MXene is a promising energy storage material for miniaturized microbatteries and microsupercapacitors (MSCs). Despite its superior electrochemical performance, only a few studies have reported MXene-based ultrahigh-rate (>1000 mV s−1) on-paper MSCs, mainly due to the reduced electrical conductance of MXene films deposited on paper. Herein, ultrahigh-rate metal-free on-paper MSCs based on heterogeneous MXene/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)-stack electrodes are fabricated through the combination of direct ink writing and femtosecond laser scribing. With a footprint area of only 20 mm2, the on-paper MSCs exhibit excellent high-rate capacitive behavior with an areal capacitance of 5.7 mF cm−2 and long cycle life (>95% capacitance retention after 10,000 cycles) at a high scan rate of 1000 mV s−1, outperforming most of the present on-paper MSCs. Furthermore, the heterogeneous MXene/PEDOT:PSS electrodes can interconnect individual MSCs into metal-free on-paper MSC arrays, which can also be simultaneously charged/discharged at 1000 mV s−1, showing scalable capacitive performance. The heterogeneous MXene/PEDOT:PSS stacks are a promising electrode structure for on-paper MSCs to serve as ultrafast miniaturized energy storage components for emerging paper electronics. 

Synchrotron radiation X-ray diffraction (XRD) with nanoscale beam size was used here for in situ and in operando study of micro-supercapacitors (MSC) with gel electrolyte and MXene Ti3C2Tx electrodes. The electrode structure was characterized as a function of applied voltage and distance from the gap separating electrodes using microscopic cells with cylindrical shape designed for transmission mode XRD. The devices with gel electrolytes based on H2SO4 (with H2O/PVA and DMSO/PVA) showed stable performance with no changes in MXene structure under voltage swaps between positive and negative values. Experiments with KI-based electrolytes demonstrated changes of MXene structure correlated with decrease of energy storage parameters under conditions of increased operation voltage starting from 0.8 V. The optimal performance of the MSCs was observed when the MXene structure remained unchanged upon switching the applied voltage polarity. The changes of inter-layer distance of MXene upon swap of applied voltage correlate with decrease of device performance and are undesirable for stable operation of MSC's. We also tested feasibility of X-ray fluorescence (XRF) for characterization of electrolyte ion migration in MSCs using 2D element mapping. Irreversible sorption of iodine by MXene was found using XRF mapping of charged electrodes using standard in-plane MSC device and KI electrolyte.

Self-charging power systems (SCPSs) are envisioned as promising solutions for emerging electronics to mitigate the increasing global concern about battery waste. However, present SCPSs suffer from large form factors, unscalable fabrication, and material complexity. Herein, a type of highly stable, eco-friendly conductive inks based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are developed for direct ink writing of multiple components in the SCPSs, including electrodes for miniaturized spacer-free triboelectric nanogenerators (TENGs) and microsupercapacitors (MSCs), and interconnects. The principle of “one ink, multiple functions” enables to almost fully print the entire SCPSs on the same paper substrate in a monolithic manner without post-integration. The monolithic fabrication significantly improves the upscaling capability for manufacturing and reduces the form factor of the entire SCPSs (a small footprint area of ≈2 cm × 3 cm and thickness of ≈1 mm). After pressing/releasing the TENGs for ≈79000 cycles, the 3-cell series-connected MSC array can be charged to 1.6 V while the 6-cell array to 3.0 V. On-paper SCPSs are promising to serve as lightweight, thin, sustainable, and low-cost power supplies. 

The rapid development of emerging electronics requires power sources with the advantages of lightweight, high efficiency, and portability. Considering the use of critical raw materials (such as Li, Co, etc.) and the increasing global concern of battery waste, self-charging power systems (SCPSs) integrating energy harvesting, power management, and energy storage devices have been envisioned as promising solutions to replace traditional batteries to avoid the use of toxic materials and the need of frequent recharging/replacement. Up to date, the reported SCPSs still hold the problem of large form factor, unscalable fabrication, noble materials, and material complexity. In our work, a highly stable and eco-friendly organic conductive ink based on poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) has been developed for monolithic fabrication on-paper SCPSs almost fully through a simple direct ink writing (DIW) process. The ink possesses multiple functions and enables to directly print almost all the key components in the SCPSs, including electrodes for triboelectric nanogenerators (TENGs, mechanical energy harvesters), electrodes for micro-supercapacitors (MSCs, energy storage devices), and interconnects, on the same paper substrate in a monolithic manner without the need for “post-integration”. The monolithic printing process exhibits excellent upscaling capability for manufacturing. In particular, the direct patterning merit of the DIW process offers great flexibility in optimizing the system performance through adjusting the cell number, electrode dimension, and thickness of the MSC arrays. By adjusting the cell numbers, the MSC arrays attain high-rate capability up to 50 V/s to match the pulsing electricity produced from the TENGs. For small-size printed SCPSs (~ 2 cm × 3 cm ×1 mm), after continuous press and release of the TENGs for ~79000 cycles, the 3-cell series-connected MSC array can be charged to 1.6 V while 6-cell array to 3.0 V. For a larger-size printed SCPS with 30 MSC cells (~ 7.5 cm × 5 cm ×0.5 mm), after charging through pressing/releasing for 10 min (nearly 1200 cycles), it can light up a LED (~ 4 W) for 5 s. The demo of successfully powering an LED device exhibited its great potential for powering various electronics. The monolithically fabricated on-paper SCPSs have great potential to serve as lightweight, thin, sustainable, eco-friendly, and low-cost power supplies for emerging electronics.

The growing demands of sustainable, portable, and wearable electronics pose new demands on miniaturized energy storage devices that can be integrated on flexible substrates such as paper. Microsupercapacitors (MSCs), especially MXene-based pseudocapacitive MSCs with fast charging/discharging rate, high power density, and long cycle life, are competitive candidates as power supply for emerging flexible and wearable on-paper electronics. However, few studies have reported MXene-based on-paper MSCs to simultaneously attain ultrahigh-rate (>1000 mV s⁻¹) capability and large areal capacitance >10 mF cm⁻². Herein, ultrafast metal-free on-paper MSCs are fabricated through leveraging the synergistic effect of conductive PEDOT:PSS and capacitive MXene (Ti₂C) to achieve a remarkable areal capacitance of 30 mF cm⁻² and long lifetime (>96% capacitance retention after 10 000 cycles) at an ultrahigh scan rate of 1000 mV s⁻¹, outperforming most of the present on-paper or MXene-containing MSCs. Moreover, the printed on-paper metal-free MSC arrays attain extended working voltage window of up to 6 V and outstanding capacitive performance at an ultrahigh scan rate of 10 V s⁻¹. The on-paper PEDOT:PSS-Ti₂C composite MSCs offer new opportunities as eco-friendly microscale power sources for emerging paper-based portable and wearable electronics.

On-paper microsupercapacitors (MSCs) are a key energy storage component for disposable electronics that are anticipated to essentially address the increasing global concern of electronic waste. However, nearly none of the present on-paper MSCs combine eco-friendliness with high electrochemical performance (especially the rate capacity). In this work, highly reliable conductive inks based on the ternary composite of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS), graphene quantum dots and graphene are developed for scalable inkjet printing of compact (footprint area ≈ 20 mm2) disposable MSCs on commercial paper substrates. Without any post treatment, the printed patterns attain a sheet resistance as low as 4 Ω ▫−1. The metal-free all-solid-state MSCs exhibit a maximum areal capacitance > 2 mF cm−2 at a high scan rate of 1000 mV s−1, long cycle life (>95% capacitance retention after 10 000 cycles), excellent flexibility, and long service time. Remarkably, the “totally metal-free” MSC arrays are fully inkjet printed on paper substrates and also exhibit high rate performance. The life cycle assessment indicates that these printed devices have much lower eco-toxicity and global warming potential than other on-paper MSCs.

Harvesting ocean wave energy through carbon-based materials, particularly graphene, is receiving increasing attention. However, the complicated fabrication process and the low output power of the present monolayer graphene-based wave energy generators limit their further application. Here, we demonstrate the facile fabrication of a new type of wave energy generator based on graphene/TiO₂ nanoparticle composite films using the doctor-blading method. The developed wave energy harvesting device exhibits a high open-circuit voltage of up to 75 millivolts and a high output power up to 1.8 microwatts. A systematic study was conducted to explore the optimal conditions for the energy harvesting performance.