide-coated LiNi0.5Mn1.5O4 as high voltage cathode for lithium ion batteries with high energy density and long cycle life Fang, Xin; Ge, Mingyuan; Rong, Jiepeng Journal of Materials Chemistry A, Vol. 1, Issue 12 https://doi.org/10.1039/c3ta01534c	journal	January 2013
Materials Challenges and Opportunities of Lithium Ion Batteries Manthiram, Arumugam The Journal of Physical Chemistry Letters, Vol. 2, Issue 3 https://doi.org/10.1021/jz1015422	journal	January 2011
A polymer electrolyte-skinned active material strategy toward high-voltage lithium ion batteries: a polyimide-coated LiNi0.5Mn1.5O4 spinel cathode material case Cho, Ju-Hyun; Park, Jang-Hoon; Lee, Myeong-Hee Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee03389e	journal	January 2012
Influence of Lattice Parameter Differences on the Electrochemical Performance of the 5 V Spinel LiMn_{1.5 − y}Ni_{0.5 − z}M_y + zO₄ (M = Li , Mg, Fe, Co, and Zn) Arunkumar, T. A.; Manthiram, A. Electrochemical and Solid-State Letters, Vol. 8, Issue 8, p. A403-A405 https://doi.org/10.1149/1.1945369	journal	January 2005
Influence of chromium doping on the electrochemical performance of the 5V spinel cathode LiMn1.5Ni0.5O4 Arunkumar, T. A.; Manthiram, A. Electrochimica Acta, Vol. 50, Issue 28 https://doi.org/10.1016/j.electacta.2005.03.033	journal	September 2005
On the application of ionic liquids for rechargeable Li batteries: High voltage systems Borgel, V.; Markevich, E.; Aurbach, D. Journal of Power Sources, Vol. 189, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.08.099	journal	April 2009
A multifunctional phosphite-containing electrolyte for 5 V-class LiNi _0.5 Mn _1.5 O ₄ cathodes with superior electrochemical performance Song, Young-Min; Han, Jung-Gu; Park, Soojin J. Mater. Chem. A, Vol. 2, Issue 25 https://doi.org/10.1039/C4TA01129E	journal	January 2014
Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries Pieczonka, Nicholas P. W.; Yang, Li; Balogh, Michael P. The Journal of Physical Chemistry C, Vol. 117, Issue 44 https://doi.org/10.1021/jp408717x	journal	October 2013
Development of novel lithium borate additives for designed surface modification of high voltage LiNi _0.5 Mn _1.5 O ₄ cathodes Xu, Mengqing; Zhou, Liu; Dong, Yingnan Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE03360H	journal	January 2016
FSI-inspired solvent and “full fluorosulfonyl” electrolyte for 4 V class lithium-metal batteries Xue, Weijiang; Shi, Zhe; Huang, Mingjun Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE02538C	journal	January 2020
Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte Xue, Weijiang; Huang, Mingjun; Li, Yutao Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00792-y	journal	March 2021
Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries Fan, Xiulin; Chen, Long; Ji, Xiao Chem, Vol. 4, Issue 1 https://doi.org/10.1016/j.chempr.2017.10.017	journal	January 2018
All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents Fan, Xiulin; Ji, Xiao; Chen, Long Nature Energy, Vol. 4, Issue 10 https://doi.org/10.1038/s41560-019-0474-3	journal	October 2019
Fluorination of MXene by Elemental F ₂ as Electrode Material for Lithium‐Ion Batteries Thapaliya, Bishnu P.; Jafta, Charl J.; Lyu, Hailong ChemSusChem, Vol. 12, Issue 7 https://doi.org/10.1002/cssc.201900003	journal	March 2019
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox House, Robert A.; Jin, Liyu; Maitra, Urmimala Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03195E	journal	January 2018
Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery Fulvio, Pasquale F.; Brown, Suree S.; Adcock, Jamie Chemistry of Materials, Vol. 23, Issue 20 https://doi.org/10.1021/cm2012395	journal	October 2011
Synthesizing High‐Capacity Oxyfluoride Conversion Anodes by Direct Fluorination of Molybdenum Dioxide (MoO ₂ ) Thapaliya, Bishnu P.; Self, Ethan C.; Jafta, Charl J. ChemSusChem, Vol. 13, Issue 15 https://doi.org/10.1002/cssc.202001006	journal	July 2020
