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

Title: Development and utility of manganese oxides as cathodes in lithiuim batteries.

Abstract

Manganese oxides have a long history of serving as a cathode in charge storage applications. Electrolytic manganese dioxide (EMD) is widely used in alkaline batteries and MnO{sub 2} originally was part of the Leclanch{acute e} wet cell patented in 1866. Leclanch{acute e} wet cells used a naturally occurring MnO{sub 2} ore with Zn metal as anode and ammonium chloride electrolyte. While there are a vast number of topics to discuss on manganese oxides, in this short paper, two topics researched at Argonne over the last 12 years are highlighted. First, the addition of lithia (Li{sub 2}O) as a stabilizing component in 3 V alpha-MnO{sub 2} is examined. Second, an overview of the evolution of layered-layered composite-structured electrodes derived from the lithium-manganese oxide (Li{sub 2}MnO{sub 3}) layered rock-salt phase is presented.

Authors:
;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
EE; USDOE Office of Science (SC)
OSTI Identifier:
919323
Report Number(s):
ANL/CMT/JA-55668
Journal ID: ISSN 0378-7753; JPSODZ; TRN: US200822%%28
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Power Sources; Journal Volume: 165; Journal Issue: 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; CATHODES; LITHIUM; MANGANESE OXIDES; METAL-NONMETAL BATTERIES; LITHIUM OXIDES

Citation Formats

Johnson, C. S., and Chemical Engineering. Development and utility of manganese oxides as cathodes in lithiuim batteries.. United States: N. p., 2007. Web. doi:10.1016/j.jpowsour.2006.10.040.
Johnson, C. S., & Chemical Engineering. Development and utility of manganese oxides as cathodes in lithiuim batteries.. United States. doi:10.1016/j.jpowsour.2006.10.040.
Johnson, C. S., and Chemical Engineering. Mon . "Development and utility of manganese oxides as cathodes in lithiuim batteries.". United States. doi:10.1016/j.jpowsour.2006.10.040.
@article{osti_919323,
title = {Development and utility of manganese oxides as cathodes in lithiuim batteries.},
author = {Johnson, C. S. and Chemical Engineering},
abstractNote = {Manganese oxides have a long history of serving as a cathode in charge storage applications. Electrolytic manganese dioxide (EMD) is widely used in alkaline batteries and MnO{sub 2} originally was part of the Leclanch{acute e} wet cell patented in 1866. Leclanch{acute e} wet cells used a naturally occurring MnO{sub 2} ore with Zn metal as anode and ammonium chloride electrolyte. While there are a vast number of topics to discuss on manganese oxides, in this short paper, two topics researched at Argonne over the last 12 years are highlighted. First, the addition of lithia (Li{sub 2}O) as a stabilizing component in 3 V alpha-MnO{sub 2} is examined. Second, an overview of the evolution of layered-layered composite-structured electrodes derived from the lithium-manganese oxide (Li{sub 2}MnO{sub 3}) layered rock-salt phase is presented.},
doi = {10.1016/j.jpowsour.2006.10.040},
journal = {J. Power Sources},
number = 2007,
volume = 165,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • The mixed-metal phases, (Li{sub 2}Mn{sub 1-y}Fe{sub y}P{sub 2}O{sub 7}, 0 {le} y {le} 1), were synthesized using a 'wet method', and found to form a solid solution in the P2{sub 1}/a space group. Both thermogravimetric analysis and magnetic susceptibility measurements confirm the 2+ oxidation state for both the Mn and Fe. The electrochemical capacity improves as the Fe concentration increases, as do the intensities of the redox peaks of the cyclic voltammogram, indicating higher lithium-ion diffusivity in the iron phase. The two Li{sup +} ions in the three-dimensional tunnel structure of the pyrophosphate phase allows for the cycling of moremore » than one lithium per redox center. Cyclic voltammograms show a second oxidation peak at 5 V and 5.3 V, indicative of the extraction of the second lithium ion, in agreement with ab initio computation predictions. Thus, electrochemical capacities exceeding 200 Ah/kg may be achieved if a stable electrolyte is found.« less
  • Li-rich and stoichiometric Li1Mn1.5Ni0.5O4 (LMNO) cathode films have been prepared by magnetron sputtering. Sputtering from a Li stoichiometric target yields Li-rich films composed of spinel, layered and monoclinic phases. Films obtained from a Li deficient target are mostly made of a spinel phase and little layered material. The resulting cathode thin films have good capacity retention and very high rate capability. The reaction mechanism has been investigated by XRD and HRTEM and evidences the reversible formation of a spinel phase, as is also found for the powder samples. The film geometry enables to understand the effect of coatings (ZnO ormore » LiPON). Coating high voltage cathodes reduces the coulombic losses but at the price of rate performance. Nonetheless, these coated sputtered electrode thin films offer a higher rate capability than other LMNO thin films obtained by other physical vapor deposition techniques.« less
  • This paper presents the fabrication and characterization of sodium manganese oxide cathode thin films for rechargeable Na-ion batteries. Layered oxide compounds of nominal compositions Na0.6MnO2 and Na1.0MnO2 have been prepared by radio frequency magnetron sputtering and post-annealing at high temperatures under various conditions. The Na0.6MnO2 thin films possess either a hexagonal or orthorhombic structure while the Na1.0MnO2 films crystallize in a monoclinic structure, as shown by X-ray diffraction and X-ray absorption spectroscopy results. The potential profiles of the film cathodes are characterized by features similar to those measured for the powders and exhibit reversible storage capacities in the range ofmore » 50-60 Ah cm-2 m-1, which correspond to about 120-140 mAh g-1, and are maintained over 80 cycles.« less
  • P2-type sodium nickel manganese oxide-based cathode materials with higher energy densities are prime candidates for applications in rechargeable sodium ion batteries. A systematic study combining in situ high energy X-ray diffraction (HEXRD), ex situ Xray absorption fine spectroscopy (XAFS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (SSNMR) techniques was carried out to gain a deep insight into the structural evolution of P2-Na 0.66Ni 0.33-xZn xMn 0.67O 2 (x = 0, 0.07) during cycling. In situ HEXRD and ex situ TEM measurements indicate that an irreversible phase transition occurs upon sodium insertion-extraction of Na 0.66Ni 0.33Mn 0.67O 2. Zincmore » doping of this system results in a high structural reversibility. XAFS measurements indicate that both materials are almost completely dependent on the Ni 4+/Ni 3+/ Ni 2+ redox couple to provide charge/discharge capacity. SS-NMR measurements indicate that both reversible and irreversible migration of transition metal ions into the sodium layer occurs in the material at the fully charged state. The irreversible migration of transition metal ions triggers a structural distortion, leading to the observed capacity and voltage fading. Our results allow a new understanding of the importance of improving the stability of transition metal layers.« less