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Probing Depth-Dependent Transition-Metal Redox of Lithium Nickel, Manganese, and Cobalt Oxides in Li-Ion Batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [1];  [1];  [2];  [1];  [3];  [4];  [4];  [5];  [2]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Research Lab. of Electronics
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. BMW Group, München (Germany)
  5. BMW Group Technology Office, Mountain View, CA (United States)
+ Show Author Affiliations
Layered lithium nickel, manganese, and cobalt oxides (NMC) are among the most promising commercial positive electrodes in the past decades. Understanding the detailed surface and bulk redox processes of Ni-rich NMC can provide useful insights into material design options to boost reversible capacity and cycle life. Both hard X-ray absorption (XAS) of metal K-edges and soft XAS of metal L-edges collected from charged LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8Mn0.1Co0.1O2 (NMC811) showed that the charge capacity up to removing ~0.7 Li/f.u. was accompanied with Ni oxidation in bulk and near the surface (up to 100 nm). Of significance to note is that nickel oxidation is primarily responsible for the charge capacity of NMC622 and 811 up to similar lithium removal (~0.7 Li/f.u.) albeit charged to different potentials, beyond which was followed by Ni reduction near the surface (up to 100 nm) due to oxygen release and electrolyte parasitic reactions. Overall, this observation points toward several new strategies to enhance reversible redox capacities of Ni-rich and/or Co-free electrodes for high-energy Li-ion batteries.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515
OSTI ID:
1768263
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 50 Vol. 12; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
Li-ion batteries
NMC
Ni-rich positive electrodes
electrode-electrolyte interfaces
lithium
oxidation
oxygen
redox reactions
transition metals
x-ray absorption spectroscopy