Formation of LiF Surface Layer During Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes Zhang, Yiman; Self, Ethan C.; Thapaliya, Bishnu P. ACS Applied Materials & Interfaces, Vol. 13, Issue 32 https://doi.org/10.1021/acsami.1c07882	journal	August 2021
Enhancing Cycling Stability and Capacity Retention of NMC811 Cathodes by Reengineering Interfaces via Electrochemical Fluorination Thapaliya, Bishnu P.; Misra, Sudhajit; Yang, Shi‐ze Advanced Materials Interfaces, Vol. 9, Issue 18 https://doi.org/10.1002/admi.202200035	journal	February 2022
Simultaneously Boosting the Ionic Conductivity and Mechanical Strength of Polymer Gel Electrolyte Membranes by Confining Ionic Liquids into Hollow Silica Nanocavities Thapaliya, Bishnu P.; Do‐Thanh, Chi‐Linh; Jafta, Charl J. Batteries & Supercaps, Vol. 2, Issue 12 https://doi.org/10.1002/batt.201900095	journal	September 2019
High rate capability of 5 V LiNi0.5Mn1.5O4 cathode material synthesized via a microwave assist method Feng, Xu-Yong; Shen, Chen; Xiang, Hong-Fa Journal of Alloys and Compounds, Vol. 695 https://doi.org/10.1016/j.jallcom.2016.10.186	journal	February 2017
Microwave rapid preparation of LiNi0.5Mn1.5O4 and the improved high rate performance for lithium-ion batteries Gao, Po; Wang, Lu; Chen, Lin Electrochimica Acta, Vol. 100 https://doi.org/10.1016/j.electacta.2013.03.153	journal	June 2013
Morphology and electrochemistry of LiMn2O4 optimized by using different Mn-sources Bao, Shu-Juan; Li, Chang-Ming; Li, Hu-Lin Journal of Power Sources, Vol. 164, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.11.015	journal	February 2007
Understanding structural, optical, magnetic and electrical performances of Fe- or Co-substituted spinel LiMn1.5Ni0.5O4 cathode materials Sanad, M. M. S.; Abdellatif, H. A.; Elnaggar, Elsayed M. Applied Physics A, Vol. 125, Issue 2 https://doi.org/10.1007/s00339-019-2445-8	journal	January 2019
Synthesis of LiNi0.5Mn1.5O4 cathode material with improved electrochemical performances through a modified solid-state method Wang, Li; Chen, Dan; Wang, Jiangfeng Powder Technology, Vol. 292 https://doi.org/10.1016/j.powtec.2016.02.002	journal	May 2016
Role of Cation Ordering and Surface Segregation in High-Voltage Spinel LiMn _1.5 Ni _{0.5– x} M _x O ₄ (M = Cr, Fe, and Ga) Cathodes for Lithium-Ion Batteries Shin, Dong Wook; Bridges, Craig A.; Huq, Ashfia Chemistry of Materials, Vol. 24, Issue 19 https://doi.org/10.1021/cm301844w	journal	September 2012
Integrated Nano-Domains of Disordered and Ordered Spinel Phases in LiNi _0.5 Mn _1.5 O ₄ for Li-Ion Batteries Kim, Jung-Hyun; Huq, Ashfia; Chi, Miaofang Chemistry of Materials, Vol. 26, Issue 15 https://doi.org/10.1021/cm501203r	journal	July 2014
Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids Fuchigami, Toshio; Inagi, Shinsuke Chemical Communications, Vol. 47, Issue 37 https://doi.org/10.1039/c1cc12414e	journal	January 2011
Insight into the Solid Electrolyte Interphase Formation in Bis(fluorosulfonyl)Imide Based Ionic Liquid Electrolytes Jafta, Charl J.; Sun, Xiao‐Guang; Lyu, Hailong Advanced Functional Materials, Vol. 31, Issue 23 https://doi.org/10.1002/adfm.202008708	journal	February 2021
Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering Jafta, Charl J.; Sun, Xiao-Guang; Veith, Gabriel M. Energy & Environmental Science, Vol. 12, Issue 6 https://doi.org/10.1039/C8EE02703J	journal	January 2019
Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries Fan, Xiulin; Chen, Long; Borodin, Oleg Nature Nanotechnology, Vol. 13, Issue 8 https://doi.org/10.1038/s41565-018-0183-2	journal	July 2018

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25 ENERGY STORAGE
conformal LiF
electrochemical fluorination
electromaterial functionalization
high energy density batteries
high-voltage spinel cathodes

Title: Conformal LiF Stabilized Interfaces via Electrochemical Fluorination on High Voltage Spinel Cathodes (≈4.9 V) for Lithium-Ion Batteries

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