skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels -- 5 V cathode materials

Abstract

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 LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels are nearly identical in structure to cubic LiMn{sub 2}O{sub 4} and successfully undergo reversible Li intercalation. The electrochemical data 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+}. The data also 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 in 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). 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 whichmore » 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 XANES data 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.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Covalent Associates, Inc., Woburn, MA (US)
Sponsoring Org.:
US Department of the Army; USDOE
OSTI Identifier:
20019158
DOE Contract Number:  
W-31109-ENG-38; AC02-76CH00016
Resource Type:
Conference
Resource Relation:
Conference: 1997 Materials Research Society Fall Meeting, Boston, MA (US), 12/01/1997--12/05/1997; Other Information: PBD: 1998; Related Information: In: Materials for electrochemical energy storage and conversion II -- Batteries, capacitors and fuel cells. Materials Research Society symposium proceedings, Volume 496, by Ginley, D.S.; Doughty, D.H.; Scrosati, B.; Takamura, T.; Zhang, Z.J. [eds.], 702 pages.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; LITHIUM OXIDES; MANGANESE OXIDES; COPPER OXIDES; CATHODES; ELECTROCHEMISTRY; CRYSTAL STRUCTURE; CLATHRATES; METAL-NONMETAL BATTERIES; PHASE STUDIES; EXPERIMENTAL DATA

Citation Formats

Ein-Eli, Y, Howard, Jr, W F, Lu, S H, Mukerjee, S, McBreen, J, Vaughey, J T, and Thackeray, M M. LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels -- 5 V cathode materials. United States: N. p., 1998. Web.
Ein-Eli, Y, Howard, Jr, W F, Lu, S H, Mukerjee, S, McBreen, J, Vaughey, J T, & Thackeray, M M. LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels -- 5 V cathode materials. United States.
Ein-Eli, Y, Howard, Jr, W F, Lu, S H, Mukerjee, S, McBreen, J, Vaughey, J T, and Thackeray, M M. Wed . "LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels -- 5 V cathode materials". United States.
@article{osti_20019158,
title = {LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels -- 5 V cathode materials},
author = {Ein-Eli, Y and Howard, Jr, W F and Lu, S H and Mukerjee, S and McBreen, J and Vaughey, J T and Thackeray, M M},
abstractNote = {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 LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels are nearly identical in structure to cubic LiMn{sub 2}O{sub 4} and successfully undergo reversible Li intercalation. The electrochemical data 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+}. The data also 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 in 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). 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 XANES data 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.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1998},
month = {7}
}

Conference:
Other availability
Please see Document Availability for additional information on obtaining the full-text document. Library patrons may search WorldCat to identify libraries that hold this conference proceeding.

Save / Share: