Dopant Distribution in Co-Free High-Energy Layered Cathode Materials

Journal Article · Thu Nov 21 00:00:00 EST 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b03603· OSTI ID:1591635

Mu, Linqin ^[1]; Zhang, Rui ^[2]; Kan, Wang Hay ^[3]; Zhang, Yan ^[4]; Li, Luxi ^[5]; Kuai, Chunguang ^[1]; Zydlewski, Benjamin ^[1]; Rahman, Muhammad Mominur ^[1]; Sun, Cheng-Jun ^[5]; Sainio, Sami ^[4]; Avdeev, Maxim ^[6]; Nordlund, Dennis ^[4]; Xin, Huolin L. ^[2]; Lin, Feng ^[1]

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1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
2. Univ. of California, Irvine, CA (United States)
3. Spallation Neutron Source Science Center, Dongguan (China); Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW (Australia)
4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
5. Argonne National Lab. (ANL), Argonne, IL (United States)
6. Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW (Australia); Univ. of Sydney, NSW (Australia)

The practical implementation of Co-free, LiNiO₂-derived cathodes has been prohibited by their poor cycle life and thermal stability, concluded from the structural instability, phase transformations, reactive surfaces, and chemomechanical breakdown. With the hierarchical distribution of Mg/Ti dual dopants in LiNiO₂, we report a Co-free layered oxide that exhibits enhanced bulk and surface stability. Ti shows a gradient distribution and is enriched at the surface, whereas Mg distributes homogeneously throughout the primary particles. The resulting Mg/Ti codoped LiNiO₂ delivers a material-level specific energy of ~780 W h/kg at C/10 with 96% retention after 50 cycles. The specific energy reaches ~680 W h/kg at 1C with 77% retention after 300 cycles. Furthermore, the Mg/Ti dual dopants improve the rate capability, thermal stability, and self-discharge resistance of LiNiO₂. Our synchrotron X-ray, electron, and electrochemical diagnostics reveal that the Mg/Ti dual dopants mitigate phase transformations, reduce nickel dissolution, and stabilize the cathode–electrolyte interface, thus leading to the favorable battery performance in lithium metal and graphite cells. The current study suggests that engineering the dopant distribution in cathodes may provide an effective path toward lower cost, safer, and higher energy density Co-free lithium batteries.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
• Sponsoring Organization: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC)
• Grant/Contract Number: AC02-06CH11357; AC02-76SF00515; EE0008444
• OSTI ID: 1591635
• Alternate ID(s): OSTI ID: 1618858
• Journal Information: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 23 Vol. 31; ISSN 0897-4756
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE