Tris(trimethylsilyl) phosphite (TMSPi) and triethyl phosphite (TEPi) as electrolyte additives for lithium ion batteries: Mechanistic insights into differences during LiNi0.5Mn0.3Co0.2O2- Graphite full cell cycling

Peebles, Cameron; Sahore, Ritu; Gilbert, James A.; Garcia, Juan C.; Tornheim, Adam; Bareno, Javier; Iddir, Hakim; Liao, Chen; Abraham, Daniel P.

doi:10.1149/2.1101707jes

Tris(trimethylsilyl) phosphite (TMSPi) and triethyl phosphite (TEPi) as electrolyte additives for lithium ion batteries: Mechanistic insights into differences during LiNi_0.5Mn_0.3Co_0.2O₂- Graphite full cell cycling

Journal Article · Sat May 27 00:00:00 EDT 2017 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.1101707jes· OSTI ID:1372387

Peebles, Cameron ^[1]; Sahore, Ritu ^[1]; Gilbert, James A. ^[1]; Garcia, Juan C. ^[1]; Tornheim, Adam ^[1]; Bareno, Javier ^[1]; Iddir, Hakim ^[1]; Liao, Chen ^[1]; Abraham, Daniel P. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)

Here, tris(trimethylsilyl) phosphite (TMSPi) has emerged as an useful electrolyte additive for lithium ion cells. This work examines the use of TMSPi and a structurally analogous compound, triethyl phosphite (TEPi), in LiNi_0.5Mn_0.3Co_0.2O₂-graphite full cells, containing a (baseline) electrolyte with 1.2 M LiPF6 in EC: EMC (3:7 w/w) and operating between 3.0-4.4 V. Galvanostatic cycling data reveal a measurable difference in capacity fade between the TMSPi and TEPi cells. Furthermore, lower impedance rise is observed for the TMSPi cells, because of the formation of a P-and O-rich surface film on the positive electrode that was revealed by X-ray photoelectron spectroscopy data. Elemental analysis on negative electrodes harvested from cycled cells show lower contents of transition metal (TM) elements for the TMSPi cells than for the baseline and TEPi cells. Our findings indicate that removal of TMS groups from the central P-O core of the TMSPi additive enables formation of the oxide surface film. This film is able to block the generation of reactive TM-oxygen radical species, suppress hydrogen abstraction from the electrolyte solvent, and minimize oxidation reactions at the positive electrode-electrolyte interface. In contrast, oxidation of TEPi does not yield a protective positive electrode film, which results in inferior electrochemical performance.

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)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1372387

