Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Thermodynamic Stability of Transition‐Metal‐Substituted LiMn 2− x M x O 4 (M=Cr, Fe, Co, and Ni) Spinels

Journal Article · · ChemPhysChem
 [1];  [1];  [2];  [2];  [1]
  1. Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California Davis One Shields Ave. Davis CA 95616 USA
  2. McKetta Department of Chemical Engineering University of Texas at Austin 200 E. Dean Keeton St. Stop C0400 Austin TX 78712 USA
+ Show Author Affiliations
Abstract

The formation enthalpies from binary oxides of LiMn 2 O 4 , LiMn 2− x Cr x O 4 ( x= 0.25, 0.5, 0.75 and 1), LiMn 2− x Fe x O 4 ( x= 0.25 and 0.5), LiMn 2− x Co x O 4 ( x= 0.25, 0.5, and 0.75) and LiMn 1.75 Ni 0.25 O 4 at 25 °C were measured by high temperature oxide melt solution calorimetry and were found to be strongly exothermic. Increasing the Cr, Co, and Ni content leads to more thermodynamically stable spinels, but increasing the Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO 4 (M=Cr, Fe and Co), become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close‐to‐zero heat of mixing in LiMn 2 O 4 —LiMnMO 4 solid solutions. These data confirm that transition‐metal doping is beneficial for stabilizing these potential cathode materials for lithium‐ion batteries.

Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-03ER46053
OSTI ID:
1400455
Journal Information:
ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 13 Vol. 17; ISSN 1439-4235
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (31)

The Cr-Substituted Spinel Mn Oxides LiCryMn2−yO4(0≤y≤1): Rietveld Analysis of the Structure Modifications Induced by the Electrochemical Lithium Deintercalation journal September 1997
Progress and new directions in high temperature calorimetry journal January 1977
Electrochemical behaviour of LiM y Mn2−y O4 (M = Cu, Cr; 0 ≤y ≤ 0.4) journal February 2001
Progress and new directions in high temperature calorimetry revisited journal April 1997
High-temperature thermal behaviour of Cr-Doped LiMn2O4 spinels synthesized by the sucrose-aided combustion method journal September 2007
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells journal April 1994
Synthesis and characterization of 5 V insertion material of Li[FeyMn2−y]O4 for lithium-ion batteries journal April 2001
Lithium insertion into host materials: the key to success for Li ion batteries journal September 1999
Valence analysis of transition metal ions in spinel LiMnMO4 (M = Ti, Cr, Mn, Co) by electron energy loss spectroscopy journal December 1996
Use of Li–M–Mn–O [M=Co, Cr, Ti] spinels prepared by a sol-gel method as cathodes in high-voltage lithium batteries journal March 1999
Electrochemical characteristics of cobalt-doped LiCoyMn2−yO4 (0≤y≤0.66) spinels synthesized at low temperature from CoxMn3−xO4 precursors journal January 2000
Three-volt lithium-ion battery with Li[Ni1/2Mn3/2]O4 and the zero-strain insertion material of Li[Li1/3Ti5/3]O4 journal June 2003
Preparation and electrochemical investigation of LiMn2 − xMexO4 (Me: Ni, Fe, and x = 0.5, 1) cathode materials for secondary lithium batteries journal October 1997
Solid-state redox potentials for Li[Me1/2Mn3/2]O4 (Me: 3d-transition metal) having spinel-framework structures: a series of 5 volt materials for advanced lithium-ion batteries journal September 1999
Electrochemical properties of LiMn2O4 thin films: suggestion of factors for excellent rechargeability journal April 2000
Enhanced cycle ability of spinel LiMn2O4 by controlling the phase purity and structural strain journal November 2012
Search for new manganese–cobalt oxides as positive electrode materials for lithium batteries journal December 2007
Lithium batteries: Status, prospects and future journal May 2010
Thermochemistry of Li1+xMn2−xO4 (0⩽x⩽1/3) spinel journal April 2005
Formation enthalpies of LaLn׳O3 (Ln׳=Ho, Er, Tm and Yb) interlanthanide perovskites journal July 2015
Charge-Coupled Substituted Garnets (Y 3– x Ca 0.5 x M 0.5 x )Fe 5 O 12 (M = Ce, Th): Structure and Stability as Crystalline Nuclear Waste Forms journal March 2015
Energetics of Ternary Nitrides:  Li−Ca−Zn−N and Ca−Ta−N Systems journal July 1997
Heat of Formation for LiMyMn2−yO4 (M=Co, Cr, Li, Mg, Ni) Spinel Solid Solution journal January 1999
First-principles study of lithium ion migration in lithium transition metal oxides with spinel structure journal January 2012
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
Progress and New Directions in Calorimetry: A 2014 Perspective journal October 2014
The Spinel Phases LiM[sub y]Mn[sub 2−y]O[sub 4] (M = Co, Cr, Ni) as the Cathode for Rechargeable Lithium Batteries journal January 1996
Capacity Fading on Cycling of 4 V Li∕LiMn[sub 2]O[sub 4] Cells journal January 1997
M[sup 3+]-Modified LiMn[sub 2]O[sub 4] Spinel Intercalation Cathodes journal January 1997
Delithiation Mechanisms in Acid of Spinel LiMn 2-x M x O 4 (M = Cr, Fe, Co, and Ni) Cathodes journal December 2014
Thermodynamics of manganese oxides: Effects of particle size and hydration on oxidation-reduction equilibria among hausmannite, bixbyite, and pyrolusite journal August 2012

Similar Records

Synthesis and characterization of Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}M{sub x}O{sub 2.625+{delta}} (M=Ga, 0.125=<x=<0.500 and M=Fe, 0.125=<x=<0.875)
Journal Article · Mon May 15 00:00:00 EDT 2006 · Journal of Solid State Chemistry · OSTI ID:20785008
ZrO{sub 2}- and Li{sub 2}ZrO{sub 3}-stabilized spinel and layered electrodes for lithium batteries.
Journal Article · Mon Sep 01 00:00:00 EDT 2003 · Electrochem. Commun. · OSTI ID:961373
The spinel phases LiM{sub y}Mn{sub 2{minus}y}O{sub 4} (M = Co, Cr, Ni) as the cathode for rechargeable lithium batteries
Journal Article · Sun Dec 31 23:00:00 EST 1995 · Journal of the Electrochemical Society · OSTI ID:201403

Related Subjects