Targeted Surface Doping with Reversible Local Environment Improves Oxygen Stability at the Electrochemical Interfaces of Nickel-Rich Cathode Materials

James D. Steiner, Hao Cheng, Julia Walsh, Yan Zhang, Benjamin Zydlewski, Linqin Mu, Zhengrui Xu, Muhammad Mominur Rahman, Huabin Sun, F. Marc Michel, Cheng Jun Sun, Dennis Nordlund, Wei Luo, Jin Cheng Zheng, Huolin L. Xin, Feng Lin

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

Elemental doping represents a prominent strategy to improve interfacial chemistry in battery materials. Manipulating the dopant spatial distribution and understanding the dynamic evolution of the dopants at the atomic scale can inform better design of the doping chemistry for batteries. In this work, we create a targeted hierarchical distribution of Ti4+, a popular doping element for oxide cathode materials, in LiNi0.8Mn0.1Co0.1O2 primary particles. We apply multiscale synchrotron/electron spectroscopy and imaging techniques as well as theoretical calculations to investigate the dynamic evolution of the doping chemical environment. The Ti4+ dopant is fully incorporated into the TMO6 octahedral coordination and is targeted to be enriched at the surface. Ti4+ in the TMO6 octahedral coordination increases the TM-O bond length and reduces the covalency between (Ni, Mn, Co) and O. The excellent reversibility of Ti4+ chemical environment gives rise to superior oxygen reversibility at the cathode-electrolyte interphase and in the bulk particles, leading to improved stability in capacity, energy, and voltage. Our work directly probes the chemical environment of doping elements and helps rationalize the doping strategy for high-voltage layered cathodes.

Original languageEnglish
Pages (from-to)37885-37891
Number of pages7
JournalACS Applied Materials and Interfaces
Volume11
Issue number41
DOIs
StatePublished - Oct 16 2019
Externally publishedYes

Funding

This material is based upon work supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Award Number: DE-EE0008444. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. This research used resources of the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences under Contract No. DE-SC0012704. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. H.C. and J.-C.Z. acknowledge Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) under Grant No. U1501501. This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. This material is based upon work supported by the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (EERE) under the Award Number: DE-EE0008444. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. This research used resources of the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences under Contract No. DE-SC0012704. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. H.C. and J.-C.Z. acknowledge Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) under Grant No. U1501501. This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

Keywords

  • battery
  • cathode
  • oxygen activity
  • surface chemistry
  • surface doping

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