Structural transformations in high-capacity Li2Cu0.5Ni0.5O2 cathodes

Ruther, Rose E.; Pandian, Amaresh Samuthira; Yan, Pengfei; Weker, Johanna Nelson; Wang, Chongmin; Nanda, Jagjit

doi:10.1021/acs.chemmater.6b05442

Title: Structural transformations in high-capacity Li₂Cu_0.5Ni_0.5O₂ cathodes

Journal Article · Thu Mar 09 00:00:00 EST 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b05442· OSTI ID:1350931

Ruther, Rose E. ^[1]; Pandian, Amaresh Samuthira ^[1]; Yan, Pengfei ^[2]; Weker, Johanna Nelson ^[3]; Wang, Chongmin ^[2]; Nanda, Jagjit ^[1]

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)

Cathode materials that can cycle >1 Li⁺ per transition metal are of substantial interest for increasing the overall energy density of lithium-ion batteries. Li₂Cu_0.5Ni_0.5O₂ has a very high theoretical capacity of ~500 mAh/g assuming both Li+ ions are cycled reversibly. The Cu^2+/3+ and Ni^2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li₂Cu_0.5Ni_0.5O₂ 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 Cu^2+/3+ or Ni^3+/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 Li₂Cu_0.5Ni_0.5O₂ during electrochemical cycling. Li₂Cu_0.5Ni_0.5O₂ is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the changes that the Li₂NiO₂ endmember undergoes. Li₂Cu_0.5Ni_0.5O₂ 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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC05-00OR22725; AC02-76SF00515

OSTI ID:: 1350931

Alternate ID(s):: OSTI ID: 1361140

Journal Information:: Chemistry of Materials, Vol. 29, Issue 7; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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