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Title: Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li7La3Zr2O12 Electrolyte and LiCoO2 Cathode

Abstract

All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model systems of LiCoO2 (LCO) thin films deposited on cubic Al-doped Li7La3Zr2O12 (LLZO) pellets were studied as a function of temperature using interface-sensitive techniques. X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, and energy-dispersive X-ray spectroscopy data indicated significant cation interdiffusion and structural changes starting at temperatures as low as 300 °C. La2Zr2O7 and Li2CO3 were identified as decomposition products after annealing at 500 °C by synchrotron X-ray diffraction. X-ray absorption spectroscopy results indicate the presence of also LaCoO3 in addition to La2Zr2O7 and Li2CO3. On the basis of electrochemical impedance spectroscopy and depth profiling of the Li distribution upon potentiostatic hold experiments on symmetric LCO|LLZO|LCO cells, the interfaces exhibited significantly increased impedance, up to 8 times that of the as-deposited samples after annealing at 500more » °C. Here, our results indicate that lower-temperature processing conditions, shorter annealing time scales, and CO2-free environments are desirable for obtaining ceramic cathode|electrolyte interfaces that enable fast Li transfer and high capacity.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [3]; ORCiD logo [3];  [4];  [4]; ORCiD logo [5]; ORCiD logo [5];  [6];  [7]; ORCiD logo [8];  [9]; ORCiD logo [2]; ORCiD logo [2]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Bogazici Univ., Istanbul (Turkey)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Imperial College of Science, London (United Kingdom)
  4. Illinois Institute of Technology, Chicago, IL (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Argonne National Lab. (ANL), Lemont, IL (United States)
  7. Univ. of Maryland, College Park, MD (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  9. Bosch Research and Technology Center, Sunnyvale, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1477177
Alternate Identifier(s):
OSTI ID: 1483239
Report Number(s):
BNL-209466-2018-JAAM
Journal ID: ISSN 0897-4756; 147393
Grant/Contract Number:  
AC02-06CH11357; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 18; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Vardar, Gulin, Bowman, William J., Lu, Qiyang, Wang, Jiayue, Chater, Richard J., Aguadero, Ainara, Seibert, Rachel, Terry, Jeff, Hunt, Adrian, Waluyo, Iradwikanari, Fong, Dillon D., Jarry, Angelique, Crumlin, Ethan J., Hellstrom, Sondra L., Chiang, Yet -Ming, and Yildiz, Bilge. Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li7La3Zr2O12 Electrolyte and LiCoO2 Cathode. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b01713.
Vardar, Gulin, Bowman, William J., Lu, Qiyang, Wang, Jiayue, Chater, Richard J., Aguadero, Ainara, Seibert, Rachel, Terry, Jeff, Hunt, Adrian, Waluyo, Iradwikanari, Fong, Dillon D., Jarry, Angelique, Crumlin, Ethan J., Hellstrom, Sondra L., Chiang, Yet -Ming, & Yildiz, Bilge. Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li7La3Zr2O12 Electrolyte and LiCoO2 Cathode. United States. doi:10.1021/acs.chemmater.8b01713.
Vardar, Gulin, Bowman, William J., Lu, Qiyang, Wang, Jiayue, Chater, Richard J., Aguadero, Ainara, Seibert, Rachel, Terry, Jeff, Hunt, Adrian, Waluyo, Iradwikanari, Fong, Dillon D., Jarry, Angelique, Crumlin, Ethan J., Hellstrom, Sondra L., Chiang, Yet -Ming, and Yildiz, Bilge. Wed . "Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li7La3Zr2O12 Electrolyte and LiCoO2 Cathode". United States. doi:10.1021/acs.chemmater.8b01713. https://www.osti.gov/servlets/purl/1477177.
@article{osti_1477177,
title = {Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li7La3Zr2O12 Electrolyte and LiCoO2 Cathode},
author = {Vardar, Gulin and Bowman, William J. and Lu, Qiyang and Wang, Jiayue and Chater, Richard J. and Aguadero, Ainara and Seibert, Rachel and Terry, Jeff and Hunt, Adrian and Waluyo, Iradwikanari and Fong, Dillon D. and Jarry, Angelique and Crumlin, Ethan J. and Hellstrom, Sondra L. and Chiang, Yet -Ming and Yildiz, Bilge},
abstractNote = {All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model systems of LiCoO2 (LCO) thin films deposited on cubic Al-doped Li7La3Zr2O12 (LLZO) pellets were studied as a function of temperature using interface-sensitive techniques. X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, and energy-dispersive X-ray spectroscopy data indicated significant cation interdiffusion and structural changes starting at temperatures as low as 300 °C. La2Zr2O7 and Li2CO3 were identified as decomposition products after annealing at 500 °C by synchrotron X-ray diffraction. X-ray absorption spectroscopy results indicate the presence of also LaCoO3 in addition to La2Zr2O7 and Li2CO3. On the basis of electrochemical impedance spectroscopy and depth profiling of the Li distribution upon potentiostatic hold experiments on symmetric LCO|LLZO|LCO cells, the interfaces exhibited significantly increased impedance, up to 8 times that of the as-deposited samples after annealing at 500 °C. Here, our results indicate that lower-temperature processing conditions, shorter annealing time scales, and CO2-free environments are desirable for obtaining ceramic cathode|electrolyte interfaces that enable fast Li transfer and high capacity.},
doi = {10.1021/acs.chemmater.8b01713},
journal = {Chemistry of Materials},
number = 18,
volume = 30,
place = {United States},
year = {2018},
month = {7}
}

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Figures / Tables:

Figure 1 Figure 1: Transmission electron microscopy (TEM) and scanning TEM (STEM) analysis of interface morphology and elemental distribution for LCO|LLZO samples, with 460 nm LCO deposited onto LLZO, in the as-deposited state (a,c,e,g) and after annealing at 500 °C (b,d,f,h). (a,b) Low-resolution TEM bright field images, with inset diffraction patterns acquiredmore » in LCO phase. (c,d) High-resolution TEM bright field images showing interface morphology. (e,f) STEM annular dark field images with energy-dispersive X-ray spectroscopy (EDX) line scan paths highlighted with horizontal lines. (g,h) Representative STEM EDX elemental profiles; signal intensities are normalized to the total X-ray signal intensity (see Equation (1) in the Methods section).« less

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