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Current computational trends in polyanionic cathode materials for Li and Na batteries
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.ORCID iD: 0000-0002-6765-2084
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.ORCID iD: 0000-0002-3548-133x
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.
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2018 (English)In: Journal of Physics: Condensed Matter, ISSN 0953-8984, E-ISSN 1361-648X, Vol. 30, no 28, article id 283003Article, review/survey (Refereed) Published
Abstract [en]

A long-standing effort has been devoted for the development of high energy density cathodes both for Li-and Na-ion batteries (LIBs and SIBs). The scientific communities in battery research primarily divide the Li- and Na-ion cathode materials into two categories: layered oxides and polyanionic compounds. Researchers are trying to improve the energy density of such materials through materials screening by mixing the transition metals or changing the concentration of Li or Na in the polyanionic compounds. Due to the fact that there is more stability in the polyanionic frameworks, batteries based on these materials mostly provide a prolonged cycling life as compared to the layered oxide materials. Nevertheless, the bottleneck for such compounds is the weight penalty from polyanionic groups that results into the lower capacity. The anion engineering could be considered as an essential way out to design such polyanionic compounds to resolve this issue and to fetch improved cathode performance. In this topical review we present a systematic overview of the polyanionic cathode materials used for LIBs and SIBs. We will also present the computational methodologies that have become significantly relevant for battery research. We will make an attempt to provide the theoretical insight with a current development in sulfate (SO4), silicate (SiO4) and phosphate (PO4) based cathode materials for LIBs and SIBs. We will end this topical review with the future outlook, that will consist of the next generation organic electrode materials, mainly based on conjugated carbonyl compounds.

Place, publisher, year, edition, pages
2018. Vol. 30, no 28, article id 283003
Keywords [en]
Li-ion batteries, Na-ion batteries, energy storage, polyanionic cathode materials, organic cathode materials, DFT investigation
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-368909DOI: 10.1088/1361-648X/aac62dISI: 000436088400001PubMedID: 29932053OAI: oai:DiVA.org:uu-368909DiVA, id: diva2:1269323
Funder
Swedish Research CouncilCarl Tryggers foundation StandUpAvailable from: 2018-12-10 Created: 2018-12-10 Last updated: 2019-04-05Bibliographically approved
In thesis
1. Defect Thermodynamics and Kinetics in Polyanionic Cathodes: A Theoretical Roadmap for Na-ion based Batteries and Hybrid Supercapacitors
Open this publication in new window or tab >>Defect Thermodynamics and Kinetics in Polyanionic Cathodes: A Theoretical Roadmap for Na-ion based Batteries and Hybrid Supercapacitors
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, the framework of the density functional theory is employed to study and predict properties of polyanionic cathodes for Na-ion batteries and hybrid supercapacitors. It consists of three main parts as follows:

The first part is primarily dedicated to kröhnkite-type Na2Fe(SO4)22H2O cathode. The major goal is to probe diffusion mechanisms of Na+ ions.  The chemical potentials diagrams for the pentrary compound are determined under thermodynamic equilibrium and are used to calculate pH value for solution-based synthesis. We find that the presence of NaFe facilitates a faster migration and reduces the channel blockage issue. Moreover, the defect concentration can be tuned by controlling the pH condition. We conclude that defects and small hole polarons play a role in ionic and electronic conductivity.

The second part focuses on alluaudite-type Na2+2δFe2-δ(SO4)3 (NFSδ). We unveil the effect of the non-stoichiometry on the thermodynamics, defect nature, and voltage profiles NFSδ with δ = 0, 0.25 and 0.5. The relation between Na ion distribution and energetics is studied and reveals the necessity of using a supercell model. Chemical potential diagrams indicate an inevitable impurity precipitation in all cases, but can be reduced at low δ. Defect formation analysis shows an unlikely formation of channel blockage and can explain the impurity precipitation in experiment. Two types of phase transition are observed after half-desodiation. A higher degree of non-stoichiometry offers an improvement in specific capacity and structural reversibility for NFS0.25 and NFS0.5. The voltage profiles and formation energy reveal the Na intercalation mechanism and strategy to enhance the specific capacity.

The third part is associated with battery-type cathodes used in hybrid supercapacitors, namely the NaMPO4 and MMoO4 (where M is a transition metal). We find that triphylite NaNiPO4 shows a better electrochemical performance as compared to maricite phase due to the merit of intercalation mechanism. A mixed-NaMn1/3Co1/3Ni1/3PO4 is predicted to show faradaic behavior, mainly contributed from the Ni and Mn redox reactions, along with an improved electronic conductivity. Moreover, the effect of M substitution on phase stability, electronic properties and charge transfer is also studied in MMoO4 with M = Mn, Co and Ni. The highest capacitance is predicted for NiMoO4 amongst the others and is attributed to the higher active surface area. To compromise the capacitance and cycling stability, Mn1/3Co1/3Ni1/3MoO4 is synthesized. We predict its crystal structure by using the SQS method. Based on electronic structure, we can identify a source of the improved cycling efficiency and specific capacitance of this mixed compound.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. p. 92
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1796
Keywords
DFT, Energy Materials, Defects, Chemical potentials, Kinetics, Hybrid supercapacitors, Na-ion batteries, Polyanionic cathodes
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-381173 (URN)978-91-513-0628-5 (ISBN)
Public defence
2019-05-22, Room 80101, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2019-04-29 Created: 2019-04-05 Last updated: 2019-06-18

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Chakraborty, SudipBanerjee, AmitavaWatcharatharapong, TeeraphatAraujo, Rafael BarrosAhuja, Rajeev

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