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Title: Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host

Abstract

We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. Here, it also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core–shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na2Se2 (hcp) and Na2Se (fcc). A nanoscale fracture of terminally sodiated Na–Se is observed by HAADF, with SSNMR, indicating a physical separation of some Se from the carbon host after the first cycle. GITT reveals a 3-fold increase in Na+ diffusivity at cycle 2, which may be explained by the creation of extra interfaces. These combined findings highlight the complex phenomenology of electrochemical phase transformations in nanoconfined materials, which may profoundly differ from their “free”more » counterparts.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3];  [5]; ORCiD logo [3]; ORCiD logo [3];  [6]; ORCiD logo [2];  [2]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [3]
  1. Ames Lab., Ames, IA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Univ. of Texas, Austin, TX (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ames Lab., Ames, IA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Electricity (OE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1600507
Alternate Identifier(s):
OSTI ID: 1606029; OSTI ID: 1615720
Report Number(s):
IS-J-10157; BNL-213860-2020-JAAM
Journal ID: ISSN 1530-6984
Grant/Contract Number:  
AC02-07CH11358; SC0012704; SC0018074
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 20; Journal Issue: 2; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; sodium−sulfur batteries; lithium−sulfur batteries; selenides; sodium metal batteries (SMBs); lithium metal batteries (LMBs); solid-state NMR; electrodes; transmission electron microscopy; batteries; nuclear magnetic resonance spectroscopy; materials; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Perras, Frédéric A., Hwang, Sooyeon, Wang, Yixian, Self, Ethan C., Liu, Pengcheng, Biswas, Rana, Nagarajan, Sudhan, Pham, Viet Hung, Xu, Yixin, Boscoboinik, J. Anibal, Su, Dong, Nanda, Jagjit, Pruski, Marek, and Mitlin, David. Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.nanolett.9b03797.
Perras, Frédéric A., Hwang, Sooyeon, Wang, Yixian, Self, Ethan C., Liu, Pengcheng, Biswas, Rana, Nagarajan, Sudhan, Pham, Viet Hung, Xu, Yixin, Boscoboinik, J. Anibal, Su, Dong, Nanda, Jagjit, Pruski, Marek, & Mitlin, David. Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host. United States. https://doi.org/10.1021/acs.nanolett.9b03797
Perras, Frédéric A., Hwang, Sooyeon, Wang, Yixian, Self, Ethan C., Liu, Pengcheng, Biswas, Rana, Nagarajan, Sudhan, Pham, Viet Hung, Xu, Yixin, Boscoboinik, J. Anibal, Su, Dong, Nanda, Jagjit, Pruski, Marek, and Mitlin, David. Mon . "Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host". United States. https://doi.org/10.1021/acs.nanolett.9b03797. https://www.osti.gov/servlets/purl/1600507.
@article{osti_1600507,
title = {Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host},
author = {Perras, Frédéric A. and Hwang, Sooyeon and Wang, Yixian and Self, Ethan C. and Liu, Pengcheng and Biswas, Rana and Nagarajan, Sudhan and Pham, Viet Hung and Xu, Yixin and Boscoboinik, J. Anibal and Su, Dong and Nanda, Jagjit and Pruski, Marek and Mitlin, David},
abstractNote = {We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. Here, it also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core–shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na2Se2 (hcp) and Na2Se (fcc). A nanoscale fracture of terminally sodiated Na–Se is observed by HAADF, with SSNMR, indicating a physical separation of some Se from the carbon host after the first cycle. GITT reveals a 3-fold increase in Na+ diffusivity at cycle 2, which may be explained by the creation of extra interfaces. These combined findings highlight the complex phenomenology of electrochemical phase transformations in nanoconfined materials, which may profoundly differ from their “free” counterparts.},
doi = {10.1021/acs.nanolett.9b03797},
journal = {Nano Letters},
number = 2,
volume = 20,
place = {United States},
year = {2019},
month = {12}
}

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