ABSTRACT
Over the last years, solid-state electrolytes made of an ionic liquid (IL) confined in a solid (inorganic or polymer) matrix, also known as ionogels, have been proposed to solve the leakage problems occurring at high temperatures in classical electrical double-layer capacitors (EDLCs) with an organic electrolyte, and thereof improve the safety. However, making ionogel-based EDLCs perform with reasonable power at low temperature is still a major challenge due to the high melting point of the confined IL. To overcome these limitations, the present contribution discloses ionogel films prepared in a totally oxygen/moisture-free atmosphere by encapsulating 70 wt % of an equimolar mixture of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide and 1-ethyl-3-methylimidazolium tetrafluoroborate - [EMIm][BF4]0.5[FSI]0.5 - into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) network. The further called "binary ionogel" films demonstrated a high flexibility and a good ionic conductivity of 5.8â mS cm-1 at 20 °C. Contrary to the ionogels prepared from either [EMIm][FSI] or [EMIm][BF4], displaying melting at Tm=-16 °C and -7 °C, respectively, the crystallization of confined [EMIm][BF4]0.5[FSI]0.5 is quenched in the binary ionogel, which shows only a glass transition at -101 °C. This quenching enables an increased ionicity and ionic diffusion at the interface with the PVdF host network, leading the binary ionogel membrane to display higher ionic conductivity below -20 °C than the parent binary [EMIm][BF4]0.5[FSI]0.5 liquid. Laminate EDLCs were built with a 100â µm thick binary ionogel separator and electrodes made from a hierarchical micro-/mesoporous MgO-templated carbon containing a reasonable proportion of mesopores to enhance the mass transport of ions, especially at low temperature where the ionic diffusion noticeably decreases. The EDLCs operated up to 3.0â V with ideal EDL characteristics from -40 °C to room temperature. Their output specific energy under a discharge power of 1â kW kg-1 is ca. 4â times larger than with a cell implementing the same carbon electrodes together with the binary [EMIm][BF4]0.5[FSI]0.5 liquid. Hence, this binary ionogel electrolyte concept paves the road for developing safe and flexible solid-state energy storage devices operating at subambient temperatures in extreme environments.
ABSTRACT
Electrochromic technology offers exciting opportunities for smart applications such as energy-saving and interactive systems. However, achieving dual-band regulation together with the multicolor function is still an unmet challenge for electrochromic devices. Herein, an ingenious electrochromic strategy based on reversible manganese oxide (MnO2) electrodeposition, different from traditional ion intercalation/deintercalation-type electrochromic materials is proposed. Such a deposition/dissolution-based MnO2 brings an intriguing electrochromic feature of dual-band regulation for the ultraviolet (UV) and visible lights with high optical modulation (93.2% and 93.6% at 400 and 550 nm, respectively) and remarkable optical memory. Moreover, a demonstrative smart window assembled by MnO2 and Cu electrodes delivers the electrochromic properties of effective dual-band regulation accompanied by multicolor changes (transparent, yellow, and brown). The robust redox deposition/dissolution process endows the MnO2-based electrochromic device with excellent rate capability and an areal capacity of 570 mAh m-2 at 0.1 mA cm-2. It is believed that the metal oxide-based reversible electrodeposition strategy would be an attractive and promising electrochromic technology and provide a train of thought for the development of multifunctional electrochromic devices and applications.
ABSTRACT
Metal-organic frameworks (MOFs) exhibit promising electrochromic (EC) performance owing to their porous structure, regular channel, and tunable component characteristics. However, few reports focus on MOF materials with the EC performance of a transparent to brown-black (neutral colored state) change that is more suitable for smart windows. In this work, we proposed a strategy for synthesizing MOF (named Ni-BPY) EC materials and corresponding films fabricated via a low-cost electrostatic spray deposition technique. The obtained film exhibits excellent EC performance with a neutral color change from transparent to brown-black, a large optical modulation of 70% at 430 nm, and a fast response within 10 s. Benefiting from good electrical and chemical stability, the Ni-BPY film can be cycled over 500 times. Notably, the Ni-BPY MOF film also delivers a stepwise-controlled process during the bleached state due to its porous characteristics. In addition, the unique color variation of the Ni-BPY film derives from the redox reaction of the Ni metal node between Ni2+ and Ni3+, which is verified by the in situ potential-dependent Raman and X-ray photoelectron spectroscopy (XPS) measurement. As a proof of application, the patterned Ni-BPY EC films and devices are additionally constructed to demonstrate their potential application in electronic tags and logo displays.
