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Abstract
Supercapacitors, with the merits of both capacitors for safe and fast charge and batteries for high energy storage have drawn tremendous attention. Recently, laser scribed graphene has been increasingly studied for supercapacitor applications due to its unique properties, such as flexible fabrication, large surface area and high electrical conductivity. With the laser direct writing process, graphene can be directly fabricated and patterned as the supercapacitor electrodes. In this review, facile laser direct writing methods for graphene were firstly summarized. Various precursors, mainly graphene oxide and polyimide were employed for laser scribed graphene and the modifications of graphene properties were also discussed. This laser scribed graphene was applied for electrochemical double-layer capacitors, pseudo-capacitors and hybrid supercapacitors. Diverse strategies including doping, composite materials and pattern design were utilized to enhance the electrochemical performances of supercapacitors. Featured supercapacitors with excellent flexible, ultrafine-structured and integrated functions were also reviewed.-
Keywords:
- laser /
- graphene /
- laser scribed graphene /
- supercapacitor
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References
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Figure 1.
Illustration of various GO precursors reduced by laser scrbing. (a) The preparative procedure of LSG microcircuit on GO film. (b–c) Optical microscopy images of laser patterned microcircuit; Scale bars, 10 μm. (d) Atomic force microscope (AFM) image of LSG microcircuit on GO film, the height profile along the white line (L2), and its 3D image. (e) Survey X-ray photoelectron spectra of GO and LSG. Inset is a photograph of a LSG square on a GO film. (f) C1s x-ray photoelectron spectroscopy (XPS) spectra of GO and LSG. (g) The experimental setup of pulsed laser reduction system. The inset is optical images of GO solution (15 mL 0,1 mg/mL) before (i) and after (ii) pulsed laser irradiation. (h) Schematic illustration of the GO aerogel treated by laser for the preparation of graphene bulks. Figures reproduced with permission from: (a–e) ref.33 and (g) ref.43, Elsevier; (h) ref.45, John Wiley and Sons.
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Figure 2.
(a) Schematic illustration of laser patterning on polyimide (PI). (b–c) SEM image of LSG on the PI substrate (b) with scale bar 1 mm and its enlarged SEM image with scale bar 10 μm (c). Inset is the corresponding SEM image with higher magnification, scale bar 1 μm. (d–e) Raman spectrum (d) and X-ray diffraction (XRD) (e) of a LSG and the PI film. (f) A photo of LSG on pine wood. (g) The letter “R” in LSG induced from bread. (h) Picture of LSG patterned into an “R” on a coconut (2 cm tall). (i–j) LSG on cloth in the shape of an owl (60 mm in height) (i) and the wrapped cloth (j). Figure reproduced with permission from: (a–e) ref.48, Springer Nature; (f) ref.52, John Wiley and Sons; (g–j) ref.53, American Chemical Society.
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Figure 3.
(a) Schematic illustration of the fabrication of LSG based supercapacitors with sandwiched structures. (b) Schematic diagram of the preparation process for an in-plane LSG supercapacitor. Figure reproduced with permission from: (a) ref.69 , AAAS; (b) ref.70 , Springer Nature.
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Figure 4.
(a) Synthetic scheme for the preparation of boron-doped LSG and its fabrication of supercapacitor. (b) The B1s spectrum of XPS spectra of PI/H3BO3 sheet and boron-doped LSG. (c–d) Cyclic voltammetry curves (c) and galvanostatic charge-discharge curves (d) of LSG SC and boron-doped LSG SC with different H3BO3 loadings. Figure reproduced with permission from ref.72 , American Chemical Society.
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Figure 5.
(a) Schematic showing the insertion of CNTs between GO layers to effectively inhibit the restacking and the fabrication process for the flexible supercapacitor (LSG/CNTs SC). (b) Digital photographs of an assembled SC. (d–e) Cyclic voltammetry curves (d), charge-discharge curves (e) and for LSG SCs, LSG/CNTs SCs with different diameters. (f) Schematic illustration and photos of fabrication of LSG/Au supercapacitors onto a paper substrate. (g) The SEM image of LSG/Au microelectrodes. (h–i) Comparison of electrochemical performances of both the LSG/Au SCs and LSG SCs: cyclic voltammetry curves (h) and galvanostatic charge/discharge curves (i). Figure reproduced with permission from: (a–e) ref.73, Elsevier; (f–i) ref.71, Royal Society of Chemistry.
