immittance spectroscopy models, data fitting, and analysis
DESCRIPTION
IMMITTANCE SPECTROSCOPY Models, data fitting, and analysis. J. Ross Macdonald IMSPEMAS Workshop Warsaw 9/2003. MATERIAL/ELECTRODE CHARACTERIZATION WITH IS. Bulk resistivity and dispersion Bulk dielectric constant Mobile charge concentrations Mobilities and valence numbers - PowerPoint PPT PresentationTRANSCRIPT
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IMMITTANCE SPECTROSCOPYModels, data fitting, and analysis
J. Ross MacdonaldIMSPEMAS Workshop
Warsaw 9/2003
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MATERIAL/ELECTRODE CHARACTERIZATION WITH IS
• Bulk resistivity and dispersion• Bulk dielectric constant• Mobile charge concentrations• Mobilities and valence numbers• Bulk dissociation and recombination rates• Electrode reaction rate constant• Electrode adsorption rate constant• Other fit-model parameters
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IMMITTANCE SPECTROSCOPY
• Impedance Spectroscopy
• Dielectric Spectroscopy
• Data Analysis• CNLS; INVERSION
• LEVM ---- LEVMW V. 8
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CNLS-LEVM-LEVMW
• CNLS: Complex nonlinear least squares fitting. Fit complex data to a model whose parts satisfy the
Kronig-Kramers transform relations
• LEVMW: Windows version of LEVM, a free general CNLS fitting and inversion program. Download it and its manual from http://www.physics.unc.edu/~macd/
• LEVMW can accurately fit data to K0, K1, and many other models. It allows temporal response to be calculated from frequency response and vice versa
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ELECTRODE EFFECTS AND SLOPES
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BULK K0 AND K1 FIT RESULTS
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NEARLY CONSTANT LOSS
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CONCLUSIONS
• The Moynihan original modulus formalism dispersion model is theoretically and experimentally incorrect and should be replaced by the corrected modulus formalism.
• The corrected modulus formalism is isomorphic to the Scher-Lax microscopic model and leads to virtually independent of temperature and ionic concentration. 1
1/3,C
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• The variable-correlation assumption of the OMF and NCM is unsupported by fits of experimental data using the CK1 CMF model.
• The cutoff model is much superior to all coupling models and requires no ad hoc assumptions.
• Nearly-constant-loss behavior is likely to be associated with coupling between vibrating ions and induced dipoles of the bulk material. A microscopic model of the process is needed.
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MATERIAL CHARACTERIZATION
• Conduction characterIntrinsically conducting:
a. Completely blocking electrodesb. Partially blocking electrodes
Intrinsically insulating:a. Dielectric: no mobile chargeb. Leaky dielectric: surface or bulk impurity conduction
• Charge characteristicsSupported: strong supporting electrolyte, as in liquidsUnsupported: no supporting electrolyte, as in glasses, solid
electrolytes, semiconductors
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