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Title: Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides

Abstract

Transition metal layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-Ni ones (LiNi xMn yCo zO 2; x ≥ 0.7) with greatly boosted capacity and reduced cost are of particular interest for large-scale applications. The high Ni loading, on the other hand, raises the concern of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi 0.7Mn 0.15Co 0.15O 2 with greatly enhanced rate capability is reflected, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface analysis, is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li 2CO 3 accumulation, formation of a Li-deficient layer and Ni reduction at the particle surface. The reconstruction process happens predominantly at high temperatures (above 350 °C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [3];  [5];  [6];  [6];  [6];  [7];  [8];  [9];  [2];  [6];  [6]; ORCiD logo [3];  [10]
  1. Peking Univ., Beijing (China); Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  3. Peking Univ., Beijing (China)
  4. Peking Univ., Beijing (China); Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.; Hebei Univ. of Technology, Tianjing (China)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Chinese Academy of Sciences (CAS), Ningbo (China). Ningbo Inst. of Materials Technology and Engineering
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
  7. Cornell Univ., Ithaca, NY (United States). Cornell High Energy Synchrotron Source
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Stanford Univ., CA (United States). Materials Science and Engineering; Imam Abdulrahman Bin Faisal Univ. (IAU), Dammam (Saudi Arabia)
  9. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  10. Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1574924
Alternate Identifier(s):
OSTI ID: 1570394
Report Number(s):
BNL-212356-2019-JAAM
Journal ID: ISSN 1614-6832
Grant/Contract Number:  
SC0012704; AC02‐06CH11357; DE‐SC0012704; DE‐AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 9; Journal Issue: 43; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; high‐Ni layered oxide cathodes; lithium‐ion batteries; quenching; solid‐state synthesis; surface reconstruction

Citation Formats

Zhang, Ming‐Jian, Hu, Xiaobing, Li, Maofan, Duan, Yandong, Yang, Luyi, Yin, Chong, Ge, Mingyuan, Xiao, Xianghui, Lee, Wah‐Keat, Ko, Jun Young Peter, Amine, Khalil, Chen, Zonghai, Zhu, Yimei, Dooryhee, Eric, Bai, Jianming, Pan, Feng, and Wang, Feng. Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides. United States: N. p., 2019. Web. doi:10.1002/aenm.201901915.
Zhang, Ming‐Jian, Hu, Xiaobing, Li, Maofan, Duan, Yandong, Yang, Luyi, Yin, Chong, Ge, Mingyuan, Xiao, Xianghui, Lee, Wah‐Keat, Ko, Jun Young Peter, Amine, Khalil, Chen, Zonghai, Zhu, Yimei, Dooryhee, Eric, Bai, Jianming, Pan, Feng, & Wang, Feng. Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides. United States. doi:10.1002/aenm.201901915.
Zhang, Ming‐Jian, Hu, Xiaobing, Li, Maofan, Duan, Yandong, Yang, Luyi, Yin, Chong, Ge, Mingyuan, Xiao, Xianghui, Lee, Wah‐Keat, Ko, Jun Young Peter, Amine, Khalil, Chen, Zonghai, Zhu, Yimei, Dooryhee, Eric, Bai, Jianming, Pan, Feng, and Wang, Feng. Mon . "Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides". United States. doi:10.1002/aenm.201901915.
@article{osti_1574924,
title = {Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides},
author = {Zhang, Ming‐Jian and Hu, Xiaobing and Li, Maofan and Duan, Yandong and Yang, Luyi and Yin, Chong and Ge, Mingyuan and Xiao, Xianghui and Lee, Wah‐Keat and Ko, Jun Young Peter and Amine, Khalil and Chen, Zonghai and Zhu, Yimei and Dooryhee, Eric and Bai, Jianming and Pan, Feng and Wang, Feng},
abstractNote = {Transition metal layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-Ni ones (LiNixMnyCozO2; x ≥ 0.7) with greatly boosted capacity and reduced cost are of particular interest for large-scale applications. The high Ni loading, on the other hand, raises the concern of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi0.7Mn0.15Co0.15O2 with greatly enhanced rate capability is reflected, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface analysis, is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li2CO3 accumulation, formation of a Li-deficient layer and Ni reduction at the particle surface. The reconstruction process happens predominantly at high temperatures (above 350 °C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials.},
doi = {10.1002/aenm.201901915},
journal = {Advanced Energy Materials},
number = 43,
volume = 9,
place = {United States},
year = {2019},
month = {10}
}

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