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Title: A basic thin film study of spinel LiMn{sub 2}O{sub 4} as a possible cathode material for lithium secondary cells

Abstract

In a series of fundamental studies on the cathode active materials for a lithium secondary cell using geometrically well-defined sample electrodes, thin films of spinel LiMn{sub 2}O{sub 4} on a platinum plate were investigated in this work in an LiClO{sub 4}/propylene carbonate solution. These pyrolytically prepared films exhibit reversible extraction/insertion behavior for lithium under galvanostatic charge/discharge cycling between 4.3--3.5 V. The chemical diffusion coefficient of lithium in Li{sub x}Mn{sub 2}O{sub 4} determined by the galvanostatic intermittent titration technique (GITT) was in the order of 10{sup {minus}7}--10{sup {minus}10} cm{sup 2} {center_dot} s{sup {minus}1} within a spinel single-phase region of 0.6 < x < 1.0 and increased with increasing x.

Authors:
;  [1]
  1. Keio Univ., Kouhoku, Yokohama (Japan)
Publication Date:
OSTI Identifier:
162906
Report Number(s):
CONF-950412-
ISBN 1-55899-296-0; TRN: IM9604%%10
Resource Type:
Book
Resource Relation:
Conference: Spring meeting of the Materials Research Society (MRS), San Francisco, CA (United States), 17-21 Apr 1995; Other Information: PBD: 1995; Related Information: Is Part Of Materials for electrochemical energy storage and conversion -- Batteries, capacitors and fuel cells; Doughty, D.H. [ed.] [Sandia National Labs., Albuquerque, NM (United States)]; Vyas, B. [ed.] [AT and T Bell Labs., Murray Hill, NJ (United States)]; Takamura, Tsutomu [ed.] [Rikkyo Univ., Tokyo (Japan)]; Huff, J.R. [ed.] [Ballard Power Corp., Albuquerque, NM (United States)]; PB: 463 p.; Materials Research Society symposium proceedings, Volume 393
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; LITHIUM OXIDES; CHEMICAL PREPARATION; MANGANESE OXIDES; ELECTRIC BATTERIES; CATHODES; VOLTAMETRY; PYROLYSIS; X-RAY DIFFRACTION; SCANNING ELECTRON MICROSCOPY; PLATINUM; LITHIUM PERCHLORATES; CARBONIC ACID ESTERS; LITHIUM; ELECTRIC CURRENTS; ELECTRIC POTENTIAL; CURRENT DENSITY; DIFFUSION; CRYSTAL LATTICES; EXPERIMENTAL DATA

Citation Formats

Miura, Takashi, and Kishi, Tomiya. A basic thin film study of spinel LiMn{sub 2}O{sub 4} as a possible cathode material for lithium secondary cells. United States: N. p., 1995. Web.
Miura, Takashi, & Kishi, Tomiya. A basic thin film study of spinel LiMn{sub 2}O{sub 4} as a possible cathode material for lithium secondary cells. United States.
Miura, Takashi, and Kishi, Tomiya. 1995. "A basic thin film study of spinel LiMn{sub 2}O{sub 4} as a possible cathode material for lithium secondary cells". United States. doi:.
@article{osti_162906,
title = {A basic thin film study of spinel LiMn{sub 2}O{sub 4} as a possible cathode material for lithium secondary cells},
author = {Miura, Takashi and Kishi, Tomiya},
abstractNote = {In a series of fundamental studies on the cathode active materials for a lithium secondary cell using geometrically well-defined sample electrodes, thin films of spinel LiMn{sub 2}O{sub 4} on a platinum plate were investigated in this work in an LiClO{sub 4}/propylene carbonate solution. These pyrolytically prepared films exhibit reversible extraction/insertion behavior for lithium under galvanostatic charge/discharge cycling between 4.3--3.5 V. The chemical diffusion coefficient of lithium in Li{sub x}Mn{sub 2}O{sub 4} determined by the galvanostatic intermittent titration technique (GITT) was in the order of 10{sup {minus}7}--10{sup {minus}10} cm{sup 2} {center_dot} s{sup {minus}1} within a spinel single-phase region of 0.6 < x < 1.0 and increased with increasing x.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 1995,
month =
}

Book:
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  • The electrochemical properties of LiMn{sub 2}O{sub 4} and LiM{sub y}Mn{sub 2{minus}y}O{sub 4} (M = Ti, Ge, Fe, Zn, or Ni) were studied for different conditions of sample preparation and different degrees of cation substitution (y). This paper reports that in the voltage range 3.5-4.5 V, cells of either spinel LiMn{sub 2}O{sub 4} or {lambda}-MnO{sub 2} (made by leaching the Li from LiMn{sub 2}O{sub 4}) reversibly insert 0.4 Li per Mn at an average voltage of 4.1 V, leading to an energy density of 480 Wh/kg of cathode. Cells cycled 50 times lost less than 10% of their initial capacity, suggestingmore » that this material could be used instead of LiCoO{sub 2} of LiNiO{sub 2} as the cathode in the new generation of rocking chair batteries. Replacing Mn with cations of valence 2 (ni, Zn) or 3 (Fe) reduces the amount of Mn{sup +3} and correspondingly reduces the capacity of the cells at 4.1 V, but does not affect their cycling performance.« less
  • Highlights: • LiMn{sub 2}O{sub 4} thin films were prepared by using the mist CVD process. • An aqueous solution of lithium and manganese acetates is used for the precursor solution. • The cell with the LiMn{sub 2}O{sub 4} thin films exhibited a capacity of about 80 mAh/g. • The cell showed good cycling performance during 10 cycles. - Abstract: LiMn{sub 2}O{sub 4} cathode thin films for thin film lithium secondary batteries were prepared by using so-called the “mist CVD process”, employing an aqueous solution of lithium acetate and manganese acetate, as the source of Li and Mn, respectively. The aqueousmore » solution of starting materials was ultrasonically atomized to form mist particles, and mists were transferred by nitrogen gas to silica glass substrate to form thin films. FE-SEM observation revealed that thin films obtained by this process were dense and smooth, and thin films with a thickness of about 750 nm were obtained. The electrochemical cell with the thin films obtained by sintering at 700 °C exhibited a capacity of about 80 mAh/g, and the cell showed good cycling performance during 10 cycles.« less
  • Vacuum-evaporated Cu-doped ZnTe films have been studied as the intermediate layer between CdTe and metal contacts in CdTe/CdS thin-film solar cells for the formation of low resistance back contacts. Different metals (Au, Ni, Co) have been investigated as the contact material to the ZnTe layer. The effects of Cu concentration, ZnTe:Cu layer thickness, and ZnTe post-deposition annealing temperature on the cell performances have been investigated. The authors found that different metal contacts on the ZnTe layer lead to different doping densities in the CdTe layer and different open-circuit photovoltages of the solar cells. The possible formation of a back contactmore » diode at the CdTe/ZnTe interface was explored, based on capacitance-voltage analysis. The series resistance of the CdTe/CdS cells was reduced significantly by the introduction of the ZnTe layer. Fill factors greater than 0.76 and an energy conversion efficiency of 12.9% have been achieved using ZnTe back contacts on electrodeposited CdTe.« less
  • LiMn{sub 2}O{sub 4} thin films with different crystallizations were respectively grown at high, medium and low temperatures by pulsed laser deposition (PLD). Structures, morphologies and electrochemical properties of these three types of thin films were comparatively studied. Films grown at high temperature ({>=}873 K) possessed flat and smooth surfaces and were highly crystallized with different textures and crystal sizes depending on the deposition pressure of oxygen. However, films deposited at low temperature (473 K) had rough surfaces with amorphous characteristics. At medium temperature (673 K), the film was found to consist mainly of nano-crystals less than 100 nm with relativelymore » loose and rough surfaces, but very dense as observed from the cross-section. The film deposited at 873 K and 100 mTorr of oxygen showed an initial discharge capacity of 54.3 {mu}Ah/cm{sup 2} {mu}m and decayed at 0.28% per cycle, while the amorphous film had an initial discharge capacity of 20.2 {mu}Ah/cm{sup 2} {mu}m and a loss rate of 0.29% per cycle. Compared with the highly crystallized and the amorphous films, nano-crystalline film exhibited higher potential, more capacity and much better cycling stability. As high as 61 {mu}Ah/cm{sup 2} {mu}m of discharge capacity can be achieved with an average decaying rate of only 0.032% per cycle up to 500 cycles. The excellent performance of nano-crystalline film was correlated to its microstructures in the present study. - Graphical abstract: LiMn{sub 2}O{sub 4} thin films with different crystal size were grown at high, medium and low temperatures by PLD. Cyclic voltammograms of LiMn{sub 2}O{sub 4} thin film electrodes deposited at different temperatures show that the excellent performance of nano-crystalline film was correlated to its microstructures.« less