Structural changes and thermal stability of charged LiNixMnyCozO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy.

Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3̅m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3̅m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. This systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

[1]  S. Adams,et al.  Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries , 2015, Scientific Reports.

[2]  Christian Martin.  Driving change in the battery industry. , 2014, Nature nanotechnology.

[3]  M. Yoshikawa,et al.  The effect of thermal stability for high-Ni-content layer-structured cathode materials, LiNi0.8Mn0.1−xCo0.1MoxO2 (x = 0, 0.02, 0.04) , 2013 .

[4]  Xiao‐Qing Yang,et al.  Thermal stability of charged LiNi0.5Co0.2Mn0.3O2 cathode for Li-ion batteries investigated by synchrotron based in situ X-ray diffraction , 2013 .

[5]  Thomas Hamacher,et al.  Optimized charging of electric vehicles with regard to battery constraints - Case study: Singaporean car park , 2013, 2013 IEEE Energytech.

[6]  Lijun Wu,et al.  Combining In Situ Synchrotron X‐Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium‐Ion Batteries , 2013 .

[7]  Xiqian Yu,et al.  Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged LixNi0.8Co0.15Al0.05O2 Cathode Materials , 2013 .

[8]  Seung-Don Choi,et al.  The Current Move of Lithium Ion Batteries Towards the Next Phase , 2012 .

[9]  Christopher M Wolverton,et al.  Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries , 2012 .

[10]  Yongseon Kim.  Lithium nickel cobalt manganese oxide synthesized using alkali chloride flux: morphology and performance as a cathode material for lithium ion batteries. , 2012, ACS applied materials & interfaces.

[11]  M. Yoshikawa,et al.  Thermal stability of Li1−yNixMn(1−x)/2Co(1−x)/2O2 layer-structured cathode materials used in Li-Ion batteries , 2011 .

[12]  Lijun Wu,et al.  Structural Origin of Overcharge-Induced Thermal Instability of Ni-Containing Layered-Cathodes for High-Energy-Density Lithium Batteries , 2011 .

[13]  J. Goodenough,et al.  Challenges for Rechargeable Li Batteries , 2010 .

[14]  Ilias Belharouak,et al.  High-energy cathode material for long-life and safe lithium batteries. , 2009, Nature materials.

[15]  Xiao‐Qing Yang,et al.  Structural changes and thermal stability of charged LiNi1/3Co1/3Mn1/3O2 cathode material for Li-ion batteries studied by time-resolved XRD , 2009 .

[16]  E. Zhecheva,et al.  Cationic distribution and electrochemical performance of LiCo1/3Ni1/3Mn1/3O2 electrodes for lithium-ion batteries , 2008 .

[17]  Jie Xiao,et al.  Layered Mixed Transition Metal Oxide Cathodes with Reduced Cobalt Content for Lithium Ion Batteries , 2008 .

[18]  Y. Shao-horn,et al.  Thermal Instability of Cycled Li x Ni 0.5 Mn 0.5 O 2 Electrodes: An in Situ Synchrotron X-ray Powder Diffraction Study , 2008 .

[19]  M. Armand,et al.  Building better batteries , 2008, Nature.

[20]  Junwei Jiang,et al.  The reactivity of delithiated Li(Ni1/3Co1/3Mn1/3)O2, Li(Ni0.8Co0.15Al0.05)O2 or LiCoO2 with non-aqueous electrolyte , 2007 .

[21]  Gerbrand Ceder,et al.  A First-Principles Approach to Studying the Thermal Stability of Oxide Cathode Materials , 2007 .

[22]  Xiao‐Qing Yang,et al.  A comparative study on structural changes of LiCo1/3Ni1/3Mn1/3O2 and LiNi0.8Co0.15Al0.05O2 during first charge using in situ XRD , 2006 .

[23]  Xiao‐Qing Yang,et al.  Time Resolved XRD Study on the Thermal Decomposition of Lithium Nickel Oxides for Li-ion Batteries , 2006 .

[24]  Ilias Belharouak,et al.  Safety characteristics of Li(Ni0.8Co0.15Al0.05)O2 and Li(Ni1/3Co1/3Mn1/3)O2 , 2006 .

[25]  Xiao‐Qing Yang,et al.  Time-Resolved XRD Study on the Thermal Decomposition of Li[sub 1−x]Ni[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2] Cathode Materials for Li-Ion Batteries , 2005 .

[26]  G. Ceder,et al.  Role of electronic structure in the susceptibility of metastable transition-metal oxide structures to transformation. , 2004, Chemical reviews.

[27]  Naixin Xu,et al.  Structural and electrochemical characteristics of Co and Al co-doped lithium nickelate cathode materials for lithium-ion batteries , 2004 .

[28]  C. Delmas,et al.  Thermal Stability of Lithium Nickel Oxide Derivatives. Part 2. LixNi0.70Co0.15Al0.15 O2 and LixNi0.90Mn0.10O2 (x = 0.50 and 0.30). Comparison with LixNi1.02O2 and LixNi0.89Al0.16O2 , 2004 .

[29]  C. Delmas,et al.  Thermal Stability of Lithium Nickel Oxide Derivatives. Part II: LixNi0.70Co0.15Al0.15O2 and LixNi0.90Mn0.10O2 (x = 0.50 and 0.30). Comparison with LixNi1.02O2 and LixNi0.89Al0.16O2 , 2003 .

[30]  C. Delmas,et al.  Thermal stability of lithium nickel oxide derivatives. Part I: LixNi1.02O2 and LixNi0.89Al0.16O2 (x = 0.50 and 0.30) , 2003 .

[31]  Gerbrand Ceder,et al.  A Combined Computational/Experimental Study on LiNi1/3Co1/3Mn1/3O2 , 2003 .

[32]  Tsutomu Ohzuku,et al.  Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries , 2003 .

[33]  Kyung-Keun Lee,et al.  Characterization of LiNi0.85Co0.10M0.05O2 (M = Al, Fe) as a cathode material for lithium secondary batteries , 2001 .

[34]  J. Weaving,et al.  Development of high energy density Li-ion batteries based on LiNi1-x-yCoxAlyO2 , 2001 .

[35]  Brian H. Toby,et al.  EXPGUI, a graphical user interface for GSAS , 2001 .

[36]  J. Dahn,et al.  Thermal stability of LixCoO2, LixNiO2 and λ-MnO2 and consequences for the safety of Li-ion cells , 1994 .

[37]  Xiqian Yu,et al.  Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode , 2013 .

[38]  G. Ceder,et al.  A Combined Computational / Experimental Study on LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 , 2022 .