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Figure 6.
(a) Schematic diagram of a high-voltage planar SC based on laser scribed graphene. (b) Schematic illustration and the related strain property of the kirigami-inspired electrodes with different geometric unit numbers (scale bar 1 cm). (c) Illustration of stacked LSG-SCs in series and parallel circuits and its structure. (d) Schematic diagram of the direct laser reduction of GO fiber for the bamboo-like series of GO-LSG fiber. (e) Bio-inspired fractal electrode design of Hilbert fractal structures. (f) Schematic structure of the Hilbert fractal electrode supercapacitor. Figure reproduced with permission from: (a) ref.74, American Chemical Society; (b) ref.96, Springer Nature; (c) ref.34, American Chemical Society; (d) ref.98, Royal Society of Chemistry; (e−f) ref.75, under a Creative Commons Attribution 4.0 International License.
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Figure 7.
Schematic and structural illustration of LSG/Ni-CAT MOF. (a) An in-plane interdigital LSG pattern. (b) Solvothermal growth of Ni-CAT MOF nanorods. (c) Structure of LSG/Ni-CAT MOF. (d) SEM images of LSG and LSG/Ni-CAT MOFs, respectively. (e) Cyclic voltammetry comparison of bare LSG and LSG/Ni-CAT MOF. (f) Galvanostatic charge/discharge curves of bare LSG and LSG/Ni-CAT MOF. Figure reproduced with permission from ref.35, John Wiley and Sons.
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Figure 8.
(a) Schematic illustration of the deposition process of laser-oxidized Fe3O4 nanoparticles anchored on porous laser scribed graphene by direct laser writing technique. (b–c) SEM images of (b) 3D porous LSG and (c) 3D LSG/Fe3O4 nanoparticle composite. (d) CV curves of LSG/Fe3O4-X at 5 mV·s−1 (e) GCD profiles of LSG/Fe3O4-X at 1 mA·cm−2 . Figure reproduced with permission from ref.77, Elsevier.
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Figure 9.
(a) Schematic of the fabrication steps for the LSG supercapacitor on textile. (b) CV measurements on LSG supercapacitors without encapsulation under different stretchable conditions for a scan rate of 5 V·s−1. (c) Capacitance retention under the maximum stretchable condition of 200% along the uniaxial direction for a scan rate of 5 V·s−1. Figure reproduced with permission from ref.112, under a Creative Commons Attribution 4.0 International License.
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Figure 10.
(a) Schematic of experimental setup using a 405 nm laser in SEM. (b) Fabrication of integrated micro-supercapacitors on a GO film using fs laser processing. (c–d) LSG electrode arrays maintain high resolution with a spacing of ~2 μm. (e–f) CV profiles of fs MSC with the interelectrode spacing of (e) 2 μm and (f) 550 μm. (g) Two-photon-induced 3D graphene micro-supercapacitor using a fs laser. Figure reproduced with permission from: (a) ref.117 and (b–f) ref.80, American Chemical Society; (g) ref.81, under a Creative Commons Attribution 4.0 International License.
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Figure 11.
(a) Schematic of the integrated energy storage with silicon solar cells. (b) Schematic illustration of the self-powered photodetection system including a commercial solar panel, a SC, and a ZnO-based photodetector. (c) Self-discharge curve of the SC after being charged by the solar panel for 1 minute. (d) Photocurrent curves of the photodetector driven by the SC. (e) Schematic illustration for the fabrication of a wireless charging and storage integrated device. (f) Potential change of the integrated SC charged by the wireless circuit placed on a commercial wireless charger. (g) Serially connected thermally chargeable SC modules whose ends are colored in black and silvery-white to create temperature differences under solar radiation. (h) The steady-state voltage of 8 thermally chargeable SC modules as a function of ΔT. Figure reproduced with permission from: (a) ref.122, AIP Publishing; (b–d) ref.124, Elsevier; (e, f) ref.57, American Chemical Society; (g, h) ref.125, Elsevier.
