How to calculate capacitance by EC methods

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Electrochemical characterization
• Cyclic voltammetry(CV) ‐ study the electrochemical properties of an analyte
in solution
• Galvanostatic charge/discharge(GCD) ‐ test the capacitance & stability of ECs • Electrochemical Impedance Spectroscopy(EIS) ‐ evaluate the R‐C property of ECs
Other forms I C= v
If Capacitance is constant and Rs→0 if j→0
C=
Qa + Qc 2ΔV
1 C= 2ΔV

V final
i dV / dt
Vinital
dV
IΔt C= ΔV
Capacitance calculated from CV
Potential/V
• • • • • • • Brunauer‐Emmett‐Teller (BET) Electron Microscopy (SEM) Transmission electron microscopy(TEM) X‐ray photoelectron spectroscopy(XPS) X‐ray powder diffraction(XRD) Fourier transform infrared (FTIR), Raman Thermogravimetic analysis (TGA)/DTA, DSC
Capacitance calculated from GCD
C= jΔt (V2 − jR − V1 ) ΔV R= j
j C= dV / dt
Current/A
Time/s
Capacitance calculated from EIS C
dl
CF
Z (ω ) = R(ω ) + Z (ω ) =
Capacitance calculated from EIS
Potential/V vs SCE 10mV
Time/s
τ=
1 1 = 2πf R RC
Comparison
CCV ≈ CGCD ≥ C EIS
CV: the redox action and surface situation change GCD: charge/discharge efficiently and the change of Capacitance EIS: more information about electrode/electrolyte interface, IR drop, time constant, etc
1 jC (ω ) × ω
C’ real part of C, is the capacitance of the supercapacitor, equal to capacitance measured by constant-current discharge. C’’ is the imaginary part of the supercapacitance, where an energy dissipation by an irreversible process that can lead to a hystersis.
Electrochemical characterization of EDLCs
Electrochemical characterization of PCs
Capacitance calculated from CV
Q ∫ idt C= = V V QV = V0 + vt ∴ dV = vdt dV i ∫ v 1 ∫ idV C= = v ΔV ΔV C Cs = m
Equivalent Ciபைடு நூலகம்cuit
1 = Z ' (ω ) + jZ '' (ω ) jC (ω ) × ω 1 − ( Z '' (ω ) + jZ ' (ω )) = C (ω ) = 2 ' '' ω ( jZ (ω ) − Z (ω )) ω Z (ω ) C (ω ) = C ' (ω ) − jC '' (ω ) − Z '' (ω ) '' − Z ' (ω ) ' C (ω ) = , C (ω ) = 2 2 ω Z (ω ) ω Z (ω )
Time/s
Why the capacitance decrease with the increasement of voltage scan rate? Chemical ‐ Ions absorption/ desorption and active surface area lost Physical ‐ Swelling and shrinkage
How to calculate capacitance by EC methods
ZENG Lin 27th, September
Content
• Physical characterization • Electrochemical characterization • Work plan
Physical characterization