Structural transformations in high-capacity Li2Cu0.5Ni0.5O2 cathodes
Abstract
Cathode materials that can cycle >1 Li+ per transition metal are of substantial interest for increasing the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~500 mAh/g assuming both Li+ ions are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen evolves before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, X-ray diffraction, transmission electron microscopy (TEM), and transmission X-ray microscopy combined with X-ray absorption near edge structure (TXM–XANES) are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the changes that the Li2NiO2 endmember undergoes. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence of particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM–XANES are used to map the different phases that emerge during cyclingmore »
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1350931
- Alternate Identifier(s):
- OSTI ID: 1361140
- Grant/Contract Number:
- AC05-00OR22725; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 29; Journal Issue: 7; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ruther, Rose E., Pandian, Amaresh Samuthira, Yan, Pengfei, Weker, Johanna Nelson, Wang, Chongmin, and Nanda, Jagjit. Structural transformations in high-capacity Li2Cu0.5Ni0.5O2 cathodes. United States: N. p., 2017.
Web. doi:10.1021/acs.chemmater.6b05442.
Ruther, Rose E., Pandian, Amaresh Samuthira, Yan, Pengfei, Weker, Johanna Nelson, Wang, Chongmin, & Nanda, Jagjit. Structural transformations in high-capacity Li2Cu0.5Ni0.5O2 cathodes. United States. https://doi.org/10.1021/acs.chemmater.6b05442
Ruther, Rose E., Pandian, Amaresh Samuthira, Yan, Pengfei, Weker, Johanna Nelson, Wang, Chongmin, and Nanda, Jagjit. Thu .
"Structural transformations in high-capacity Li2Cu0.5Ni0.5O2 cathodes". United States. https://doi.org/10.1021/acs.chemmater.6b05442. https://www.osti.gov/servlets/purl/1350931.
@article{osti_1350931,
title = {Structural transformations in high-capacity Li2Cu0.5Ni0.5O2 cathodes},
author = {Ruther, Rose E. and Pandian, Amaresh Samuthira and Yan, Pengfei and Weker, Johanna Nelson and Wang, Chongmin and Nanda, Jagjit},
abstractNote = {Cathode materials that can cycle >1 Li+ per transition metal are of substantial interest for increasing the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~500 mAh/g assuming both Li+ ions are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen evolves before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, X-ray diffraction, transmission electron microscopy (TEM), and transmission X-ray microscopy combined with X-ray absorption near edge structure (TXM–XANES) are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the changes that the Li2NiO2 endmember undergoes. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence of particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM–XANES are used to map the different phases that emerge during cycling ex situ and in situ. Lastly, significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.},
doi = {10.1021/acs.chemmater.6b05442},
journal = {Chemistry of Materials},
number = 7,
volume = 29,
place = {United States},
year = {Thu Mar 09 00:00:00 EST 2017},
month = {Thu Mar 09 00:00:00 EST 2017}
}
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