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Title: Unravelling Solid-State Redox Chemistry in Li 1.3Nb 0.3Mn 0.4O 2 Single-Crystal Cathode Material

Abstract

Recent reports on high capacities delivered by Li-excess transition-metal oxide cathodes have triggered intense interest in utilizing reversible oxygen redox for high-energy battery applications. To control oxygen electrochemical activities, fundamental understanding of redox chemistry is essential yet has so far proven challenging. In the present study, micrometer-sized Li 1.3Nb 0.3Mn 0.4O 2 single crystals were synthesized for the first time and used as a platform to understand the charge compensation mechanism during Li extraction and insertion. We explicitly demonstrate that the oxidation of O 2- to O n- (0 < n < 2) and O 2 loss from the lattice dominates at 4.5 and 4.7 V, respectively. While both processes occur in the first cycle, only the redox of O 2-/O n- participates in the following cycles. The lattice anion redox process triggers irreversible changes in Mn redox, which likely causes the voltage and capacity fade observed on this oxide. Two drastically different redox activity regions, a single-phase behavior involving only Mn 3+/4+ and a two-phase behavior involving O 2-/O n- (0 ≤ n < 2), were found in Li xNb 0.3Mn 0.4O 2 (0 < x < 1.3). Morphological damage with particle cracking and fracturing was broadly observed whenmore » O redox is active, revealing additional challenges in utilizing O redox for high-energy cathode development.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [3];  [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1532306
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 5; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Kan, Wang Hay, Chen, Dongchang, Papp, Joseph K., Shukla, Alpesh Khushalchand, Huq, Ashfia, Brown, Craig M., McCloskey, Bryan D., and Chen, Guoying. Unravelling Solid-State Redox Chemistry in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode Material. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b05036.
Kan, Wang Hay, Chen, Dongchang, Papp, Joseph K., Shukla, Alpesh Khushalchand, Huq, Ashfia, Brown, Craig M., McCloskey, Bryan D., & Chen, Guoying. Unravelling Solid-State Redox Chemistry in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode Material. United States. doi:10.1021/acs.chemmater.7b05036.
Kan, Wang Hay, Chen, Dongchang, Papp, Joseph K., Shukla, Alpesh Khushalchand, Huq, Ashfia, Brown, Craig M., McCloskey, Bryan D., and Chen, Guoying. Fri . "Unravelling Solid-State Redox Chemistry in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode Material". United States. doi:10.1021/acs.chemmater.7b05036. https://www.osti.gov/servlets/purl/1532306.
@article{osti_1532306,
title = {Unravelling Solid-State Redox Chemistry in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode Material},
author = {Kan, Wang Hay and Chen, Dongchang and Papp, Joseph K. and Shukla, Alpesh Khushalchand and Huq, Ashfia and Brown, Craig M. and McCloskey, Bryan D. and Chen, Guoying},
abstractNote = {Recent reports on high capacities delivered by Li-excess transition-metal oxide cathodes have triggered intense interest in utilizing reversible oxygen redox for high-energy battery applications. To control oxygen electrochemical activities, fundamental understanding of redox chemistry is essential yet has so far proven challenging. In the present study, micrometer-sized Li1.3Nb0.3Mn0.4O2 single crystals were synthesized for the first time and used as a platform to understand the charge compensation mechanism during Li extraction and insertion. We explicitly demonstrate that the oxidation of O2- to On- (0 < n < 2) and O2 loss from the lattice dominates at 4.5 and 4.7 V, respectively. While both processes occur in the first cycle, only the redox of O2-/On- participates in the following cycles. The lattice anion redox process triggers irreversible changes in Mn redox, which likely causes the voltage and capacity fade observed on this oxide. Two drastically different redox activity regions, a single-phase behavior involving only Mn3+/4+ and a two-phase behavior involving O2-/On- (0 ≤ n < 2), were found in LixNb0.3Mn0.4O2 (0 < x < 1.3). Morphological damage with particle cracking and fracturing was broadly observed when O redox is active, revealing additional challenges in utilizing O redox for high-energy cathode development.},
doi = {10.1021/acs.chemmater.7b05036},
journal = {Chemistry of Materials},
number = 5,
volume = 30,
place = {United States},
year = {2018},
month = {2}
}

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