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Title: Lithium Superoxide Hydrolysis and Relevance to Li–O 2 Batteries

Fundamental understanding of reactions of lithium peroxides and superoxides is essential for the development of Li–O 2 batteries. In this context, an investigation is reported of the hydrolysis of lithium superoxide, which has recently been synthesized in a Li–O 2 battery. Surprisingly, the hydrolysis of solid LiO 2 is significantly different from that of NaO 2 and KO 2. Unlike KO 2 and NaO 2, the hydrolysis of LiO 2 does not produce H 2O 2. Similarly, the reactivity of Li 2O 2 toward water differs from LiO 2, in that Li 2O 2 results in H 2O 2 as a product. The difference in the LiO 2 reactivity with water is due to the more exothermic nature of the formation of LiOH and O 2 compared with the corresponding reactions of NaO 2 and KO 2. Here, we also show that a titration method used in this study, based on reaction of the discharge product with a Ti(IV)OSO 4 solution, provides a useful diagnostic technique to provide information on the composition of a discharge product in a Li–O 2 battery.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [1] ;  [1] ; ORCiD logo [1] ;  [2] ;  [2] ;  [2] ;  [4] ;  [5] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Hanyang Univ., Seoul (Republic of Korea)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
  4. Univ. of Illinois, Chicago, IL (United States)
  5. California State Univ. (CalState), Northridge, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1374608

Wang, Hsien -Hau, Lee, Yun Jung, Assary, Rajeev S., Zhang, Chengji, Luo, Xiangyi, Redfern, Paul C., Lu, Jun, Lee, Young Joo, Kim, Do Hyung, Kang, Tae -Geun, Indacochea, Ernesto, Lau, Kah Chun, Amine, Khalil, and Curtiss, Larry A.. Lithium Superoxide Hydrolysis and Relevance to Li–O2 Batteries. United States: N. p., Web. doi:10.1021/acs.jpcc.6b12950.
Wang, Hsien -Hau, Lee, Yun Jung, Assary, Rajeev S., Zhang, Chengji, Luo, Xiangyi, Redfern, Paul C., Lu, Jun, Lee, Young Joo, Kim, Do Hyung, Kang, Tae -Geun, Indacochea, Ernesto, Lau, Kah Chun, Amine, Khalil, & Curtiss, Larry A.. Lithium Superoxide Hydrolysis and Relevance to Li–O2 Batteries. United States. doi:10.1021/acs.jpcc.6b12950.
Wang, Hsien -Hau, Lee, Yun Jung, Assary, Rajeev S., Zhang, Chengji, Luo, Xiangyi, Redfern, Paul C., Lu, Jun, Lee, Young Joo, Kim, Do Hyung, Kang, Tae -Geun, Indacochea, Ernesto, Lau, Kah Chun, Amine, Khalil, and Curtiss, Larry A.. 2017. "Lithium Superoxide Hydrolysis and Relevance to Li–O2 Batteries". United States. doi:10.1021/acs.jpcc.6b12950. https://www.osti.gov/servlets/purl/1374608.
@article{osti_1374608,
title = {Lithium Superoxide Hydrolysis and Relevance to Li–O2 Batteries},
author = {Wang, Hsien -Hau and Lee, Yun Jung and Assary, Rajeev S. and Zhang, Chengji and Luo, Xiangyi and Redfern, Paul C. and Lu, Jun and Lee, Young Joo and Kim, Do Hyung and Kang, Tae -Geun and Indacochea, Ernesto and Lau, Kah Chun and Amine, Khalil and Curtiss, Larry A.},
abstractNote = {Fundamental understanding of reactions of lithium peroxides and superoxides is essential for the development of Li–O2 batteries. In this context, an investigation is reported of the hydrolysis of lithium superoxide, which has recently been synthesized in a Li–O2 battery. Surprisingly, the hydrolysis of solid LiO2 is significantly different from that of NaO2 and KO2. Unlike KO2 and NaO2, the hydrolysis of LiO2 does not produce H2O2. Similarly, the reactivity of Li2O2 toward water differs from LiO2, in that Li2O2 results in H2O2 as a product. The difference in the LiO2 reactivity with water is due to the more exothermic nature of the formation of LiOH and O2 compared with the corresponding reactions of NaO2 and KO2. Here, we also show that a titration method used in this study, based on reaction of the discharge product with a Ti(IV)OSO4 solution, provides a useful diagnostic technique to provide information on the composition of a discharge product in a Li–O2 battery.},
doi = {10.1021/acs.jpcc.6b12950},
journal = {Journal of Physical Chemistry. C},
number = 18,
volume = 121,
place = {United States},
year = {2017},
month = {4}
}