Effects of ion insertion on cycling performance of miniaturized electrochemical capacitor of carbon nanotubes array.

Capacity degradation and ion insertion of a miniaturized electrochemical capacitor are studied using ionic liquid [EMI] [TFSI] as the electrolyte. This capacitor is featured with two comb-like electrodes of vertical carbon nanotubes, ∼70 µm in height and 20 µm in interelectrode gap. We quantify the levels of ion insertion damage with Raman spectroscopy after the electrode experiences 120 consecutive voltammetric cycles to various potential limits. Distinct structural damage emerges due to [EMI] when the negative potential reaches -1.7 V, and those due to [TFSI] arise when the positive potential reaches 1.7 V vs. RHE. Judging from the peak broadenings, [EMI] is more detrimental than [TFSI]. When the voltage window ΔU is set as less than or equal to 2.8 V, both electrode potentials are within the two intercalation limits, little or no decay is observed in 10(4) charge/discharge cycles. When ΔU is 3.4 V, the positive potential exceeds the upper limit, but the negative potential stays within the lower limit, the cell capacitance decreases moderately. When ΔU increases to 3.8 V, both electrodes suffer from damages because of exceeding the intercalation limits. And the cell capacitance decreases substantially, even leading to a premature failure.

Cycle stability of the electrochemical capacitors patterned with vertically aligned carbon nanotubes in an LiPF6-based electrolyte.

The miniature ultracapacitors, with interdigitated electrodes of vertically aligned carbon nanotubes (VACNTs) and an inter-electrode gap of 20 µm, have been prepared in the LiPF6 organic electrolyte with and without PVdF-HFP gel. PVdF-HFP between two opposing electrodes enhances the device reliability, but lessens its power performance because of the extra diffusion resistance. Also noteworthy are the gel influences on the cycle stability. When the applied voltage is 2.0 or 2.5 V, both the LiPF6 and the gel capacitors exhibit excellent stability, typified by a retention ratio of ≥95% after 10,000 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. Nonetheless, when the applied voltage is 3.5 or 4.0 V, the cycle stability deteriorates, since the negative electrode potential descends below 0.9 V (vs. Li), leading to electrolyte decomposition and SEI formation. For the LiPF6 capacitor, its retention ratio could be around 60% after 10,000 cycles and the coulombic efficiency of 100% is difficult to reach throughout its cycle life. On the other hand, the gel capacitor cycles energy with a much higher retention ratio, >80% after 10,000 cycles, and a better coulombic efficiency, even though electrolyte decomposition still occurs. We attribute the superior stability of the gel capacitor to its extra diffusion resistance which slows down the performance deterioration.