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Title: Divalent Iron Nitridophosphates: A New Class of Cathodes Materials for Li-ion Batteries

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL)
Sponsoring Org.:
USDOE SC OFFICE OF SCIENCE (SC)
OSTI Identifier:
1122777
Report Number(s):
BNL-103475-2013-JA
R&D Project: EST431; KC0207010
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 20
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Divalent Iron Nitridophosphates

Citation Formats

Liu J., Yu X., Hu, E., Nam, KW, Yang, XQ, and Khalifah, P.G.. Divalent Iron Nitridophosphates: A New Class of Cathodes Materials for Li-ion Batteries. United States: N. p., 2013. Web. doi:10.1021/cm402567e.
Liu J., Yu X., Hu, E., Nam, KW, Yang, XQ, & Khalifah, P.G.. Divalent Iron Nitridophosphates: A New Class of Cathodes Materials for Li-ion Batteries. United States. doi:10.1021/cm402567e.
Liu J., Yu X., Hu, E., Nam, KW, Yang, XQ, and Khalifah, P.G.. Wed . "Divalent Iron Nitridophosphates: A New Class of Cathodes Materials for Li-ion Batteries". United States. doi:10.1021/cm402567e.
@article{osti_1122777,
title = {Divalent Iron Nitridophosphates: A New Class of Cathodes Materials for Li-ion Batteries},
author = {Liu J. and Yu X. and Hu, E. and Nam, KW and Yang, XQ and Khalifah, P.G.},
abstractNote = {},
doi = {10.1021/cm402567e},
journal = {Chemistry of Materials},
number = ,
volume = 20,
place = {United States},
year = {Wed Sep 18 00:00:00 EDT 2013},
month = {Wed Sep 18 00:00:00 EDT 2013}
}
  • A series of electroactive spinel compounds, LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} (0.1{le}x{le}0.5), has been studied by crystallographic, spectroscopic, and electrochemical methods and by electron microscopy. These spinels are nearly identical in structure to cubic LiMn{sub 2}O{sub 4} and successfully undergo reversible Li intercalation. The electrochemical data show a remarkable reversible electrochemical process at 4.9 V which is attributed to the oxidation of Cu{sup 2+} to Cu{sup 3+}. The inclusion of Cu in the spinel structure enhances the electrochemical stability of these materials upon cycling. The initial capacity of LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels decreases with increasing x from 130 mAh/g inmore » LiMn{sub 2}O{sub 4} (x = 0) to 70 mAh/g in LiMn{sub 1.5}Cu{sub 0.5}O{sub 4} (x = 0.5). The data also show slight shifts to higher voltage for the delithiation reaction that normally occurs at 4.1 V in standard Li{sub 1{minus}x}Mn{sub 2}O{sub 4} electrodes (1{ge}x{ge}0) corresponding to the oxidation of Mn{sup 3+} to Mn{sup 4+}. Although the powder X-ray diffraction pattern of LiMn{sub 1.5}Cu{sub 0.5}O{sub 4} shows a single-phase spinel product, neutron diffraction data show a small but significant quantity of an impurity phase, the composition and structure of which could not be identified. X-ray absorption spectroscopy was used to gather information about the oxidation states of the manganese and copper ions. The composition of the spinel component in the LiMn{sub 1.5}Cu{sub 0.5}O{sub 4} was determined from X-ray diffraction and X-ray absorption near-edge spectroscopy to be Li{sub 1.01}Mn{sub 1.67}Cu{sub 0.32}O{sub 4}, suggesting to a best approximation that the impurity in the sample was a lithium-copper-oxide phase. The substitution of manganese by copper enhances the reactivity of the spinel structure toward hydrogen: the compounds are more easily reduced at moderate temperature ({approximately} 200 C) than LiMn{sub 2}O{sub 4}.« less
  • Electrochemical data obtained from lithium cycling in LiCu{sub x}Mn{sub 2{minus}x}O{sub 4} spinels (0.1 {le} x {le} 0.5) show a remarkable, highly reversible, electrochemical cycling behavior at 4.9 V. In situ X-ray absorption near edge structure spectroscopy revealed that this ultrahigh voltage is due to the existence of the Cu{sup 2+}/Cu{sup 3+} redox couple. The origin of the high stability at the 5 V region was studied with the in situ X-ray diffraction technique. It was found that the unit cell dimension undergoes minimal change during charge-discharge cycles at the 5 V plateau.