Na3FePO4CO3 as a cathode for hybrid-ion batteries—study of Na+/Li+ electrochemical exchange
- 47 Downloads
The Na+/Li+ electrochemical exchange in Na3FePO4CO3 (NFPC) carbonophosphate is studied for the first time in a hybrid cell using Li metal anode and Li-based electrolyte. The resulting ion-exchanged product is investigated. It is shown that the complete substitution of Na for Li is not achieved. The Na+/Li+ electrochemical exchange does not cause noticeable structural changes in the mixed Na/Li iron carbonophosphate; the initial monoclinic structure is preserved. During the first few cycles, a concurrent insertion of the Li+ and Na+ ions occurs, which is changed for the predominant Li intercalation/de-intercalation subsequently. Discharge capacity of NFPC/C achieves 61 mAh g−1 at 1 C, which is superior to that in a Na cell; the operating voltage is about 0.3 V higher. The Li/Na intercalation kinetics in the in situ formed mixed Na/Li iron carbonophosphate exceeds the sodium intercalation kinetics for NFPC cycled in a Na cell (DA+ = 1 × 10−15 cm2 s−1).
KeywordsNa3FePO4CO3 Hybrid-ion batteries Na+/Li+ electrochemical exchange
The authors are grateful to their colleagues from ISSCM SB RAS: Dr. A.A. Matvienko for registration of the SEM and EDX, Dr. I.Yu. Prosanov for registration of the FTIR spectra, S.A. Petrov for registration of the Mӧssbauer spectra, T.A. Chuprikova for registration of XRD patters.
This research was carried out within the State Assignment to ISSCM SB RAS (project 0301-2018-0001).
- 2.Nitta N, Wu F, Lee JT, Yushin G (2015) Li-ion battery materials: present and future. Mater Today 18:252–264. https://doi.org/10.1016/ j.mattod.2014.10.040Google Scholar
- 8.Kim H, Park I, Seo DH, Lee S, Kim SW, Kwon WJ, Park YU, Kim CS, Jeon S, Kang K (2012) New iron-based mixed-polyanion cathodes for lithium and sodium rechargeable batteries: combined first principles calculations and experimental study. J Am Chem Soc 134:10369–10372. dx.doi.org/. https://doi.org/10.1021/ja3038646 CrossRefPubMedGoogle Scholar
- 16.Huang W, Zhou J, Li B, Ma J, Tao S, Xia D, Chu W, Wu Z (2014) Detailed investigation of Na2.24FePO4CO3 as a cathode material for Na-ion batteries. Sci Rep 4(4188). https://doi.org/10.1038/srep04188
- 17.Kosova NV, Podugolnikov VR, Devyatkina ET, Slobodyuk AB (2014) Structure and electrochemistry of NaFePO4 and Na2FePO4F cathode materials prepared via mechanochemical route. Mater Res Bull 60:849–857. https://doi.org/10.1016/j.materresbull.2014.09.081 CrossRefGoogle Scholar
- 21.Kim H, Park I, Seo DH, Lee S, Kim SW, Kwon WJ, Park YU, Kim CS, Jeon S, Kang K (2012) New iron-based mixed-polyanion cathodes for lithium and sodium rechargeable batteries: combined first principles calculations and experimental study. J Am Chem Soc 134:10369–10372. https://doi.org/10.1021/ja3038646 CrossRefPubMedGoogle Scholar