Defect Chemistry and Li-ion Diffusion in LiRuO

Overview

Journal Sci Rep

Specialty Science

Date 2019 Jan 26

PMID 30679560

Citations 5

Authors

Navaratnarajah Kuganathan

Apostolos Kordatos

Alexander Chroneos

Affiliations

Soon will be listed here.

Abstract

Layered LiRuO is an important candidate cathode material in rechargeable lithium ion batteries because of its novel anionic redox process and high reversible capacity. Atomistic scale simulations are used to calculate the intrinsic defect process, favourable dopants and migration energies of lithium ion diffusions together with migration paths in LiRuO. The Li Frenkel is calculated to be the most favourable intrinsic defect type. The cation anti-site defect, in which Li and Ru ions exchange their positions is 1.89 eV/defect suggesting that this defect would be observed at high temperatures. Long range vacancy assisted lithium diffusion paths were calculated and it is confirmed that the lowest overall activation energy (0.73 eV) migration path is along the ab plane. Trivalent dopants (Al, Co, Sc, In, Y, Gd and La) were considered to create additional Li in LiRuO. Here we show that Al or Co are the ideal dopants and this is in agreement with the experimental studies reported on Co doping in LiRuO.

Citing Articles

Tailoring electronic-ionic local environment for solid-state Li-O battery by engineering crystal structure.

Sun X, Song Y, Liu Q, Zhang X, An H, Sun N Sci Adv. 2022; 8(35):eabq6261.

PMID: 36054349 PMC: 10848956. DOI: 10.1126/sciadv.abq6261.

Defect Chemistry, Sodium Diffusion and Doping Behaviour in NaFeO Polymorphs as Cathode Materials for Na-Ion Batteries: A Computational Study.

Kuganathan N, Kelaidis N, Chroneos A Materials (Basel). 2019; 12(19).

PMID: 31590230 PMC: 6803870. DOI: 10.3390/ma12193243.

Defects, Diffusion, and Dopants in LiTiO: Atomistic Simulation Study.

Kuganathan N, Ganeshalingam S, Chroneos A Materials (Basel). 2019; 12(18).

PMID: 31487892 PMC: 6766017. DOI: 10.3390/ma12182851.

Defect Chemistry and Na-Ion Diffusion in NaFe(PO) Cathode Material.

Kuganathan N, Chroneos A Materials (Basel). 2019; 12(8).

PMID: 31027175 PMC: 6515689. DOI: 10.3390/ma12081348.

Defects, dopants and Mg diffusion in MgTiO.

Kuganathan N, Iyngaran P, Vovk R, Chroneos A Sci Rep. 2019; 9(1):4394.

PMID: 30867514 PMC: 6416248. DOI: 10.1038/s41598-019-40878-y.

References

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

Winter M, Brodd R . What are batteries, fuel cells, and supercapacitors?. Chem Rev. 2005; 104(10):4245-69. DOI: 10.1021/cr020730k. View

Ellis B, Makahnouk W, Makimura Y, Toghill K, Nazar L . A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries. Nat Mater. 2007; 6(10):749-53. DOI: 10.1038/nmat2007. View

Armand M, Tarascon J . Building better batteries. Nature. 2008; 451(7179):652-7. DOI: 10.1038/451652a. View

Nishimura S, Kobayashi G, Ohoyama K, Kanno R, Yashima M, Yamada A . Experimental visualization of lithium diffusion in LixFePO4. Nat Mater. 2008; 7(9):707-11. DOI: 10.1038/nmat2251. View

Nishimura S, Hayase S, Kanno R, Yashima M, Nakayama N, Yamada A . Structure of Li2FeSiO4. J Am Chem Soc. 2008; 130(40):13212-3. DOI: 10.1021/ja805543p. View

Simon P, Gogotsi Y . Materials for electrochemical capacitors. Nat Mater. 2008; 7(11):845-54. DOI: 10.1038/nmat2297. View

Nishimura S, Nakamura M, Natsui R, Yamada A . New lithium iron pyrophosphate as 3.5 V class cathode material for lithium ion battery. J Am Chem Soc. 2010; 132(39):13596-7. DOI: 10.1021/ja106297a. View

Armstrong A, Kuganathan N, Islam M, Bruce P . Structure and lithium transport pathways in Li2FeSiO4 cathodes for lithium batteries. J Am Chem Soc. 2011; 133(33):13031-5. DOI: 10.1021/ja2018543. View

10.

Masquelier C, Croguennec L . Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries. Chem Rev. 2013; 113(8):6552-91. DOI: 10.1021/cr3001862. View

11.

Sathiya M, Rousse G, Ramesha K, Laisa C, Vezin H, Sougrati M . Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat Mater. 2013; 12(9):827-35. DOI: 10.1038/nmat3699. View

12.

Afyon S, Worle M, Nesper R . A lithium-rich compound Li7Mn(BO3)3 containing Mn2+ in tetrahedral coordination: a cathode candidate for lithium-ion batteries. Angew Chem Int Ed Engl. 2013; 52(48):12541-4. DOI: 10.1002/anie.201307655. View

13.

Jay E, Rushton M, Chroneos A, Grimes R, Kilner J . Genetics of superionic conductivity in lithium lanthanum titanates. Phys Chem Chem Phys. 2014; 17(1):178-83. DOI: 10.1039/c4cp04834b. View

14.

Kempaiah Devaraju M, Truong Q, Hyodo H, Sasaki Y, Honma I . Synthesis, characterization and observation of antisite defects in LiNiPO4 nanomaterials. Sci Rep. 2015; 5:11041. PMC: 4473642. DOI: 10.1038/srep11041. View

15.

Kuganathan N, Iyngaran P, Chroneos A . Lithium diffusion in LiFeO. Sci Rep. 2018; 8(1):5832. PMC: 5895795. DOI: 10.1038/s41598-018-24168-7. View

16.

Kordatos A, Kuganathan N, Kelaidis N, Iyngaran P, Chroneos A . Defects and lithium migration in LiCuO. Sci Rep. 2018; 8(1):6754. PMC: 5928103. DOI: 10.1038/s41598-018-25239-5. View

17.

Kuganathan N, Ganeshalingam S, Chroneos A . Defects, Dopants and Lithium Mobility in Li V (P O ) (PO ) . Sci Rep. 2018; 8(1):8140. PMC: 5970228. DOI: 10.1038/s41598-018-26597-w. View

18.

Kuganathan N, Kordatos A, Chroneos A . LiSnO as a Cathode Material for Lithium-ion Batteries: Defects, Lithium Ion Diffusion and Dopants. Sci Rep. 2018; 8(1):12621. PMC: 6105723. DOI: 10.1038/s41598-018-30554-y. View

19.

Vanderbilt . Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys Rev B Condens Matter. 1990; 41(11):7892-7895. DOI: 10.1103/physrevb.41.7892. View