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Title: Resolving the degradation pathways in high-voltage oxides for high-energy-density lithium-ion batteries; Alternation in chemistry, composition and crystal structures

Our development of stable high-voltage (HV), high capacity (HC) cathode oxides is indispensable to enhancing the performance of current high-energy-density (HED) lithium-ion batteries. Overstoichiometric, layered Li- and Mn-rich (LMR) composite oxides are promising materials for HV-HC cathodes for HED batteries; however, their practical use is limited. By probing the crystal structure, magnetic structure, and microstructure of the Li 1.2Mn 0.55Ni 0.15Co 0.1O 2 LMR oxide, we demonstrate that the oxide loses its pristine chemistry, structure, and composition during the first charge-discharge cycle and that it proceeds through a series of progressive events that introduce impediments on the ion mobility pathways. Here, we discovered i) the presence of tetrahedral Mn 3+, interlayer cation intermixing, interface of layered-spinel, and structurally rearranged domains, cation segregation at an HV charged state, and ii) the loss of Li ions, inhomogeneous distribution of Li/Ni, and structurally transformed domains after the first discharge. Our results will advance our fundamental understanding of the obstacles related to ion migration pathways in HV-HC cathode systems and will enable us to formulate design rules for use of such materials in high-energy-density electrochemical-energy-storage devices.
ORCiD logo [1] ;  [2] ;  [3] ; ORCiD logo [4] ; ORCiD logo [5] ; ORCiD logo [1] ; ORCiD logo [5] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Energy and Transportation Science Division
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
Publication Date:
Report Number(s):
Journal ID: ISSN 2211-2855; VT1201000; CEVT110
Grant/Contract Number:
AC05-00OR22725; AC05-76RL01830; UP # 48930
Published Article
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 36; Journal Issue: C; Journal ID: ISSN 2211-2855
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS) and Spallation Neutron Source; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; lithium-ion batteries; nano domains; cathode; TEM; atom probe tomography; atom probe tomography (APT); TRANSITION-METAL OXIDES; RICH CATHODE MATERIALS; X-RAY-DIFFRACTION; MN; CHALLENGES; CAPACITY; STORAGE; FADE; PERSPECTIVE; ELECTRODES; Environmental Molecular Sciences Laboratory
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1362204; OSTI ID: 1364398; OSTI ID: 1368120; OSTI ID: 1394413