Thermally Driven Interfacial Degradation between Li7La3Zr2O12 Electrolyte and LiNi0.6Mn0.2Co0.2O2 Cathode

Kim, Younggyu; Kim, Dongha; Bliem, Roland; Vardar, Gülin; Waluyo, Iradwikanari; Hunt, Adrian; Wright, Joshua T.; Katsoudas, John P.; Yildiz, Bilge

doi:10.1021/acs.chemmater.0c02261

Thermally Driven Interfacial Degradation between Li₇La₃Zr₂O₁₂ Electrolyte and LiNi_0.6Mn_0.2Co_0.2O₂ Cathode

Journal Article · Thu Nov 05 00:00:00 EST 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c02261· OSTI ID:1763324

^[1]; ^[1]; ^[1]; ^[1]; ^[2]; Hunt, Adrian ^[2]; Wright, Joshua T. ^[3]; Katsoudas, John P. ^[3]; ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)

Solid-state batteries offer higher energy density and enhanced safety compared to the present lithium-ion batteries using liquid electrolytes. A challenge to implement them is the high resistances, especially at the solid electrolyte interface with the cathode. Sintering at elevated temperature is needed in order to get good contact between the ceramic solid electrolyte and oxide cathodes and thus to reduce contact resistances. Many solid electrolyte and cathode materials react to form secondary phases. It is necessary to find out which phases arise as a result of interface sintering and evaluate their effect on electrochemical properties. Herein, we assessed the interfacial reactions between LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) and Li₇La₃Zr₂O₁₂ (LLZO) as a function of temperature in air. We prepared model systems by depositing thin-film NMC622 cathode layers on LLZO pellets. The thin-film cathode approach enabled us to use interface-sensitive techniques such as X-ray absorption spectroscopy in the near-edge as well as the extended regimes and identify the onset of detrimental reactions. We found that the Ni and Co chemical environments change already at moderate temperatures, on-setting from 500 °C and becoming especially prominent at 700 °C. By analyzing spectroscopy results along with X-ray diffraction, we identified Li₂CO₃, La₂Zr₂O₇, and La(Ni,Co)O₃ as the secondary phases that formed at 700 °C. The interfacial resistance for Li transfer, measured by electrochemical impedance spectroscopy, increases significantly upon the onset and evolution of the detected interface chemistry. Our findings suggest that limiting the bonding temperature and avoiding CO₂ in the sintering environment can help to remedy the interfacial degradation.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: National Science Foundation (NSF); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1763324

Report Number(s):: BNL--220912-2021-JAAM

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 22 Vol. 32; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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