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Title: The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results

Abstract

Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessitymore » of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [1]; ORCiD logo [2];  [4];  [5];  [1]
  1. Virginia Tech
  2. BATTELLE (PACIFIC NW LAB)
  3. Argonne National Laboratory
  4. University of California, Irvine
  5. SLAC National Accelerator Laboratory
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1673611
Report Number(s):
PNNL-SA-153847
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry A
Additional Journal Information:
Journal Volume: 8; Journal Issue: 34
Country of Publication:
United States
Language:
English
Subject:
surface chemistry, Co-free Ni-rich cathodes, Istability, sample handling and preparation

Citation Formats

Mu, Linqin, Yang, Zhenzhong, Tao, Lei, Waters, Crystal K., Xu, Zhengrui, Li, Luxi, Sainio, Sami, Du, Yingge, Xin, Huolin L., Nordlund, Dennis, and Lin, Feng. The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results. United States: N. p., 2020. Web. doi:10.1039/D0TA06375D.
Mu, Linqin, Yang, Zhenzhong, Tao, Lei, Waters, Crystal K., Xu, Zhengrui, Li, Luxi, Sainio, Sami, Du, Yingge, Xin, Huolin L., Nordlund, Dennis, & Lin, Feng. The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results. United States. doi:10.1039/D0TA06375D.
Mu, Linqin, Yang, Zhenzhong, Tao, Lei, Waters, Crystal K., Xu, Zhengrui, Li, Luxi, Sainio, Sami, Du, Yingge, Xin, Huolin L., Nordlund, Dennis, and Lin, Feng. Mon . "The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results". United States. doi:10.1039/D0TA06375D.
@article{osti_1673611,
title = {The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results},
author = {Mu, Linqin and Yang, Zhenzhong and Tao, Lei and Waters, Crystal K. and Xu, Zhengrui and Li, Luxi and Sainio, Sami and Du, Yingge and Xin, Huolin L. and Nordlund, Dennis and Lin, Feng},
abstractNote = {Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessity of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.},
doi = {10.1039/D0TA06375D},
journal = {Journal of Materials Chemistry A},
number = 34,
volume = 8,
place = {United States},
year = {2020},
month = {9}
}

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