ABSTRACT
Flexible three-dimensional interconnected carbon nanotubes on the carbon cloth (3D-CNTs/CC) were obtained through simple magnesium reduction reactions. According to the Nernst equation, the cell voltage based on these pure carbon electrodes without any additives could reach 1.5 V due to the higher di-hydrogen evolution over potential in neutral 3.5 M LiCl electrolytes. In order to improve the electrochemical performance of the electrodes, 3D-CNTs/CC electrodes covered with polyaniline barrier layer (3D-PANI/CNTs/CC) were prepared byin situelectropolymerization using interfacial engineering method. The assembled symmetric supercapacitors display a broadened voltage of 1.8 V, high areal capacitance of 380 mF cm-2, outstanding areal energy density of 85.5µWh cm-2and 84% of its initial capacitance after 20 000 charge-discharge cycles. This work demonstrated that the interface engineering strategy provides a promising way to improve the energy density of carbon-based aqueous supercapacitors by widening the voltage and boosting the capacitance simultaneously.
ABSTRACT
Exploring materials with high electrochemical activity is of keen interest for electrochemistry-controlled optical and energy storage devices. However, it remains a great challenge for transition metal oxides to meet this feature due to their low electron conductivity and insufficient reaction sites. Here, we propose a type of transition metal phosphate (NiHPO4·3H2O, NHP) by a facile and scalable electrodeposition method, which can achieve the capability of efficient ion accommodation and injection/extraction for electrochromic energy storage applications. Specifically, the NHP film with an ultra-high transmittance (approach to 100%) achieves a large optical modulation (90.8% at 500 nm), high coloration efficiency (75.4 cm2 C-1 at 500 nm), and a high specific capacity of 47.8 mAh g-1 at 0.4 A g-1. Furthermore, the transformation mechanism of NHP upon electrochemical reaction is systematically elucidated using in situ and ex situ techniques. Ultimately, a large-area electrochromic smart window with 100 cm2 is constructed based on the NHP electrode, displaying superior electrochromic energy storage performance in regulating natural light and storing electrical charges. Our findings may open up new strategies for developing advanced electrochromic energy storage materials and smart windows.
ABSTRACT
Fiber-shaped supercapacitors (FSCs) have great promises in wearable electronics applications. However, the limited specific surface area and inadequate structural stability caused by the weak interfacial interactions of the electrodes result in relatively low specific capacitance and unsatisfactory cycle lifetime. Herein, solid-state FSCs with high energy density and ultralong cycle lifetime based on polyaniline (PANI)/sulfur-doped TiO2 nanotube arrays (PANI/S-TiO2) are fabricated by interfacial engineering. The experimental results and ab initio calculations reveal that S doping can effectively promote the conductivity of titania nanotubes and increase the binding energy of PANI anchored on the electrode surface, leading to a much stronger binding of PANI on the surface of the electrode and excellent electrode structure stability. As a result, the FSCs using the PANI/S-TiO2 electrodes deliver a high specific capacitance of 91.9 mF cm-2, a capacitance retention of 93.78% after 12 000 charge-discharge cycles, and an areal energy density of 3.2 µW h cm-2. Meanwhile, the all-solid-state FSC device retains its excellent flexibility and stable electrochemical capacitance even after bending 150 cycles. The enhanced performances of FSCs could be attributed to the large surface area, reduced ion diffusion path, improved electrical conductivity, and engineered interfacial interaction of the rationally designed electrodes.