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 7 Vol. 164; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy Miller, Dean J.; Proff, Christian; Wen, J. G. Advanced Energy Materials, Vol. 3, Issue 8 https://doi.org/10.1002/aenm.201300015	journal	May 2013
Understanding the Degradation Mechanisms of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Cathode Material in Lithium Ion Batteries Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300787	journal	August 2013
Performance of high-power lithium-ion cells under pulse discharge and charge conditions Abraham, D. P.; Dees, D. W.; Christophersen, J. International Journal of Energy Research, Vol. 34, Issue 2 https://doi.org/10.1002/er.1665	journal	December 2009
Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2 Belharouak, Ilias; Lu, Wenquan; Vissers, Donald Electrochemistry Communications, Vol. 8, Issue 2 https://doi.org/10.1016/j.elecom.2005.12.007	journal	February 2006
The influence of different conducting salts on the metal dissolution and capacity fading of NCM cathode material Gallus, Dennis Roman; Schmitz, René; Wagner, Ralf Electrochimica Acta, Vol. 134 https://doi.org/10.1016/j.electacta.2014.04.091	journal	July 2014
Tris(trimethylsilyl)phosphite as electrolyte additive for high voltage layered lithium nickel cobalt manganese oxide cathode of lithium ion battery Mai, Shaowei; Xu, Mengqing; Liao, Xiaolin Electrochimica Acta, Vol. 147 https://doi.org/10.1016/j.electacta.2014.09.157	journal	November 2014
Distinct Reaction Characteristics of Electrolyte Additives for High-Voltage Lithium-Ion Batteries: Tris(trimethylsilyl) Phosphite, Borate, and Phosphate Han, Young-Kyu; Yoo, Jaeik; Yim, Taeeun Electrochimica Acta, Vol. 215 https://doi.org/10.1016/j.electacta.2016.08.131	journal	October 2016
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
Phosphorus derivatives as electrolyte additives for lithium-ion battery: The removal of O 2 generated from lithium-rich layered oxide cathode Lee, Dong Joon; Im, Dongmin; Ryu, Young-Gyoon Journal of Power Sources, Vol. 243 https://doi.org/10.1016/j.jpowsour.2013.06.091	journal	December 2013
From coin cells to 400 mAh pouch cells: Enhancing performance of high-capacity lithium-ion cells via modifications in electrode constitution and fabrication Trask, Stephen E.; Li, Yan; Kubal, Joseph J. Journal of Power Sources, Vol. 259 https://doi.org/10.1016/j.jpowsour.2014.02.077	journal	August 2014
Exploiting chemically and electrochemically reactive phosphite derivatives for high-voltage spinel LiNi0.5Mn1.5O4 cathodes Song, Young-Min; Kim, Choon-Ki; Kim, Ko-Eun Journal of Power Sources, Vol. 302 https://doi.org/10.1016/j.jpowsour.2015.10.043	journal	January 2016
Failure mechanism of layered lithium-rich oxide/graphite cell and its solution by using electrolyte additive Zhu, Yunmin; Luo, Xueyi; Xu, Mengqing Journal of Power Sources, Vol. 317 https://doi.org/10.1016/j.jpowsour.2016.03.090	journal	June 2016
Electrocatalysis Paradigm for Protection of Cathode Materials in High-Voltage Lithium-Ion Batteries Shkrob, Ilya A.; Abraham, Daniel P. The Journal of Physical Chemistry C, Vol. 120, Issue 28 https://doi.org/10.1021/acs.jpcc.6b05756	journal	July 2016
Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries Han, Jung-Gu; Lee, Sung Jun; Lee, Jaegi ACS Applied Materials & Interfaces, Vol. 7, Issue 15 https://doi.org/10.1021/acsami.5b01770	journal	April 2015
Mechanistic Insight in the Function of Phosphite Additives for Protection of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Cathode in High Voltage Li-Ion Cells He, Meinan; Su, Chi-Cheung; Peebles, Cameron ACS Applied Materials & Interfaces, Vol. 8, Issue 18 https://doi.org/10.1021/acsami.6b01544	journal	April 2016
Role of Manganese Deposition on Graphite in the Capacity Fading of Lithium Ion Batteries Vissers, Daniel R.; Chen, Zonghai; Shao, Yuyan ACS Applied Materials & Interfaces, Vol. 8, Issue 22 https://doi.org/10.1021/acsami.6b02061	journal	May 2016
Structural Changes and Thermal Stability of Charged LiNi _x Mn _y Co _z O ₂ Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning ACS Applied Materials & Interfaces, Vol. 6, Issue 24 https://doi.org/10.1021/am506712c	journal	December 2014
Manganese in Graphite Anode and Capacity Fade in Li Ion Batteries Shkrob, Ilya A.; Kropf, A. Jeremy; Marin, Timothy W. The Journal of Physical Chemistry C, Vol. 118, Issue 42 https://doi.org/10.1021/jp507833u	journal	October 2014
Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries Choi, Nam-Soon; Han, Jung-Gu; Ha, Se-Young RSC Advances, Vol. 5, Issue 4 https://doi.org/10.1039/C4RA11575A	journal	January 2015
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
5V-class high-voltage batteries with over-lithiated oxide and a multi-functional additive Yim, Taeeun; Woo, Sang-Gil; Lim, Sang Hoo Journal of Materials Chemistry A, Vol. 3, Issue 11 https://doi.org/10.1039/C4TA06531J	journal	January 2015
The truth about the 1st cycle Coulombic efficiency of LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (NCM) cathodes Kasnatscheew, J.; Evertz, M.; Streipert, B. Physical Chemistry Chemical Physics, Vol. 18, Issue 5 https://doi.org/10.1039/C5CP07718D	journal	January 2016
Why is tris(trimethylsilyl) phosphite effective as an additive for high-voltage lithium-ion batteries? Han, Young-Kyu; Yoo, Jaeik; Yim, Taeeun Journal of Materials Chemistry A, Vol. 3, Issue 20 https://doi.org/10.1039/C5TA01253H	journal	January 2015
Lifetime limit of tris(trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries Qi, Xin; Tao, Liang; Hahn, Hendrik RSC Advances, Vol. 6, Issue 44 https://doi.org/10.1039/C6RA06555D	journal	January 2016
Role of surface coating on cathode materials for lithium-ion batteries Chen, Zonghai; Qin, Yan; Amine, Khalil Journal of Materials Chemistry, Vol. 20, Issue 36, p. 7606-7612 https://doi.org/10.1039/c0jm00154f	journal	January 2010
Fluorinated electrolytes for 5 V lithium-ion battery chemistry Zhang, Zhengcheng; Hu, Libo; Wu, Huiming Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee24414h	journal	January 2013
Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations Sallis, S.; Pereira, N.; Mukherjee, P. Applied Physics Letters, Vol. 108, Issue 26 https://doi.org/10.1063/1.4954800	journal	June 2016
Towards high throughput screening of electrochemical stability of battery electrolytes Borodin, Oleg; Olguin, Marco; Spear, Carrie E. Nanotechnology, Vol. 26, Issue 35 https://doi.org/10.1088/0957-4484/26/35/354003	journal	August 2015
An Attempt to Formulate Nonflammable Lithium Ion Electrolytes with Alkyl Phosphates and Phosphazenes Xu, Kang; Ding, Michael S.; Zhang, Shengshui Journal of The Electrochemical Society, Vol. 149, Issue 5 https://doi.org/10.1149/1.1467946	journal	January 2002
Microscopy and Spectroscopy of Lithium Nickel Oxide-Based Particles Used in High Power Lithium-Ion Cells Abraham, D. P.; Twesten, R. D.; Balasubramanian, M. Journal of The Electrochemical Society, Vol. 150, Issue 11 https://doi.org/10.1149/1.1613291	journal	January 2003
Understanding Long-Term Cycling Performance of Li _1.2 Ni _0.15 Mn _0.55 Co _0.1 O ₂ –Graphite Lithium-Ion Cells Li, Y.; Bettge, M.; Polzin, B. Journal of The Electrochemical Society, Vol. 160, Issue 5 https://doi.org/10.1149/2.002305jes	journal	January 2013
Cycling Behavior of NCM523/Graphite Lithium-Ion Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes Gilbert, James A.; Bareño, Javier; Spila, Timothy Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0081701jes	journal	September 2016
Ternary Electrolyte Additive Mixtures for Li-Ion Cells that Promote Long Lifetime and Less Reactivity with Charged Electrodes at Elevated Temperatures Ma, Lin; Xia, Jian; Dahn, J. R. Journal of The Electrochemical Society, Vol. 162, Issue 7 https://doi.org/10.1149/2.0181507jes	journal	January 2015
Fluorinated Electrolytes for 5-V Li-Ion Chemistry: Probing Voltage Stability of Electrolytes with Electrochemical Floating Test He, Meinan; Hu, Libo; Xue, Zheng Journal of The Electrochemical Society, Vol. 162, Issue 9 https://doi.org/10.1149/2.0231509jes	journal	January 2015
A Systematic Study of Electrolyte Additives in Li[Ni _1/3 Mn _1/3 Co _1/3 ]O ₂ (NMC)/Graphite Pouch Cells Wang, David Yaohui; Xia, Jian; Ma, Lin Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0511412jes	journal	January 2014
Enabling High-Energy, High-Voltage Lithium-Ion Cells: Standardization of Coin-Cell Assembly, Electrochemical Testing, and Evaluation of Full Cells Long, Brandon R.; Rinaldo, Steven G.; Gallagher, Kevin G. Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0691614jes	journal	January 2016
Positive Electrode Passivation by LiDFOB Electrolyte Additive in High-Capacity Lithium-Ion Cells Zhu, Ye; Li, Yan; Bettge, Martin Journal of The Electrochemical Society, Vol. 159, Issue 12 https://doi.org/10.1149/2.083212jes	journal	January 2012
Comparative Study of Tris(trimethylsilyl) Phosphate and Tris(trimethylsilyl) Phosphite as Electrolyte Additives for Li-Ion Cells Sinha, Nupur Nikkan; Burns, J. C.; Dahn, J. R. Journal of The Electrochemical Society, Vol. 161, Issue 6 https://doi.org/10.1149/2.087406jes	journal	January 2014
Improving the High Voltage Cycling of Li[Ni _0.42 Mn _0.42 Co _0.16 ]O ₂ (NMC442)/Graphite Pouch Cells Using Electrolyte Additives Ma, Lin; Xia, Jian; Dahn, J. R. Journal of The Electrochemical Society, Vol. 161, Issue 14 https://doi.org/10.1149/2.1041414jes	journal	January 2014
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells Gilbert, James A.; Shkrob, Ilya A.; Abraham, Daniel P. Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.1111702jes	journal	December 2016

