Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries
Abstract
Here, 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.
- Authors:
-
- Chemistry and Materials and ‡Department of Geology, Binghamton University, Binghamton, New York 13902-6000, United States, Materials Science and Engineering Program and ∥Department of NanoEngineering, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093, United States
- Publication Date:
- Research Org.:
- Univ. of California, San Diego, La Jolla, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1241419
- Alternate Identifier(s):
- OSTI ID: 1436505
- Grant/Contract Number:
- AC02-98CH10886; SC0012583; SC0001294
- Resource Type:
- Published Article
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Name: ACS Applied Materials and Interfaces Journal Volume: 8 Journal Issue: 11; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cathode; electrolyte; Li-ion battery; oxides; phosphates; thermal stability
Citation Formats
Huang, Yiqing, Lin, Yuh-Chieh, Jenkins, David M., Chernova, Natasha A., Chung, Youngmin, Radhakrishnan, Balachandran, Chu, Iek-Heng, Fang, Jin, Wang, Qi, Omenya, Fredrick, Ong, Shyue Ping, and Whittingham, M. Stanley. Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries. United States: N. p., 2016.
Web. doi:10.1021/acsami.5b12081.
Huang, Yiqing, Lin, Yuh-Chieh, Jenkins, David M., Chernova, Natasha A., Chung, Youngmin, Radhakrishnan, Balachandran, Chu, Iek-Heng, Fang, Jin, Wang, Qi, Omenya, Fredrick, Ong, Shyue Ping, & Whittingham, M. Stanley. Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries. United States. https://doi.org/10.1021/acsami.5b12081
Huang, Yiqing, Lin, Yuh-Chieh, Jenkins, David M., Chernova, Natasha A., Chung, Youngmin, Radhakrishnan, Balachandran, Chu, Iek-Heng, Fang, Jin, Wang, Qi, Omenya, Fredrick, Ong, Shyue Ping, and Whittingham, M. Stanley. Fri .
"Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries". United States. https://doi.org/10.1021/acsami.5b12081.
@article{osti_1241419,
title = {Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries},
author = {Huang, Yiqing and Lin, Yuh-Chieh and Jenkins, David M. and Chernova, Natasha A. and Chung, Youngmin and Radhakrishnan, Balachandran and Chu, Iek-Heng and Fang, Jin and Wang, Qi and Omenya, Fredrick and Ong, Shyue Ping and Whittingham, M. Stanley},
abstractNote = {Here, 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.},
doi = {10.1021/acsami.5b12081},
journal = {ACS Applied Materials and Interfaces},
number = 11,
volume = 8,
place = {United States},
year = {Fri Mar 11 00:00:00 EST 2016},
month = {Fri Mar 11 00:00:00 EST 2016}
}
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