Gas Evolution in LiNi0.5Mn1.5O4/Graphite Cells Studied In Operando by a Combination of Differential Electrochemical Mass Spectrometry, Neutron Imaging, and Pressure Measurements.

The cycling performance and in operando gas analysis of LiNi0.5Mn1.5O4 (LNMO)/graphite cells with reasonably high loading, containing a "standard" carbonate-based electrolyte is reported. The gas evolution over the first couple of cycles was thoroughly investigated via differential electrochemical mass spectrometry (DEMS), neutron imaging and pressure measurements. The main oxidation and reduction products were identified as CO2, H2 and C2H4. In different sets of experiments graphite was substituted with delithiated LiFePO4 (LFP) and LNMO with LFP to distinguish between processes occurring at either anode or cathode and gain mechanistic insights. Both C2H4 and H2 were found to be mainly formed at the anode side, while CO2 is generated at the cathode. The results from DEMS analysis further suggest that the Ni redox couples play a profound role in the evolution of CO2 at the LNMO/electrolyte interface. Lastly, it is shown that the cycling stability and capacity retention of LNMO/graphite cells can be considerably improved by a simple cell formation procedure.

[1]  J. Janek,et al.  Simultaneous acquisition of differential electrochemical mass spectrometry and infrared spectroscopy data for in situ characterization of gas evolution reactions in lithium-ion batteries , 2015 .

[2]  J. Janek,et al.  Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging , 2015, Scientific Reports.

[3]  J. Janek,et al.  Online Continuous Flow Differential Electrochemical Mass Spectrometry with a Realistic Battery Setup for High-Precision, Long-Term Cycling Tests. , 2015, Analytical chemistry.

[4]  Eric D. Rus,et al.  CO₂ and O₂ evolution at high voltage cathode materials of Li-ion batteries: a differential electrochemical mass spectrometry study. , 2014, Analytical chemistry.

[5]  B. Lucht,et al.  Generation of Cathode Passivation Films via Oxidation of Lithium Bis(oxalato) Borate on High Voltage Spinel (LiNi0.5Mn1.5O4) , 2014 .

[6]  Arumugam Manthiram,et al.  A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries , 2014 .

[7]  Jung-Hyun Kim,et al.  Understanding Transition-Metal Dissolution Behavior in LiNi0.5Mn1.5O4 High-Voltage Spinel for Lithium Ion Batteries , 2013 .

[8]  Seung M. Oh,et al.  Failure mechanisms of LiNi0.5Mn1.5O4 electrode at elevated temperature , 2012 .

[9]  A. Manthiram,et al.  Role of Oxygen Vacancies on the Performance of Li[Ni0.5–xMn1.5+x]O4 (x = 0, 0.05, and 0.08) Spinel Cathodes for Lithium-Ion Batteries , 2012 .

[10]  C. Grünzweig,et al.  The ICON beamline – A facility for cold neutron imaging at SINQ , 2011 .

[11]  A. Manthiram,et al.  Surface-segregated, high-voltage spinel LiMn1.5Ni0.42Ga0.08O4 cathodes with superior high-temperature cyclability for lithium-ion batteries , 2011 .

[12]  E. Lehmann,et al.  Imaging with cold neutrons , 2011 .

[13]  Anna G. Stefanopoulou,et al.  Neutron Imaging of Lithium Concentration in LFP Pouch Cell Battery , 2011 .

[14]  B. Rambabu,et al.  Research progress in high voltage spinel LiNi0.5Mn1.5O4 material , 2010 .

[15]  Doron Aurbach,et al.  Revisiting LiClO4 as an Electrolyte for Rechargeable Lithium-Ion Batteries , 2010 .

[16]  Shinichi Kinoshita,et al.  Identification of the Source of Evolved Gas in Li-Ion Batteries Using #2#1 -labeled Solvents , 2008 .

[17]  J. Vetter,et al.  Oxygen, hydrogen, ethylene and CO2 development in lithium-ion batteries , 2007 .

[18]  Linda F. Nazar,et al.  Review on electrode–electrolyte solution interactions, related to cathode materials for Li-ion batteries , 2007 .

[19]  M. Wohlfahrt‐Mehrens,et al.  Ageing mechanisms in lithium-ion batteries , 2005 .

[20]  P. Kolář,et al.  Prediction of gas solubility in battery formulations , 2005 .

[21]  H. Baltruschat.  Differential electrochemical mass spectrometry , 2004, Journal of the American Society for Mass Spectrometry.

[22]  P. Novák,et al.  In situ neutron radiography of lithium-ion batteries: the gas evolution on graphite electrodes during the charging , 2004 .

[23]  S. Komaba,et al.  Influence of manganese(II), cobalt(II), and nickel(II) additives in electrolyte on performance of graphite anode for lithium-ion batteries , 2002 .

[24]  M. Yoshio,et al.  In Situ XAFS Analysis of Li(Mn, M)2O4 (M=Cr, Co, Ni) 5V Cathode Materials for Lithium-Ion Secondary Batteries , 2001 .

[25]  Petr Novák,et al.  In Situ Investigation of the Electrochemical Reduction of Carbonate Electrolyte Solutions at Graphite Electrodes , 1998 .

[26]  E. Peled,et al.  Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes , 1997 .

[27]  K. Yoneda,et al.  Application of Neutron Radiography to Visualize the Motion of Lithium Ions in Lithium‐Ion Conducting Materials , 1996 .

[28]  D. Aurbach,et al.  The Use of EQCM for the Study of Nonactive Metal Electrodes in Propylene Carbonate ‐ LiAsF6 Solutions Significance of the Data Obtained , 1995 .

[29]  Doron Aurbach,et al.  The behaviour of lithium electrodes in propylene and ethylene carbonate: Te major factors that influence Li cycling efficiency , 1992 .

[30]  J. C. Hunter.  Preparation of a new crystal form of manganese dioxide: λ-MnO2 , 1981 .

[31]  J. Dahn,et al.  A Survey of In Situ Gas Evolution during High Voltage Formation in Li-Ion Pouch Cells , 2015 .

[32]  B. Lucht,et al.  Failure Mechanism of Graphite/LiNi0.5Mn1.5O4 Cells at High Voltage and Elevated Temperature , 2013 .

[33]  Hubert A. Gasteiger,et al.  A Novel On-Line Mass Spectrometer Design for the Study of Multiple Charging Cycles of a Li-O2 Battery , 2013 .

[34]  Vincent S. Battaglia,et al.  In situ neutron radiography analysis of graphite/NCA lithium-ion battery during overcharge , 2011, Journal of Applied Electrochemistry.