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

Abstract

The practical implementation of Co-free, LiNiO2-derived cathodes has been prohibited by their poor cycle life and thermal stability, resulting 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 similar to 780 W h/kg at C/10 with 96% retention after 50 cycles. The specific energy reaches similar to 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 present 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.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5];  [1];  [1]; ORCiD logo [1];  [5]; ORCiD logo [4]; ORCiD logo [6];  [4];  [2]; ORCiD logo [1]
  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)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC)
OSTI Identifier:
1591635
Alternate Identifier(s):
OSTI ID: 1618858
Grant/Contract Number:  
AC02-76SF00515; EE0008444; 21704105; 11805034; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 23; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Mu, Linqin, Zhang, Rui, Kan, Wang Hay, Zhang, Yan, Li, Luxi, Kuai, Chunguang, Zydlewski, Benjamin, Rahman, Muhammad Mominur, Sun, Cheng-Jun, Sainio, Sami, Avdeev, Maxim, Nordlund, Dennis, Xin, Huolin L., and Lin, Feng. Dopant Distribution in Co-Free High-Energy Layered Cathode Materials. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.9b03603.
Mu, Linqin, Zhang, Rui, Kan, Wang Hay, Zhang, Yan, Li, Luxi, Kuai, Chunguang, Zydlewski, Benjamin, Rahman, Muhammad Mominur, Sun, Cheng-Jun, Sainio, Sami, Avdeev, Maxim, Nordlund, Dennis, Xin, Huolin L., & Lin, Feng. Dopant Distribution in Co-Free High-Energy Layered Cathode Materials. United States. doi:10.1021/acs.chemmater.9b03603.
Mu, Linqin, Zhang, Rui, Kan, Wang Hay, Zhang, Yan, Li, Luxi, Kuai, Chunguang, Zydlewski, Benjamin, Rahman, Muhammad Mominur, Sun, Cheng-Jun, Sainio, Sami, Avdeev, Maxim, Nordlund, Dennis, Xin, Huolin L., and Lin, Feng. Thu . "Dopant Distribution in Co-Free High-Energy Layered Cathode Materials". United States. doi:10.1021/acs.chemmater.9b03603. https://www.osti.gov/servlets/purl/1591635.
@article{osti_1591635,
title = {Dopant Distribution in Co-Free High-Energy Layered Cathode Materials},
author = {Mu, Linqin and Zhang, Rui and Kan, Wang Hay and Zhang, Yan and Li, Luxi and Kuai, Chunguang and Zydlewski, Benjamin and Rahman, Muhammad Mominur and Sun, Cheng-Jun and Sainio, Sami and Avdeev, Maxim and Nordlund, Dennis and Xin, Huolin L. and Lin, Feng},
abstractNote = {The practical implementation of Co-free, LiNiO2-derived cathodes has been prohibited by their poor cycle life and thermal stability, resulting 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 similar to 780 W h/kg at C/10 with 96% retention after 50 cycles. The specific energy reaches similar to 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 present 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.},
doi = {10.1021/acs.chemmater.9b03603},
journal = {Chemistry of Materials},
number = 23,
volume = 31,
place = {United States},
year = {2019},
month = {11}
}

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