No Cover Image

Journal article 264 views

LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries

Mohammad Ali Nowroozi, Kerstin Wissel, Jochen Rohrer, Anji Munnangi Orcid Logo, Oliver Clemens

Chemistry of Materials, Volume: 29, Issue: 8, Pages: 3441 - 3453

Swansea University Author: Anji Munnangi Orcid Logo

Full text not available from this repository: check for access using links below.

Abstract

This article reports on the investigation of LaSrMnO4 with K2NiF4 type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF2 based anodes and shows that fluoride intercalation proceeds stepw...

Full description

Published in: Chemistry of Materials
ISSN: 0897-4756 1520-5002
Published: American Chemical Society (ACS) 2017
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa51554
Tags: Add Tag
No Tags, Be the first to tag this record!
first_indexed 2019-08-27T15:30:54Z
last_indexed 2019-09-04T14:49:31Z
id cronfa51554
recordtype SURis
fullrecord <?xml version="1.0"?><rfc1807><datestamp>2019-09-04T11:04:44.5642034</datestamp><bib-version>v2</bib-version><id>51554</id><entry>2019-08-27</entry><title>LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries</title><swanseaauthors><author><sid>3ed0b4f2ff4fb9e87c7a73e7a3c39da7</sid><ORCID>0000-0001-9101-0252</ORCID><firstname>Anji</firstname><surname>Munnangi</surname><name>Anji Munnangi</name><active>true</active><ethesisStudent>false</ethesisStudent></author></swanseaauthors><date>2019-08-27</date><deptcode>MTLS</deptcode><abstract>This article reports on the investigation of LaSrMnO4 with K2NiF4 type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF2 based anodes and shows that fluoride intercalation proceeds stepwise to form LaSrMnO4F and LaSrMnO4F2&#x2013;x. Ex-situ X-ray diffraction experiments were recorded for different cutoff voltages for a deeper understanding of the charging process, highlighting additional potential of the method to be used to adjust fluorine contents more easily than using conventional fluorination methods. A discharging capacity of approximately 20&#x2013;25 mAh/g was found, which is &#x223C;4&#x2013;5 times higher compared to what was reported previously on the discharging of BaFeO2.5/BaFeO2.5F0.5, approaching discharge capacities for conversion based fluoride ion batteries. Density functional theory based calculations confirm the observed potential steps of approximately 1 and 2 V for the first (LaSrMnO4 &#x2192; LaSrMnO4F) and second (LaSrMnO4F &#x2192; LaSrMnO4F2&#x2013;x) intercalation steps against Pb-PbF2, respectively. Additionally, a detailed structure analysis was performed for chemically prepared LaSrMnO4F2&#x2013;x (x &#x223C; 0.2), showing strong similarity to the product which is obtained after charging the batteries to voltages above 2 V against Pb-PbF2. It was observed that charging and discharging kinetics as well as coulomb efficiencies are limited for the batteries in the current state, which can be partly assigned to overpotentials arising from the use of conversion based anode composites and the stability of the charged sample toward carbon black and the current collectors. Therefore, the structural stability of LaSrMnO4F2 on the deintercalation of fluoride ions was demonstrated by a galvanostatic discharging to &#x2212;3 V against Pb-PbF2, which can be used to compensate such overpotentials, resulting in almost complete recovery of fluorine free LaSrMnO4 with a discharge capacity of &#x223C;100 mAh/g. This is the first report showing that selective extraction of fluoride ions from an oxyfluoride matrix is possible, and it highlights that compounds with K2NiF4 type structure can be considered as interesting host lattices for the reversible intercalation/deintercalation of fluoride ions within intercalation based FIBs.</abstract><type>Journal Article</type><journal>Chemistry of Materials</journal><volume>29</volume><journalNumber>8</journalNumber><paginationStart>3441</paginationStart><paginationEnd>3453</paginationEnd><publisher>American Chemical Society (ACS)</publisher><issnPrint>0897-4756</issnPrint><issnElectronic>1520-5002</issnElectronic><keywords/><publishedDay>25</publishedDay><publishedMonth>4</publishedMonth><publishedYear>2017</publishedYear><publishedDate>2017-04-25</publishedDate><doi>10.1021/acs.chemmater.6b05075</doi><url/><notes/><college>COLLEGE NANME</college><department>Materials Science and Engineering</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>MTLS</DepartmentCode><institution>Swansea University</institution><apcterm/><lastEdited>2019-09-04T11:04:44.5642034</lastEdited><Created>2019-08-27T12:04:37.4517413</Created><path><level id="1">College of Engineering</level><level id="2">Engineering</level></path><authors><author><firstname>Mohammad Ali</firstname><surname>Nowroozi</surname><order>1</order></author><author><firstname>Kerstin</firstname><surname>Wissel</surname><order>2</order></author><author><firstname>Jochen</firstname><surname>Rohrer</surname><order>3</order></author><author><firstname>Anji</firstname><surname>Munnangi</surname><orcid>0000-0001-9101-0252</orcid><order>4</order></author><author><firstname>Oliver</firstname><surname>Clemens</surname><order>5</order></author></authors><documents/><OutputDurs/></rfc1807>
