On-chip and freestanding elastic carbon films for micro-supercapacitors
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The fabrication of high performance on-chip 3D micro-supercapacitors (MSCs) based on MnO 2 pseudocapacitive binder-free thin film electrodes (< 500 nm thick) with interdigitated topology is reported. An original technological process easily scalable to pilot production line is proposed on 3-inch silicon wafers. High areal energy (> 10 μWh.cm -2 ) and power densities (> 10 mW.cm -2 ) are reached on small footprint micro-supercapacitors (4 mm 2 ) tested in aqueous electrolyte (0.8 V). Furthermore, the cell voltage of such MSC can be increased up to 1.5 V with EMI TFSI ionic liquids but at the expense of the areal capacitance. The performance in ionic liquid is in the same order of magnitude than the one obtained for aqueous electrolyte. The benefit from the 3D topology is clearly demonstrated when the surface performance are normalized to the electrode thickness allowing to obtain an interesting energy vs power tradeoff (> 10 μWh.cm -2 μm -1 and > 1 mw.cm -2 μm -1 ). Here, this paper aims at improving the energy density of MSCs while keeping high power capability, by combining the use of ionic liquids and the deposition of MnO 2 thin film onto robust and efficient 3D scaffolds.
Direct printing of functional inks is critical for applications in diverse areas including electrochemical energy storage, smart electronics and healthcare. However, the available printable ink formulations are far from ideal. Either surfactants/additives are typically involved or the ink concentration is low, which add complexity to the manufacturing and compromises the printing resolution. Here, we demonstrate two types of two-dimensional titanium carbide (Ti 3 C 2 T x ) MXene inks, aqueous and organic in the absence of any additive or binary-solvent systems, for extrusion printing and inkjet printing, respectively. We show examples of all-MXene-printed structures, such as micro-supercapacitors, conductive tracks and ohmic resistors on untreated plastic and paper substrates, with high printing resolution and spatial uniformity. The volumetric capacitance and energy density of the all-MXene-printed micro-supercapacitors are orders of magnitude greater than existing inkjet/extrusion-printed active materials. The versatile direct-ink-printing technique highlights the promise of additive-free MXene inks for scalable fabrication of easy-to-integrate components of printable electronics.
Selective wetting-induced micro-electrode patterning is used to fabricate flexible micro-supercapacitors (mSCs). Here, the resulting mSCs exhibit high performance, mechanical stability, stable cycle life, and hold great promise for facile integration into flexible devices requiring on-chip energy storage.
Micro-supercapacitors (MSCs) have drawn tremendous attention as promising candidates to power miniaturized portable/wearable electronics, but they still suffer from unsatisfactory electrochemical performance (e.g., insufficient energy density, mediocre rate capability), thus impeding their widespread applications. Here, a synergistic surface and structure engineering strategy achieved by downsizing to quantum dot scale, doping of heteroatoms, and introducing defects and functional groups is proposed to regulate the physicochemical properties of Ti 3 C 2 T x MXene. Encouragingly, the resulting MSCs based on defect-rich nitrogen-doped Ti 3 C 2 T x quantum dots (QDs) possess excellent electrochemical performance as demonstrated by large operating voltage (3.0 V in ionic liquid and 1.0 V in aqueous electrolyte), perfect rectangular CV shape even at 1000 V·s -1 , high volumetric capacitance of 33.1 F·cm -3 , and superior cycling stability after 10000 cycles. By employing experimental characterizations and density functional theory calculations, the remarkable performance of the MSCs is mainly due to the special chemical states as well as the unique surface and structural features of Ti 3 C 2 T x QDs, which offer abundant active sites, shorten ion diffusion pathways, promote ion/electron transports, and provide enhanced capacitance. Finally, this work provides a new strategy for the design of high-performance MSCs and a reference for the applications of MXene QDs in other energy-related fields.
Direct laser-reduction of graphene oxide (GO), as a lithography-free approach, has been proven effective in manufacturing in-plane micro-supercapacitors (MSCs) with fast ion diffusion. However, the power density and the charge/discharge rate are still limited by the relatively low conductivity of electrodes. Here, we report a facile approach by exploiting femtolaser in situ reduction of the hydrated GO and chloroauric acid (HAuCl 4 ) nanocomposite simultaneously, which incorporates both the patterning of rGO electrodes and the fabrication of Au current collectors in a single step. These flexible MSCs boast achievements of one-hundred fold increase in electrode conductivities of up to 1.1 × 10 6 S m –1 , which provide superior rate capability (50% for the charging rate increase from 0.1 V s –1 to 100 V s –1 ), sufficiently high frequency responses (362 Hz, 2.76 ms time constant), and large specific capacitances of 0.77 mF cm –2 (17.2 F cm –3 for volumetric capacitance) at 1 V s –1 , and 0.46 mF cm –2 (10.2 F cm –3 ) at 100 V s –1 . The use of photo paper substrates enables the flexibility of this fabrication protocol. Moreover, proof-of-concept 3D MSCs are demonstrated with enhanced areal capacitance (up to 3.84 mF cm –2 at 1 V s –1 ) while keeping high rate capabilities. As a result, this prototype of all solid-state MSCs demonstrates the broad range of potentials of thin-film based energy storage device applications for flexible, portable, and wearable electronic devices that require a fast charge/discharge rate and high power density.
