uu.seUppsala University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)(3) Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights
Indian Inst Sci, Mat Res Ctr, Faraday Mat Lab, CV Raman Ave, Bangalore 560012, Karnataka, India..
Univ Sydney, Sch Chem, Bldg F11, Sydney, NSW 2006, Australia..
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
Show others and affiliations
2016 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 8, no 11, p. 6982-6991Article in journal (Refereed) Published
Resource type
Text
Abstract [en]

Exploring future cathode materials for sodium-ion batteries, alluaudite class of Na2Fe2II(SO4)(3) has been recently unveiled as a 3.8 V positive insertion candidate (Barpanda et al. Nat. Commun. 2014, 5, 4358). It forms an Fe-based polyanionic compound delivering the highest Fe-redox potential along with excellent rate kinetics and reversibility. However, like all known SO4-based insertion materials, its synthesis is cumbersome that warrants careful processing avoiding any aqueous exposure. Here, an alternate low temperature ionothermal synthesis has been described to produce the alluaudite Na2+2xFe2-xII(SO4)(3). It marks the first demonstration of solvothermal synthesis of alluaudite Na2+2xM2-xII(SO4)(3) (M = 3d metals) family of cathodes. Unlike classical solid-state route, this solvothermal route favors sustainable synthesis of homogeneous nanostructured alluaudite products at only 300 degrees C, the lowest temperature value until date. The current work reports the synthetic aspects of pristine and modified ionothermal synthesis of Na2+2xFe2-xII(SO4)(3) having tunable size (300 nm similar to 5 mu m) and morphology. It shows antiferromagnetic ordering below 12 K. A reversible capacity in excess of 80 mAh/g was obtained with good rate kinetics and cycling stability over 50 cycles. Using a synergistic approach combining experimental and ab initio DFT analysis, the structural, magnetic, electronic, and electrochemical properties and the structural limitation to extract full capacity have been described.

Place, publisher, year, edition, pages
2016. Vol. 8, no 11, p. 6982-6991
Keyword [en]
sodium-ion battery, alluaudite, Na2Fe2(SO4)(3), ionothermal synthesis, DFT
National Category
Materials Engineering
Identifiers
URN: urn:nbn:se:uu:diva-294306DOI: 10.1021/acsami.5b11302ISI: 000372946600024PubMedID: 26931644OAI: oai:DiVA.org:uu-294306DiVA, id: diva2:929458
Funder
Carl Tryggers foundation Swedish Research CouncilStandUp
Available from: 2016-05-18 Created: 2016-05-18 Last updated: 2017-11-30Bibliographically approved
In thesis
1. Energy Storage Materials: Insights From ab Initio Theory: Diffusion, Structure, Thermodynamics and Design.
Open this publication in new window or tab >>Energy Storage Materials: Insights From ab Initio Theory: Diffusion, Structure, Thermodynamics and Design.
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The development of science and technology have provided a lifestyle completely dependent on energy consumption. Devices such as computers and mobile phones are good examples of how our daily life depends on electric energy. In this scenario, energy storage technologies emerge with strategic importance providing efficient ways to transport and commercialize the produced energy. Rechargeable batteries come as the most suitable alternative to fulfill the market demand due to their higher energy- and power- density when compared with other electrochemical energy storage systems. In this context, during the production of this thesis, promising compounds for advanced batteries application were investigated from the theoretical viewpoint. The framework of the density functional theory has been employed together with others theoretical tools to study properties such as ionic diffusion, redox potential, electronic structure and crystal structure prediction.

Different organic materials were theoretically characterized with quite distinct objectives. For instance, a protocol able to predict the redox potential in solution of long oligomers were developed and tested against experimental measurements. Strategies such as anchoring of small active molecules on polymers backbone have also been investigated through a screening process that determined the most promising candidates. Methods such as evolutionary simulation and basin-hopping algorithm were employed to search for global minimum crystal structures of small molecules and inorganic compounds working as a cathode of advanced sodium batteries. The crystal structure evolution of C6Cl4O2 upon Na insertion was unveiled and the main reasons behind the lower specific capacity obtained in the experiment were clarified. Ab initio molecular dynamics and the nudged elastic band method were employed to understand the underlying ionic diffusion mechanisms in the recently proposed Alluaudite and Eldfellite cathode materials. Moreover, it was demonstrated that electronic conduction in Na2O2, a byproduct of the Na-O2 battery, occurs via hole polarons hopping. Important physical and chemical insights were obtained during the production of this thesis. It finally supports the development of low production cost, environmental friendliness and efficient electrode compounds for advanced secondary batteries. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. p. 83
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1584
Keyword
Density Functional Theory, Defects Diffusion, Thermodynamics and Batteries.
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-331399 (URN)978-91-513-0122-8 (ISBN)
Public defence
2017-12-07, Polhemsalen, Ångström Laboratory, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2017-11-15 Created: 2017-10-19 Last updated: 2018-03-07

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMed

Authority records BETA

Araujo, Rafael B.Chakraborty, SudipAhuja, Rajeev

Search in DiVA

By author/editor
Araujo, Rafael B.Chakraborty, SudipAhuja, Rajeev
By organisation
Materials Theory
In the same journal
ACS Applied Materials and Interfaces
Materials Engineering

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 356 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf