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Title: The Science of Electrode Materials for Lithium Batteries

Abstract

Rechargeable lithium batteries continue to play the central role in power systems for portable electronics, and could play a role of increasing importance for hybrid transportation systems that use either hydrogen or fossil fuels. For example, fuel cells provide a steady supply of power, whereas batteries are superior when bursts of power are needed. The National Research Council recently concluded that for dismounted soldiers "Among all possible energy sources, hybrid systems provide the most versatile solutions for meeting the diverse needs of the Future Force Warrior. The key advantage of hybrid systems is their ability to provide power over varying levels of energy use, by combining two power sources." The relative capacities of batteries versus fuel cells in a hybrid power system will depend on the capabilities of both. In the longer term, improvements in the cost and safety of lithium batteries should lead to a substantial role for electrochemical energy storage subsystems as components in fuel cell or hybrid vehicles. We have completed a basic research program for DOE BES on anode and cathode materials for lithium batteries, extending over 6 years with a 1 year phaseout period. The emphasis was on the thermodynamics and kinetics of the lithiationmore » reaction, and how these pertain to basic electrochemical properties that we measure experimentally — voltage and capacity in particular. In the course of this work we also studied the kinetic processes of capacity fade after cycling, with unusual results for nanostructued Si and Ge materials, and the dynamics underlying electronic and ionic transport in LiFePO4. This document is the final report for this work.« less

Authors:
Publication Date:
Research Org.:
California Institute of Technology
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
900899
Report Number(s):
DOE/ER/15035-1
DE-FG03-00ER15035; TRN: US200722%%278
DOE Contract Number:
FG02-00ER15035
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; ELECTRODES; ENERGY SOURCES; ENERGY STORAGE; FOSSIL FUELS; FUEL CELLS; HYBRID SYSTEMS; LITHIUM; POWER SYSTEMS; RESEARCH PROGRAMS; TRANSPORTATION SYSTEMS; Lithium, Battery, Nanophase Anode, Cathode, TEM, Cycle Lifetimes, Phase Stability, Electrode Materials, Olivine, LiFePO4, CiCoO2, EELS,

Citation Formats

Fultz, Brent. The Science of Electrode Materials for Lithium Batteries. United States: N. p., 2007. Web. doi:10.2172/900899.
Fultz, Brent. The Science of Electrode Materials for Lithium Batteries. United States. doi:10.2172/900899.
Fultz, Brent. Thu . "The Science of Electrode Materials for Lithium Batteries". United States. doi:10.2172/900899. https://www.osti.gov/servlets/purl/900899.
@article{osti_900899,
title = {The Science of Electrode Materials for Lithium Batteries},
author = {Fultz, Brent},
abstractNote = {Rechargeable lithium batteries continue to play the central role in power systems for portable electronics, and could play a role of increasing importance for hybrid transportation systems that use either hydrogen or fossil fuels. For example, fuel cells provide a steady supply of power, whereas batteries are superior when bursts of power are needed. The National Research Council recently concluded that for dismounted soldiers "Among all possible energy sources, hybrid systems provide the most versatile solutions for meeting the diverse needs of the Future Force Warrior. The key advantage of hybrid systems is their ability to provide power over varying levels of energy use, by combining two power sources." The relative capacities of batteries versus fuel cells in a hybrid power system will depend on the capabilities of both. In the longer term, improvements in the cost and safety of lithium batteries should lead to a substantial role for electrochemical energy storage subsystems as components in fuel cell or hybrid vehicles. We have completed a basic research program for DOE BES on anode and cathode materials for lithium batteries, extending over 6 years with a 1 year phaseout period. The emphasis was on the thermodynamics and kinetics of the lithiation reaction, and how these pertain to basic electrochemical properties that we measure experimentally — voltage and capacity in particular. In the course of this work we also studied the kinetic processes of capacity fade after cycling, with unusual results for nanostructued Si and Ge materials, and the dynamics underlying electronic and ionic transport in LiFePO4. This document is the final report for this work.},
doi = {10.2172/900899},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}