Current microfabrication of micro–supercapacitors often involves multistep processing and delicate lithography protocols. In this study, simple fabrication of an asymmetric MXene–based micro–supercapacitor that is flexible, binder–free, and current–collector–free is reported. Here, the interdigitated device architecture is fabricated using a custom–made mask and a scalable spray coating technique onto a flexible, transparent substrate. The electrode materials are comprised of titanium carbide MXene (Ti 3 C 2 T x ) and reduced graphene oxide (rGO), which are both 2D layered materials that contribute to the fast ion diffusion in the interdigitated electrode architecture. This MXene–based asymmetric micro–supercapacitor operates at a 1 V voltage window, while retaining 97% of the initial capacitance after ten thousand cycles, and exhibits an energy density of 8.6 mW h cm –3 at a power density of 0.2 W cm –3 . Further, these micro–supercapacitors show a high level of flexibility during mechanical bending. Utilizing the ability of Ti 3 C 2 T x – MXene electrodes to operate at negative potentials in aqueous electrolytes, it is shown that using Ti 3 C 2 T x as a negative electrode and rGO as a positive one in asymmetric architectures is a promising strategy for increasing both energy and power densities of micro–supercapacitors.
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Additive-free, single step formulations of MXene-in-water inks are developed from clay-like titanium carbide (Ti 3 C 2 ) sediments. Solution-processable Ti 3 C 2 inks are compatible with stamping, printing, painting, and writing on a variety of substrates. Specifically, MXene-in-water inks at higher concentrations of 30 mg mL -1 are employed in commercially available pens for dispensing and patterning 2D MXene directly. These MXene pens are employed either manually or automatically using an AxiDraw, enabling direct-writing and complex patterning of functional MXene devices. Versatile MXene pens show compatible writing on a variety of substrates, including paper and polymers, where the deposited ink is used as a passive circuit, similar to silver and copper nanoparticle inks. Written MXene lines without additional post-treatment exhibit length dependent resistance, showing typical resistivity values between carbon based and metal nanoparticle inks. Current collector-free fabrication of MXene micro-supercapacitors is demonstrated on unconventional platforms including paper, textiles, and curved surfaces directly.
Recycling processes for lithium-ion batteries (LIBs) are imperative to support the sustainable growth of global energy storage systems. This study introduces a scalable method for the upcycling of spent graphite anodes from LIBs to produce electronic-grade graphene nanoplatelets. In addition to comprehensive materials characterization, the electronic quality of the upcycled graphene is demonstrated by formulating it into a screen printing ink that achieves high-resolution patterning and thin-film electrical conductivity exceeding 104 S m−1. This screen printing ink is also used to print planar micro-supercapacitors with exceptional areal capacitance (1.78 mF cm−2), areal energy density (0.247 µWh cm−2), and cycling stability (> 10 000 cycles). Life cycle assessment (LCA) and techno-economic analysis (TEA) highlight the environmental benefits and cost reductions attainable through upcycling of graphite from LIBs. By capturing economic value from spent LIBs, this work fosters a sustainable battery supply chain and provides an abundant and geographically distributed raw material for electronic-grade graphene.
We report on the impact of laser processing on material and device performance characteristics for integrated energy applications. A femtosecond laser was used for development of flexible and transparent supercapacitors, while a nanosecond laser was successfully exploited for high-performance Al–air battery development. A laser direct-write process enabled integration of a three-dimensional-structured micro-supercapacitor on flexible polymer substrate, exhibiting peak specific capacitance of 42.6 mF/cm 2 at current density of 0.1 mA/cm 2 . Femtosecond laser processing was also exploited for development of a novel transparent supercapacitor on silk substrate. The MnO 2 -coated transparent supercapacitors exhibited high transmittance exceeding 59%. Laser processing in combination with printing technique was used for development of a novel Al–air battery. The nanosecond laser process was effective in sintering the anode printed using Al nanoparticle ink. The efficiency of the laser sintering process was reflected in good battery discharge performance.
A graphene oxide (GO) membrane can be used in structural dielectric capacitors and planar micro-supercapacitors as a dielectric separator material due to its excellent through-plane and in-plane dielectric properties. The ability to tailor the dielectric properties of the GO membrane is crucial for dielectric applications. We believe this to be the first demonstration describing how Al 3+ ions impact the dielectric properties of the GO membrane through cation to oxygenated functional groups interactions. In this work, the Al 3+ -modification to the GO membrane was realized through a facile pre-coordination method followed by layer-by-layer assembling. The influence of Al 3+ on the GO membranes’ through-plane and in-plane dielectric properties (dielectric constant and dielectric loss) was investigated in the frequency range from 0.01 Hz to 10 5 Hz. Plane-to-plane and edge-to-edge Al 3+ coordination with the functional group on the basal plane or edge of the GO sheets was proposed to understand the metal ion's impact on the dielectric properties. The results demonstrated that the Al 3+ modification was an effective strategy to tailoring the GO membranes’ dielectric properties in a low frequency regime and further suggested the possibility of designing dielectric GO membranes with controllable dielectric performance. At a low frequency range (0.01–1 Hz), the addition of Al 3+ increased the through-plane dielectric constant and decreased the in-plane dielectric constant. In terms of dielectric loss, unmodified GO membranes exhibited a higher in-plane dielectric loss than the through-plane dielectric loss. Al 3+ -modified GO membranes exhibited increased through-plane dielectric loss and decreased in-plane dielectric loss compared to the unmodified GO membranes.