Li{sub 2}O removal from Li{sub 5}FeO{sub 4} - a cathode precursor for lithium-ion batteries.
Lithium has been extracted both electrochemically and chemically from the defect antifluorite-type structure, Li{sub 5}FeO{sub 4} (5Li{sub 2}O {center_dot} Fe{sub 2}O{sub 3}). The electrochemical data show that four lithium ions can be removed from Li{sub 5}FeO{sub 4} between 3.5 and 4.5 V. vs Li{sup 0}. X-ray absorption spectroscopy (XAS) data of electrochemically delithiated samples show evidence of some Fe{sup 3+} to Fe{sup 4+} oxidation during the initial charge. On the other hand, XAS data of chemically delithiated samples show no evidence of Fe{sup 3+} to Fe{sup 4+} oxidation, but rather a change in coordination of the Fe{sup 3+} ions from tetrahedral to octahedral coordination, suggesting that lithium extraction from Li{sub 5}FeO{sub 4} is accompanied predominantly by the release of oxygen, the net loss being lithia (Li{sub 2}O); the residual lithium-iron-oxide product has a Fe{sub 2}O{sub 3}-rich composition. The high lithium content in Li{sub 5}FeO{sub 4} renders it an attractive cathode precursor for loading the graphite (C{sub 6}) anode of lithium-ion electrochemical cells with sufficient lithium to enable the discharge of a charged component in the parent cathode, Li{sub 1.2}V{sub 3}O{sub 8}, as well as the residual Fe{sub 2}O{sub 3}-rich component. The electrochemical behavior of C{sub 6}/Li{sub 5}FeO{sub 4}?Li{sub 1/2}V{sub 3}O{sub 8} lithium-ion cells is compared to C{sub 6}/Li{sub 2}MnO{sub 3}?Li{sub 1.2}V{sub 3}O{sub 8} cells containing a layered Li{sub 2}MnO{sub 3} (Li{sub 2}O {center_dot} MnO{sub 2}) cathode precursor with a lower Li{sub 2}O content, from which lithia can be extracted at higher potentials, typically >4 V vs metallic lithium. The ability to remove Li{sub 2}O electrochemically from metal oxide host structures with a high lithium content, such as Li{sub 5}FeO{sub 4}, has implications for Li-air cells.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- EE; NSERC - Canada
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 973035
- Report Number(s):
- ANL/CSE/JA-65785
- Journal Information:
- Chem. Mater., Journal Name: Chem. Mater. Journal Issue: 3 ; Feb. 9, 2010 Vol. 22; ISSN CMATEX; ISSN 0897-4756
- Country of Publication:
- United States
- Language:
- ENGLISH
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