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Differentiating Double-Layer, Psuedocapacitance, and Battery-like Mechanisms by Analyzing Impedance Measurements in
Jesse S Ko1, Chun-Han Lai2, Jeffrey W Long3
1Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
ACS Applied Materials & Interfaces
|March 3, 2020
Summary
A new 3D Bode analysis technique precisely distinguishes electrochemical energy storage mechanisms. This method aids in understanding fast lithium-ion storage in advanced materials by analyzing capacitance and phase angle across voltage and frequency.
Area of Science:
- Electrochemistry
- Materials Science
- Energy Storage
Background:
- Electrochemical energy storage involves capacitive, pseudocapacitive, and battery-like mechanisms.
- Advanced materials often combine multiple storage mechanisms, complicating behavior analysis.
- Understanding these mechanisms is crucial for developing high-capacity, high-rate energy storage.
Purpose of the Study:
- To introduce and validate a "3D Bode analysis" technique for studying electrochemical energy storage.
- To identify key descriptors for fast lithium-ion storage processes.
- To differentiate between capacitive, pseudocapacitive, and battery-like storage behaviors.
Main Methods:
- Applied AC impedance spectroscopy, measuring real capacitance (C") and phase angle (ϕ).
- Utilized a 3D Bode analysis, plotting C" and ϕ against frequency (f) and applied DC cell voltage.
- Compared 3D Bode analysis with traditional cyclic voltammetry kinetic analyses.
Main Results:
- Double-layer processes showed constant C"/ϕ across voltage, decreasing linearly at higher frequencies.
- Pseudocapacitance exhibited increased C" with high retention at higher frequencies; low ϕ indicated kinetic limitations.
- Battery-like processes displayed high C" only at specific charge-storage voltages.
Conclusions:
- 3D Bode analysis provides detailed mapping of charge-storage dynamics.
- This technique offers superior delineation of storage mechanisms compared to cyclic voltammetry.
- The study identifies key descriptors for fast Li-ion storage, aiding material design.
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