Technical Report:

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  • OAK-B135 (IPLD Cleared) Basic materials science research on materials for anodes and cathodes in electrochemical cells. The work is a mix of electrochemical measurements and analysis of the materials by transmission electron microscopy and x-ray diffractometry. The emphasis is on the thermodynamics and kinetics of how lithium is intercalated and de-intercalleted into anode and cathod materials.
  • The object of this project is to develop new electrolyte and cathode materials for rechargeable lithium batteries, especially for lithium ion and lithium polymer batteries. Enhancing performance, reducing cost, and replacing toxic materials by environmentally benign materials, are strategic goals of DOE in lithium battery research. This proposed project will address these goals on two important material studies, namely the new electrolytes and new cathode materials. For the new electrolyte materials, aza based anion receptors as additives, organic lithium salts and plasticizers which have been developed by BNL team under Energy Research programs of DOE, will be evaluated by Gouldmore » for potential use in commercial battery cells. All of these three types of compounds are aimed to enhance the conductivity and lithium transference number of lithium battery electrolytes and reduce the use of toxic salts in these electrolytes. BNL group will be working closely with Gould to further develop these compounds for commercialization. For the cathode material studies, BNL efforts wi U be focused on developing new superior characterization methclds, especially in situ techniques utilize the unique user facility of DOE at BNL, namely the National Synchrotrons Light Source (NSLS). In situ x-ray absorption and x-ray diftlaction spectroscopy will be used to study the relationship between performance and the electronic and structural characteristics of intercalation compounds such as LiNi0 2, LiCo0 2, and LiMn 20 4 spinel. The study will be focused on LiMn 20 4 spinel materials. Gould team will contribute their expertise in choosing the most promising compounds, providing overall performance requirements, and will use the results of this study to guide their procedure for quality control. The knowledge gained through this project will not only benefit Gould and BNL, but will be very valuable to the scientific community in battery research.« less
  • Surface layers on lithium electrodes formed in several solvents including dimethyl carbonate (DMC), diethyl carbonate (DEC), polyethylene glycol 400 dimethyl ether (PEG400DME), and propylene carbonate (PC) have been studied by Raman spectroscopy. Both DMC and DEC were used singly, and also mixed with either methyl acetate or methyl formate. The Raman spectra showed that passive films formed on the Li surface in different solvents may have different chemical structures, which changed during the charging and discharging processes. A solid film of fullerene C6O, which could be used as a cathode in Li rechargeable batteries, was examined in the PEG400DME solutionmore » by both electrochemical and Raman spectroscopy. Cyclic voltammograms (CVs) showed five redox peaks which suggested the formation of C6O(-), C6O(2-), C6O(3-), C6O(4-), and C6O(5-). Raman spectra obtained from thin C6O film indicated that the thin fulleride film dissolved in the PEG400DME/LiClO(4) solution at negative potentials.... Lithium electrode, Fullerenes, Electrochemistry, Raman spectroscopy.« less
  • (ALTC = active lithium/thionyl chloride.) We have investigated the corrosion susceptibilities of eight alternate battery pin materials in 1.5M LiAlCl/sub 4//SOCl/sub 2/ electrolyte using ampule exposure and electrochemical tests. The thermal expansion coefficients of these candidate materials are expected to match Sandia-developed Li-corrosion resistant glasses. The corrosion resistances of the candidate materials, which included three stainless steels (15-5 PH, 17-4 PH, and 446), three Fe-Ni glass sealing alloys (Kovar, Alloy 52, and Niromet 426), a Ni-based alloy (Hastelloy B-2) and a zirconium-based alloy (Zircaloy), were compared to the reference materials Ni and 316L SS. All of the candidate materials showedmore » some evidence of corrosion and, therefore, did not perform as well as the reference materials. The Hastelloy B-2 and Zircaloy are clearly unacceptable materials for this application. Of the remaining alternate materials, the 446 SS and Alloy 52 are the most promising candidates.« less