Title
Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries
Document Type
Article
Publication Date
2016
Keywords
Li-ion battery, cathode, electrolyte, thermal stability, oxides, phosphates
Abstract
The thermal stability of electrochemically delithiated Li0.1Ni0.8Co0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4, and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability of the delithiated materials is found to be in the order of NCA < VOPO4 < MFP < FP. Unlike the layered oxides and MFP, VOPO4 does not evolve O2 on heating. Thus, VOPO4 is less likely to cause a thermal run-away phenomenon in batteries at elevated temperature and so is inherently safer. The lithiated materials LiVOPO4, Li2VOPO4, and LiNi0.8Co0.15Al0.05O2 are found to be stable in the presence of electrolyte, but sealed-capsule high-pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC/DMC = 1:1) between 200 and 300 °C. Using first-principles calculations, we confirm that the charged VOPO4 cathode is indeed predicted to be marginally less stable than FP but significantly more stable than NCA in the absence of electrolyte. An analysis of the reaction equilibria between VOPO4 and EC using a multicomponent phase diagram approach yields products and reaction enthalpies that are highly consistent with the experiment results.
Publisher Attribution
The final publication is available from ACS Publications via doi: 10.1021/acsami.5b12081
Recommended Citation
Huang, Y., Lin, Y. C., Jenkins, D. M., Chernova, N. A., Chung, Y., Radhakrishnan, B., ... & Ong, S. P. (2016). Thermal stability and reactivity of cathode materials for Li-ion batteries. ACS applied materials & interfaces, 8(11), 7013-7021. doi: 10.1021/acsami.5b12081
Comments
ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.