spelling 2019-09-04T11:04:44.5642034 v2 51554 2019-08-27 LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries 3ed0b4f2ff4fb9e87c7a73e7a3c39da7 0000-0001-9101-0252 Anji Munnangi Anji Munnangi true false 2019-08-27 MTLS This article reports on the investigation of LaSrMnO4 with K2NiF4 type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF2 based anodes and shows that fluoride intercalation proceeds stepwise to form LaSrMnO4F and LaSrMnO4F2–x. Ex-situ X-ray diffraction experiments were recorded for different cutoff voltages for a deeper understanding of the charging process, highlighting additional potential of the method to be used to adjust fluorine contents more easily than using conventional fluorination methods. A discharging capacity of approximately 20–25 mAh/g was found, which is ∼4–5 times higher compared to what was reported previously on the discharging of BaFeO2.5/BaFeO2.5F0.5, approaching discharge capacities for conversion based fluoride ion batteries. Density functional theory based calculations confirm the observed potential steps of approximately 1 and 2 V for the first (LaSrMnO4 → LaSrMnO4F) and second (LaSrMnO4F → LaSrMnO4F2–x) intercalation steps against Pb-PbF2, respectively. Additionally, a detailed structure analysis was performed for chemically prepared LaSrMnO4F2–x (x ∼ 0.2), showing strong similarity to the product which is obtained after charging the batteries to voltages above 2 V against Pb-PbF2. It was observed that charging and discharging kinetics as well as coulomb efficiencies are limited for the batteries in the current state, which can be partly assigned to overpotentials arising from the use of conversion based anode composites and the stability of the charged sample toward carbon black and the current collectors. Therefore, the structural stability of LaSrMnO4F2 on the deintercalation of fluoride ions was demonstrated by a galvanostatic discharging to −3 V against Pb-PbF2, which can be used to compensate such overpotentials, resulting in almost complete recovery of fluorine free LaSrMnO4 with a discharge capacity of ∼100 mAh/g. This is the first report showing that selective extraction of fluoride ions from an oxyfluoride matrix is possible, and it highlights that compounds with K2NiF4 type structure can be considered as interesting host lattices for the reversible intercalation/deintercalation of fluoride ions within intercalation based FIBs. Journal Article Chemistry of Materials 29 8 3441 3453 American Chemical Society (ACS) 0897-4756 1520-5002 25 4 2017 2017-04-25 10.1021/acs.chemmater.6b05075 COLLEGE NANME Materials Science and Engineering COLLEGE CODE MTLS Swansea University 2019-09-04T11:04:44.5642034 2019-08-27T12:04:37.4517413 College of Engineering Engineering Mohammad Ali Nowroozi 1 Kerstin Wissel 2 Jochen Rohrer 3 Anji Munnangi 0000-0001-9101-0252 4 Oliver Clemens 5
title LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
spellingShingle LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
Anji Munnangi
title_short LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
title_full LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
title_fullStr LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
title_full_unstemmed LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
title_sort LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries
author_id_str_mv 3ed0b4f2ff4fb9e87c7a73e7a3c39da7
author_id_fullname_str_mv 3ed0b4f2ff4fb9e87c7a73e7a3c39da7_***_Anji Munnangi
author Anji Munnangi
author2 Mohammad Ali Nowroozi
Kerstin Wissel
Jochen Rohrer
Anji Munnangi
Oliver Clemens
format Journal article
container_title Chemistry of Materials
container_volume 29
container_issue 8
container_start_page 3441
publishDate 2017
institution Swansea University
issn 0897-4756
1520-5002
doi_str_mv 10.1021/acs.chemmater.6b05075
publisher American Chemical Society (ACS)
college_str College of Engineering
hierarchytype
hierarchy_top_id collegeofengineering
hierarchy_top_title College of Engineering
hierarchy_parent_id collegeofengineering
hierarchy_parent_title College of Engineering
department_str Engineering{{{_:::_}}}College of Engineering{{{_:::_}}}Engineering
document_store_str 0
active_str 0
description This article reports on the investigation of LaSrMnO4 with K2NiF4 type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF2 based anodes and shows that fluoride intercalation proceeds stepwise to form LaSrMnO4F and LaSrMnO4F2–x. Ex-situ X-ray diffraction experiments were recorded for different cutoff voltages for a deeper understanding of the charging process, highlighting additional potential of the method to be used to adjust fluorine contents more easily than using conventional fluorination methods. A discharging capacity of approximately 20–25 mAh/g was found, which is ∼4–5 times higher compared to what was reported previously on the discharging of BaFeO2.5/BaFeO2.5F0.5, approaching discharge capacities for conversion based fluoride ion batteries. Density functional theory based calculations confirm the observed potential steps of approximately 1 and 2 V for the first (LaSrMnO4 → LaSrMnO4F) and second (LaSrMnO4F → LaSrMnO4F2–x) intercalation steps against Pb-PbF2, respectively. Additionally, a detailed structure analysis was performed for chemically prepared LaSrMnO4F2–x (x ∼ 0.2), showing strong similarity to the product which is obtained after charging the batteries to voltages above 2 V against Pb-PbF2. It was observed that charging and discharging kinetics as well as coulomb efficiencies are limited for the batteries in the current state, which can be partly assigned to overpotentials arising from the use of conversion based anode composites and the stability of the charged sample toward carbon black and the current collectors. Therefore, the structural stability of LaSrMnO4F2 on the deintercalation of fluoride ions was demonstrated by a galvanostatic discharging to −3 V against Pb-PbF2, which can be used to compensate such overpotentials, resulting in almost complete recovery of fluorine free LaSrMnO4 with a discharge capacity of ∼100 mAh/g. This is the first report showing that selective extraction of fluoride ions from an oxyfluoride matrix is possible, and it highlights that compounds with K2NiF4 type structure can be considered as interesting host lattices for the reversible intercalation/deintercalation of fluoride ions within intercalation based FIBs.
published_date 2017-04-25T04:19:57Z
_version_ 1732951353902235648
score 10.872977