A novel electrochromic device (ECD) based on an electroactive ambipolar system was constructed and designed through an absorption-complementary approach. The system consisted of electroactive polyamides (PAs) with N,N,N′,N′-tetraphenyl-pphenylenediamine (TPPA) and tetraphenylbenzidine (TPB) units in the backbone and heptyl viologen (HV) in the supporting electrolyte. Each of the electrochromic materials (ECMs), including TPPA-PA, TPB-PA and HV, provided one of the three primary colors that merged into a black color. Because of the suitable counter electrode materials used in this study, the overall operating voltage was effectively reduced; thus, the electrochemical stability and lifetime of the ECD were greatly enhanced. Furthermore, the whole system was completely transparent in its neutral or bleaching state, and the transmittance was reduced to only 6% in the colored state in both the visible and near-infrared (NIR) regions. The ECD demonstrated a high L* change (ΔL*) of 81 and a significant transmittance change (ΔT) of 60% in the visible region. Thus, through the excellent combination of the electrochromic and ambipolar characteristics of the system, a genuine 'highly transparent to truly black' ECD was successfully fabricated, implying the great potential of this device as a shutter in transparent displays and related devices.
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