Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

Gao, Han; Maglia, Filippo; Lamp, Peter; Amine, Khalil; Chen, Zonghai

doi:10.1021/acsami.7b15395

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

Journal Article · Tue Dec 05 23:00:00 EST 2017 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b15395· OSTI ID:1426673

Gao, Han ^[1]; Maglia, Filippo ^[2]; Lamp, Peter ^[2]; ^[1]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
BMW Group, Munich (Germany)

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi_0.6Mn_0.2Co_0.2O₂ (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. In conclusion, more importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1426673

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 51 Vol. 9; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (33)

Study of Thermal Decomposition of Li _1-x (Ni _1/3 Mn _1/3 Co _1/3 ) _0.9 O ₂ Using In-Situ High-Energy X-Ray Diffraction Chen, Zonghai; Ren, Yang; Lee, Eungje Advanced Energy Materials, Vol. 3, Issue 6 https://doi.org/10.1002/aenm.201201059	journal	March 2013
Recent Progress in Research on High-Voltage Electrolytes for Lithium-Ion Batteries Tan, Shi; Ji, Ya J.; Zhang, Zhong R. ChemPhysChem, Vol. 15, Issue 10 https://doi.org/10.1002/cphc.201402175	journal	July 2014
Recent advances in lithium ion battery materials Scrosati, Bruno Electrochimica Acta, Vol. 45, Issue 15-16 https://doi.org/10.1016/S0013-4686(00)00333-9	journal	May 2000
An unique lithium salt for the improved electrolyte of Li-ion battery Shui Zhang, Sheng Electrochemistry Communications, Vol. 8, Issue 9 https://doi.org/10.1016/j.elecom.2006.06.016	journal	September 2006
Improvement of high voltage cycling performance and thermal stability of lithium–ion cells by use of a thiophene additive Lee, Ki-Soo; Sun, Yang-Kook; Noh, Jaegeun Electrochemistry Communications, Vol. 11, Issue 10 https://doi.org/10.1016/j.elecom.2009.08.012	journal	October 2009
Cathode materials modified by surface coating for lithium ion batteries Li, C.; Zhang, H. P.; Fu, L. J. Electrochimica Acta, Vol. 51, Issue 19 https://doi.org/10.1016/j.electacta.2005.11.015	journal	May 2006
A review on electrolyte additives for lithium-ion batteries Zhang, Sheng Shui Journal of Power Sources, Vol. 162, Issue 2, p. 1379-1394 https://doi.org/10.1016/j.jpowsour.2006.07.074	journal	November 2006
Lithium difluoro(oxalato)borate/ethylene carbonate+propylene carbonate+ethyl(methyl) carbonate electrolyte for LiMn2O4 cathode Fu, M. H.; Huang, K. L.; Liu, S. Q. Journal of Power Sources, Vol. 195, Issue 3 https://doi.org/10.1016/j.jpowsour.2009.08.042	journal	February 2010
Improving electrochemical performance of Li3V2(PO4)3 in a thiophene-containing electrolyte Hu, Meng; Wei, Jinping; Xing, Liying Journal of Power Sources, Vol. 222 https://doi.org/10.1016/j.jpowsour.2012.09.005	journal	January 2013
Nanostructured electrodes for high-power lithium ion batteries Mukherjee, Rahul; Krishnan, Rahul; Lu, Toh-Ming Nano Energy, Vol. 1, Issue 4 https://doi.org/10.1016/j.nanoen.2012.04.001	journal	July 2012
Kinetic Study of Parasitic Reactions in Lithium-Ion Batteries: A Case Study on LiNi _0.6 Mn _0.2 Co _0.2 O ₂ Zeng, Xiaoqiao; Xu, Gui-Liang; Li, Yan ACS Applied Materials & Interfaces, Vol. 8, Issue 5 https://doi.org/10.1021/acsami.5b11800	journal	January 2016
Conjugated poly(thiophenes): synthesis, functionalization, and applications Roncali, Jean Chemical Reviews, Vol. 92, Issue 4 https://doi.org/10.1021/cr00012a009	journal	June 1992
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes Borodin, Oleg; Behl, Wishvender; Jow, T. Richard The Journal of Physical Chemistry C, Vol. 117, Issue 17 https://doi.org/10.1021/jp400527c	journal	April 2013
Mechanistic Insight into the Protective Action of Bis(oxalato)borate and Difluoro(oxalate)borate Anions in Li-Ion Batteries. Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W. The Journal of Physical Chemistry C, Vol. 117, Issue 45 https://doi.org/10.1021/jp407714p	journal	October 2013
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
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Lithium batteries: To the limits of lithium Evarts, Eric C. Nature, Vol. 526, Issue 7575 https://doi.org/10.1038/526S93a	journal	October 2015
Transition metal dissolution and deposition in Li-ion batteries investigated by operando X-ray absorption spectroscopy Wandt, Johannes; Freiberg, Anna; Thomas, Rowena Journal of Materials Chemistry A, Vol. 4, Issue 47 https://doi.org/10.1039/C6TA08865A	journal	January 2016
Mechanism of capacity fade of MCMB/Li1.1[Ni1/3Mn1/3Co1/3]0.9O2 cell at elevated temperature and additives to improve its cycle life Amine, Khalil; Chen, Zonghai; Zhang, Z. Journal of Materials Chemistry, Vol. 21, Issue 44 https://doi.org/10.1039/c1jm11584g	journal	January 2011
Significance of the Tetrahedral A Site on the Electrochemical Performance of Substituted Li[sub 1.05]M[sub 0.05]Mn[sub 1.90]O[sub 4] Spinel Electrodes (M=Li, Mg, Zn, Al) in Lithium Cells Kim, J. -S.; Vaughey, J. T.; Johnson, C. S. Journal of The Electrochemical Society, Vol. 150, Issue 11 https://doi.org/10.1149/1.1614798	journal	January 2003
Functional Electrolyte: Additives for Improving the Cyclability of Cathode Materials Abe, Koji; Takaya, Tsukasa; Yoshitake, Hideya Electrochemical and Solid-State Letters, Vol. 7, Issue 12 https://doi.org/10.1149/1.1809557	journal	January 2004
A New Three‐Volt Spinel Li_1 + xMn_1.5Ni_0.5 O ₄ for Secondary Lithium Batteries Amine, K.; Tukamoto, H.; Yasuda, H. Journal of The Electrochemical Society, Vol. 143, Issue 5, p. 1607-1613 https://doi.org/10.1149/1.1836686	journal	January 1996
Synthesis and Electrochemistry of LiNi[sub x]Mn[sub 2−x]O[sub 4] Zhong, Qiming Journal of The Electrochemical Society, Vol. 144, Issue 1 https://doi.org/10.1149/1.1837386	journal	January 1997
The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li₂MnO₃ ∙ 0.5 LiNi_0.44Co_0.25Mn_0.31O₂ Electrodes in Lithium Cells Kang, S.-H.; Johnson, C. S.; Vaughey, J. T. Journal of The Electrochemical Society, Vol. 153, Issue 6, p. A1186-A1192 https://doi.org/10.1149/1.2194764	journal	January 2006
3-Hexylthiophene as a Stabilizing Additive for High Voltage Cathodes in Lithium-Ion Batteries Abouimrane, Ali; Odom, Susan A.; Tavassol, Hadi Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.039302jes	journal	December 2012
Countering the Voltage Decay in High Capacity xLi ₂ MnO ₃ •(1–x)LiMO ₂ Electrodes (M=Mn, Ni, Co) for Li ⁺ -Ion Batteries Croy, Jason R.; Kim, Donghan; Balasubramanian, Mahalingam Journal of The Electrochemical Society, Vol. 159, Issue 6 https://doi.org/10.1149/2.080206jes	journal	January 2012
Origin of H ₂ Evolution in LIBs: H ₂ O Reduction vs. Electrolyte Oxidation Metzger, Michael; Strehle, Benjamin; Solchenbach, Sophie Journal of The Electrochemical Society, Vol. 163, Issue 5 https://doi.org/10.1149/2.1151605jes	journal	January 2016
Layered Lithium Insertion Material of LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ for Lithium-Ion Batteries Ohzuku, Tsutomu; Makimura, Yoshinari Chemistry Letters, Vol. 30, Issue 7 https://doi.org/10.1246/cl.2001.642	journal	July 2001
Insight into the Gassing Problem of Li-ion Battery Zhang, Sheng S. Frontiers in Energy Research, Vol. 2 https://doi.org/10.3389/fenrg.2014.00059	journal	December 2014

