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Title: Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries

Here, the thermal stability of electrochemically delithiated Li 0.1Ni 0.8Co 0.15Al 0.05O 2 (NCA), FePO 4 (FP), Mn 0.8Fe 0.2PO 4 (MFP), hydrothermally synthesized VOPO 4, LiVOPO 4, and electrochemically lithiated Li 2VOPO 4 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 < VOPO 4 < MFP < FP. Unlike the layered oxides and MFP, VOPO 4 does not evolve O 2 on heating. Thus, VOPO 4 is less likely to cause a thermal run-away phenomenon in batteries at elevated temperature and so is inherently safer. The lithiated materials LiVOPO 4, Li 2VOPO 4, and LiNi 0.8Co 0.15Al 0.05O 2 are found to be stable in the presence of electrolyte, but sealed-capsule high-pressure experiments show a phase transformation of VOPO 4 → HVOPO 4 → H 2VOPO 4 when VOPO 4 reacts with electrolyte (1 M LiPF 6 in EC/DMC = 1:1) between 200 and 300 °C. Using first-principles calculations, we confirm that the charged VOPO 4 cathode is indeed predicted to be marginally less stable than FP but significantly more stable than NCA in the absencemore » of electrolyte. An analysis of the reaction equilibria between VOPO 4 and EC using a multicomponent phase diagram approach yields products and reaction enthalpies that are highly consistent with the experiment results.« less
Authors:
 [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1]
  1. Binghamton Univ., Binghamton, NY (United States)
  2. Univ. of California, San Diego, La Jolla, CA (United States)
Publication Date:
Grant/Contract Number:
SC0012583; AC02-98CH10886
Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of California, San Diego, La Jolla, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; cathode; electrolyte; Li-ion battery; oxides; phosphates; thermal stability
OSTI Identifier:
1241419
Alternate Identifier(s):
OSTI ID: 1436505

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., 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. 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, and Whittingham, M. Stanley. 2016. "Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries". United States. doi: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 = {2016},
month = {2}
}