title: Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells.
abstract: Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi2MnO3·(1-x)LiMO2(M = Ni, Mn, or Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to that of manganese and nickel ions in close-packed oxides and (2) their higher potential (∼3.6 V vs Li0) relative to manganese oxide spinels (∼2.9 V vs Li0) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we revisited the structural and electrochemical properties of lithiated spinels in the LiCo1-xNixO2(0 ≤ x ≤ 0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo1-xNixO2structures when prepared in air between 400 and 800 °C and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentrations, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Eungje
authors.initials: E
authors.lastname: Lee
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Joel
authors.initials: J
authors.lastname: Blauwkamp
authors.forename: Fernando C
authors.initials: FC
authors.lastname: Castro
authors.forename: Jinsong
authors.initials: J
authors.lastname: Wu
authors.forename: Vinayak P
authors.initials: VP
authors.lastname: Dravid
authors.affiliation: Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory , Richland, Washington 99352, United States.
authors.forename: Pengfei
authors.initials: P
authors.lastname: Yan
authors.affiliation: Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory , Richland, Washington 99352, United States.
authors.forename: Chongmin
authors.initials: C
authors.lastname: Wang
authors.forename: Soo
authors.initials: S
authors.lastname: Kim
authors.forename: Christopher
authors.initials: C
authors.lastname: Wolverton
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Roy
authors.initials: R
authors.lastname: Benedek
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Fulya
authors.initials: F
authors.lastname: Dogan
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Joong Sun
authors.initials: JS
authors.lastname: Park
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Jason R
authors.initials: JR
authors.lastname: Croy
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Michael M
authors.initials: MM
authors.lastname: Thackeray
keywords: lithium-cobalt-nickel oxide; lithium-ion battery; spinel; stabilizer; structure