Cited By (7)

Highly Tough, Li‐Metal Compatible Organic–Inorganic Double‐Network Solvate Ionogel Yu, Le; Guo, Songtao; Lu, Yue Advanced Energy Materials, Vol. 9, Issue 22 https://doi.org/10.1002/aenm.201900257	journal	April 2019
Effects of Charge Cutoff Potential on an Electrolyte Additive for LiNi _0.6 Co _0.2 Mn _0.2 O ₂ –Mesocarbon Microbead Full Cells Deng, Bangwei; Wang, Hao; Li, Xiang Energy Technology, Vol. 7, Issue 4 https://doi.org/10.1002/ente.201800981	journal	March 2019
Boron additive passivated carbonate electrolytes for stable cycling of 5 V lithium–metal batteries Yue, Hongyun; Yang, Yange; Xiao, Yan Journal of Materials Chemistry A, Vol. 7, Issue 2 https://doi.org/10.1039/c8ta09380f	journal	January 2019
A Multifunctional Thiophene-Based Electrolyte Additive for Lithium Metal Batteries Using High-Voltage LiCoO ₂ Cathode Zheng, Yi; Fang, Wei; Zheng, Hao Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0291914jes	journal	January 2019
Hot Formation for Improved Low Temperature Cycling of Anode-Free Lithium Metal Batteries Genovese, Matthew; Louli, A. J.; Weber, Rochelle Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0661914jes	journal	January 2019
Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes RWTH Aachen University https://doi.org/10.18154/rwth-2020-04543	text	January 2020
Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes Batteries, Vol. 6, Issue 1 https://doi.org/10.3390/batteries6010008	journal	January 2020

Similar Records

Electrolytes Containing Triethyl Phosphate Solubilized Lithium Nitrate for Improved Silicon Anode Performance

Journal Article · Sun Apr 17 20:00:00 EDT 2022 · Journal of the Electrochemical Society · OSTI ID:1863476

Related Subjects

25 ENERGY STORAGE
3HT
HFiP
LiDFOB
electrode-electrolyte interface
electrolyte additives
high voltage
lithium-ion batteries
protection mechanisms

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

Citation Formats

References (33)

Cited By (7)

Similar Records

Related Subjects