Facile and Scalable Fabrication of High-Performance Microsupercapacitors Based on Laser-Scribed In Situ Heteroatom-Doped Porous Graphene

Abstract

This study proposes an efficient, facile, and scalable strategy to synthesize in situ heteroatom-doped porous graphene via laser direct writing on the precursor-doped polyimide (PI) film, which is fabricated for the first time through incorporating PI powder and precursors with sodium carboxymethyl cellulose (CMC) binder by a drop-casting and low-temperature drying process. The resulting microsupercapacitors (MSCs) based on the as-prepared heteroatom-doped porous graphene exhibit remarkable capacitive performance. The typical boron-doped MSC prepared on borax-doped polyimide film possesses an ultrahigh areal capacitance of 60.6 mF cm–2 at 0.08 mA cm–2, which is approximately 20 times larger than that of undoped MSC. Furthermore, the boron-doped MSC has impressive cycling stability (with the capacitance retention of 96.3% after 20 000 cycles), exceptional mechanical flexibility, tunable capacitance, and voltage output through arbitrary modular serial and parallel integration. Besides, the nitrogen-doped porous graphene with excellent capacitive performance is also prepared by laser direct scribing on the sulfonated melamine-doped polyimide film, demonstrating excellent scalability and generality of this strategy. Hence, one-step laser direct writing on precursor-doped polyimide films can realize in situ heteroatom doping and generation of hierarchical porous graphene electrodes simultaneously, which opens a new avenue for the facile, cost-effective, and scalable fabrication of heteroatom-doped porous graphene, thus promising for MSCs and various flexible and wearable electronics at large-scale production.

Tuning the Laser‐Induced Processing of 3D Porous Graphenic Nanostructures by Boron‐Doped Diamond Particles for Flexible Microsupercapacitors

“…The ionogel integrated into the LIG-based devices and their EC performances are discussed below. MOF-LIG (MOF-199@ZIF-67) 8.1@1 mV s −1 6.2@10 mV s −1 5.0@0.2 mA cm −2 [66] LIG prepared from GO films 2.3@10 mV s −1 1.6@0.2 mA cm −2 [1] LIG prepared from PI films 4.1@1 mV s −1 3.9@0.2 mA cm −2 [8] LIG prepared from lignin films 15.4@10 mV s −1 12@0.2 mA cm −2 [67] Laser-induced graphenization of SPEEK film 5.6@3 mV s −1 1.9@0.2 mA cm −2 [68] TiO 2 decorated LIG -≈3.3@0.1 mA cm −2 [17] Boron-doped LIG (5B-LIG) -9.54@0.1 mA cm −2 [69] MXene-rGO composite 34.6 [70] Laser-induced and KOH-activated 3D grapheme -32@0.05 mA cm −2 [71] Laser-induced nitrogen-self-doped graphite nanofibers -57.96@0.02 mA cm −2 [72] Phosphorus-doped porous LIG 40.4@10 mV s −1 55.5@0.05 mA cm −2 [73] Boron-doped porous LIG -60.6@0.08 mA cm −2 [74] Nitrogen and boron co-doped LIG -40.4@0.05 mA cm −2 [75] Ruthenium oxide-based LIG 16@20 mV s −1 - [76] BDNW decorated oxidized LIG 25.2@1 mV s −1 18@10 mV s −1 9.4@0.1 mA cm −2 7.77@0.2 mA cm −2 Present work…”

Dual Defocused Laser Pyrolysis: A Lasing‐Centric Strategy for Defect and Morphological Optimization in Microsupercapacitor Electrodes

“…The G peak is related to the in‐plane vibration band of sp 2 carbon atoms, indicating the formation of graphitized and amorphous carbon structures. [ 61 ] The presence of 2D peaks indicates the formation of stacked graphene layers. [ 31 ] Remarkably, defocused lasing resulted in two significant changes: (1) the D and G peaks are narrow, and (2) the intensity ratio of the D and G peak ( I D / I G ) is significantly reduced from 0.817 of FLIG to 0.083.…”

“…[33] The areal energy density of the MSC is comparable to that of LIG with KOH activation based MSC on PI substrate. [57] Moreover, compared to MSCs on PI and silicone, [33,57,61,71,73] the proposed method of fabricating MSC on CPU substrate provides a facile and scalable route. Overall, the proposed MSC is at the forefront of performance but with a more controllable and scalable fabrication method.…”

Laser Processing of Flexible In-Plane Micro-supercapacitors: Progresses in Advanced Manufacturing of Nanostructured Electrodes

“…Great progress has been made in the manufacturing of heteroatom-doped electrodes, but there are still some issues in the preparation of PAA-based composite films, such as cumbersome operations, high temperature requirements, long reaction durations, and high cost. In light of this, a method of compounding microsized PI powder and polymer matrix (such as sodium carboxymethyl cellulose and PVA) to form a composite functional PI film was proposed by Yuan et al 243 In addition to laser doping with heteroatom sources in the form of composite materials, laser or xenon lamp doping of heteroatoms in a gas environment containing target atom has also gained attention. 44,244 For instance, Guo et al 44 demonstrated the simultaneous laser reduction and N doping of GO using a visible fs laser in an ammonia (NH 3 ) atmosphere, and successfully manufactured diverse micropatterns of Ndoped LrGO for device fabrication (Figure 21D).…”