Cited By (5)

Scavenging Materials to Stabilize LiPF ₆ ‐Containing Carbonate‐Based Electrolytes for Li‐Ion Batteries Han, Jung‐Gu; Kim, Koeun; Lee, Yongwon Advanced Materials, Vol. 31, Issue 20 https://doi.org/10.1002/adma.201804822	journal	November 2018
Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries Xu, Zhengrui; Rahman, Muhammad Mominur; Mu, Linqin Journal of Materials Chemistry A, Vol. 6, Issue 44 https://doi.org/10.1039/c8ta06875e	journal	January 2018
Some Physical Properties of Ethylene Carbonate-Free Electrolytes Xiong, D. J.; Bauer, M.; Ellis, L. D. Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0511802jes	journal	January 2018
Preformed Anodes for High-Voltage Lithium-Ion Battery Performance: Fluorinated Electrolytes, Crosstalk, and the Origins of Impedance Rise Tornheim, Adam; Sahore, Ritu; He, Meinan Journal of The Electrochemical Society, Vol. 165, Issue 14 https://doi.org/10.1149/2.0611814jes	journal	January 2018
Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds Tornheim, Adam; Garcia, Juan C.; Sahore, Ritu Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.0951902jes	journal	January 2019

Similar Records

Chemical “Pickling” of Phosphite Additives Mitigates Impedance Rise in Li Ion Batteries

Journal Article · Fri Apr 20 00:00:00 EDT 2018 · Journal of Physical Chemistry. C · OSTI ID:1460835

Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach

Journal Article · Fri Sep 01 00:00:00 EDT 2017 · Journal of Power Sources · OSTI ID:1393196

Tetrakis(triethyl phosphite)(nickel(O): catalyst for the reactions of aryl halides with trialkyl phosphites

Journal Article · Fri Oct 10 00:00:00 EDT 1986 · J. Gen. Chem. USSR (Engl. Transl.); (United States) · OSTI ID:5387491

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrolyte additive
high energy
high voltage
lithium-ion battery
oxide surface film
phosphite compound