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

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

doi:10.1021/acsami.5b12081

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

Journal Article · Fri Mar 11 00:00:00 EST 2016 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5b12081· OSTI ID:1241419

Huang, Yiqing ^[1]; Lin, Yuh-Chieh ^[1]; Jenkins, David M. ^[1]; Chernova, Natasha A. ^[1]; Chung, Youngmin ^[1]; Radhakrishnan, Balachandran ^[1]; Chu, Iek-Heng ^[1]; Fang, Jin ^[1]; Wang, Qi ^[1]; Omenya, Fredrick ^[1]; Ong, Shyue Ping ^[1]; Whittingham, M. Stanley ^[1]

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

Here, the thermal stability of electrochemically delithiated Li_0.1Ni_0.8Co_0.15Al_0.05O₂ (NCA), FePO₄ (FP), Mn_0.8Fe_0.2PO₄ (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 LiNi_0.8Co_0.15Al_0.05O₂ 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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-98CH10886; SC0012583; SC0001294

OSTI ID:: 1241419

Alternate ID(s):: OSTI ID: 1436505

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Vol. 8 Journal Issue: 11; ISSN 1944-8244

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 88 works

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

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