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Title: Injection of oxygen vacancies in the bulk lattice of layered cathodes

Abstract

Surfaces, interfaces, and grain boundaries are, classically, known to be sinks at which defects generated within bulk lattice will preferentially migrate to and get annihilated, therefore rejuvenating a crystalline lattice to restore the intended functionalities.1, 2, 3 Here we report an inverse case by which the defects generated at the particle surface are continuously pumped into the bulk lattice and consequentially compromising the intended functionalities. We discovered that during the operation of a rechargeable battery, oxygen vacancies generated at cathode particle surfaces migrate toward inside of a perfect lattice in lithium-rich layered cathodes, featuring electrochemical driven surface vacancy creation, injection and condensation phenomenon and revealing an unrecognized surface process induced bulk lattice degradation featured with void formation and lattice reorganization. This process is associated with a high-cutoff voltage at which the anionic redox is activated. Coupling with calculations, we substantiate that triggering of anionic redox leads to sharply lowering of both formation energy of oxygen vacancy and migration barrier of oxidized oxide ions, therefore enabling migration of oxygen vacancy via oxidized oxide ion and leading to the injection of oxygen vacancy generated at the particle surface into the bulk lattice. This work unveils unpredicted behavior of oxidized oxide ion, leadingmore » to essential insight for designing of high capacity cathode for better batteries through coupled cationic and anionic redox dynamics in layered cathodes. In a broad term, this work provides insight on the intimate coupling between interfacial process and bulk lattice behavior for governing electrode functionality.« less

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [3];  [4]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. Beihang University
  3. Lawrence Berkeley National Laboratory
  4. Argonne National Laboratory
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1544606
Report Number(s):
PNNL-SA-141286
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 14; Journal Issue: 6
Country of Publication:
United States
Language:
English

Citation Formats

Yan, Pengfei, Zheng, Jianming, Tang, Zhen-Kun, Devaraj, Arun, Chen, Guoying, Amine, Khalil, Zhang, Jiguang, Liu, Li-Min, and Wang, Chongmin. Injection of oxygen vacancies in the bulk lattice of layered cathodes. United States: N. p., 2019. Web. doi:10.1038/s41565-019-0428-8.
Yan, Pengfei, Zheng, Jianming, Tang, Zhen-Kun, Devaraj, Arun, Chen, Guoying, Amine, Khalil, Zhang, Jiguang, Liu, Li-Min, & Wang, Chongmin. Injection of oxygen vacancies in the bulk lattice of layered cathodes. United States. doi:10.1038/s41565-019-0428-8.
Yan, Pengfei, Zheng, Jianming, Tang, Zhen-Kun, Devaraj, Arun, Chen, Guoying, Amine, Khalil, Zhang, Jiguang, Liu, Li-Min, and Wang, Chongmin. Mon . "Injection of oxygen vacancies in the bulk lattice of layered cathodes". United States. doi:10.1038/s41565-019-0428-8.
@article{osti_1544606,
title = {Injection of oxygen vacancies in the bulk lattice of layered cathodes},
author = {Yan, Pengfei and Zheng, Jianming and Tang, Zhen-Kun and Devaraj, Arun and Chen, Guoying and Amine, Khalil and Zhang, Jiguang and Liu, Li-Min and Wang, Chongmin},
abstractNote = {Surfaces, interfaces, and grain boundaries are, classically, known to be sinks at which defects generated within bulk lattice will preferentially migrate to and get annihilated, therefore rejuvenating a crystalline lattice to restore the intended functionalities.1, 2, 3 Here we report an inverse case by which the defects generated at the particle surface are continuously pumped into the bulk lattice and consequentially compromising the intended functionalities. We discovered that during the operation of a rechargeable battery, oxygen vacancies generated at cathode particle surfaces migrate toward inside of a perfect lattice in lithium-rich layered cathodes, featuring electrochemical driven surface vacancy creation, injection and condensation phenomenon and revealing an unrecognized surface process induced bulk lattice degradation featured with void formation and lattice reorganization. This process is associated with a high-cutoff voltage at which the anionic redox is activated. Coupling with calculations, we substantiate that triggering of anionic redox leads to sharply lowering of both formation energy of oxygen vacancy and migration barrier of oxidized oxide ions, therefore enabling migration of oxygen vacancy via oxidized oxide ion and leading to the injection of oxygen vacancy generated at the particle surface into the bulk lattice. This work unveils unpredicted behavior of oxidized oxide ion, leading to essential insight for designing of high capacity cathode for better batteries through coupled cationic and anionic redox dynamics in layered cathodes. In a broad term, this work provides insight on the intimate coupling between interfacial process and bulk lattice behavior for governing electrode functionality.},
doi = {10.1038/s41565-019-0428-8},
journal = {Nature Nanotechnology},
number = 6,
volume = 14,
place = {United States},
year = {2019},
month = {4}
}