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Electrochemical Science Advances

Profile image of Maria R HepelMaria R Hepel

2022, Electrochemical Science Advances

https://doi.org/10.1002/ELSA.202100222
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Abstract

Supercapacitors are a new brand of high-performance nanoengineered devices that match the high capacity of batteries for electric energy storage with the ability of dry capacitors for ultra-fast charging or discharging rates. Thus, supercapacitors are capable of simultaneously providing the high energy-density and high power-density, demanded in a plethora of biosensors and portable elec

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FIGURE 1 _ Theelectrochemical energy storage devices: a comparison of the main stationary and dynamic characteristics of double-layer capacitors, supercapacitors and batteries
FIGURE 1 _ Theelectrochemical energy storage devices: a comparison of the main stationary and dynamic characteristics of double-layer capacitors, supercapacitors and batteries
FIGURE 2 Electrochemical energy storage devices: (a) pseudocapacitor based on electrochemically active redox materials, ROx; (b) double-layer capacitor, based on accumulation of ions on porous electrodes, such as carbon nanoforms C and in solution near the electrode surface; and (c) supercapacitor with fast charge or discharge and high energy density capabilities. In all devices, the nanoporous polymer separators P are filled with electrolyte
FIGURE 2 Electrochemical energy storage devices: (a) pseudocapacitor based on electrochemically active redox materials, ROx; (b) double-layer capacitor, based on accumulation of ions on porous electrodes, such as carbon nanoforms C and in solution near the electrode surface; and (c) supercapacitor with fast charge or discharge and high energy density capabilities. In all devices, the nanoporous polymer separators P are filled with electrolyte
*Evaluated from Refs. [23, 28, 48]. **High surface-area materials; values of Cy estimated on the basis of total capacitance and BET surface area measurements. TABLE 1 Typical values of the electric double-layer specific capacitance Cy, for materials utilized in supercapacitor designs*
*Evaluated from Refs. [23, 28, 48]. **High surface-area materials; values of Cy estimated on the basis of total capacitance and BET surface area measurements. TABLE 1 Typical values of the electric double-layer specific capacitance Cy, for materials utilized in supercapacitor designs*
FIGURE 3 Schematics of the equivalent electric circuits for electrochemical supercapacitors: (a) the equivalent circuit showing how the capacitances of electrodes, C, and C,, contribute to the total capacitance C,a, of the device (see Eq. [8]); (b) a detailed circuit delineating the contributions of double-layer capacitances Cg and film pseudocapacitances C,,, to the total capacitance C,,,
FIGURE 3 Schematics of the equivalent electric circuits for electrochemical supercapacitors: (a) the equivalent circuit showing how the capacitances of electrodes, C, and C,, contribute to the total capacitance C,a, of the device (see Eq. [8]); (b) a detailed circuit delineating the contributions of double-layer capacitances Cg and film pseudocapacitances C,,, to the total capacitance C,,,
FIGURE 4 Schematic view of the 3D hybrid structure engineering with decreasing CNT spacer loading (from a to d). Reproduced with permission from Ref. [49]. Copyright 2011 American Chemical Society
FIGURE 4 Schematic view of the 3D hybrid structure engineering with decreasing CNT spacer loading (from a to d). Reproduced with permission from Ref. [49]. Copyright 2011 American Chemical Society
FIGURE 5 AFM image of graphene monolayers (a) and Raman spectra for a graphite rod (b) and graphene nanosheets (c) obtained by electrochemical reduction of graphene oxide (erGO). The ratio of peak heights D/G and the appearance of the 2D band are diagnostic tools for the evaluation of the material properties. (M Hepel, unpublished results)
FIGURE 5 AFM image of graphene monolayers (a) and Raman spectra for a graphite rod (b) and graphene nanosheets (c) obtained by electrochemical reduction of graphene oxide (erGO). The ratio of peak heights D/G and the appearance of the 2D band are diagnostic tools for the evaluation of the material properties. (M Hepel, unpublished results)
FIGURE 6 _ Oxidation steps of polyaniline (PAni) contributing to the high pseudocapacitance of GNS/PAni supercapacitors
FIGURE 6 _ Oxidation steps of polyaniline (PAni) contributing to the high pseudocapacitance of GNS/PAni supercapacitors
FIGURE 7 _ Scheme of the preparation procedure for a grafted PAni-rGO material and the TEM image of the sample (inset). Reproduced with permission from Ref. [103]. Copyright 2012 American Chemical Society
FIGURE 7 _ Scheme of the preparation procedure for a grafted PAni-rGO material and the TEM image of the sample (inset). Reproduced with permission from Ref. [103]. Copyright 2012 American Chemical Society
FIGURE 8 _ FESEM images of (a) CNT/PAni, (b) GNS/PAni and (c) GNS/CNT/PAni. (d) TEM image of GNS/CNT/PAni. Reproduced with permission from Ref. [106]. Copyright 2013 American Chemical Society
FIGURE 8 _ FESEM images of (a) CNT/PAni, (b) GNS/PAni and (c) GNS/CNT/PAni. (d) TEM image of GNS/CNT/PAni. Reproduced with permission from Ref. [106]. Copyright 2013 American Chemical Society
FIGURE 9 _ Electrochemical impedance Nyquist plot for CNT/PAni, GNS/PAni and GNS/CNT/PAni electrodes in a1 M H,SO, solution in the frequency range from 0.01 Hz to 100 kHz. Inset: the equivalent electronic circuit for the electrode. Reproduced with permission from Ref. [106]. Copyright 2013 American Chemical Society
FIGURE 9 _ Electrochemical impedance Nyquist plot for CNT/PAni, GNS/PAni and GNS/CNT/PAni electrodes in a1 M H,SO, solution in the frequency range from 0.01 Hz to 100 kHz. Inset: the equivalent electronic circuit for the electrode. Reproduced with permission from Ref. [106]. Copyright 2013 American Chemical Society
FIGURE 10 _ SEM images of PAni-HS36@erGO hybrids with sphere size: (a) 330 nm, (b) 2.4 wm. Reproduced with permission from Ref. [66]. Copyright 2013 American Chemical Society
FIGURE 10 _ SEM images of PAni-HS36@erGO hybrids with sphere size: (a) 330 nm, (b) 2.4 wm. Reproduced with permission from Ref. [66]. Copyright 2013 American Chemical Society
FIGURE 11 _ Thecharge-discharge characteristics for current density of 1 A/g (a) and the dependence of specific capacitance for PAni-HS36 and PAni-HS36@erGO hybrids on current density (b). Reproduced with permission from Ref. [66]. Copyright 2013 American Chemical Society
FIGURE 11 _ Thecharge-discharge characteristics for current density of 1 A/g (a) and the dependence of specific capacitance for PAni-HS36 and PAni-HS36@erGO hybrids on current density (b). Reproduced with permission from Ref. [66]. Copyright 2013 American Chemical Society
*See details on material preparation in text (further details available in origina references). CNT, carbon nanotubes. TABLE 2 __ Specific capacitance of selected graphene-polyaniline-based composite materials
*See details on material preparation in text (further details available in origina references). CNT, carbon nanotubes. TABLE 2 __ Specific capacitance of selected graphene-polyaniline-based composite materials
TABLE 3 _ Specific capacitance of CNF-RuO, based composite materials
TABLE 3 _ Specific capacitance of CNF-RuO, based composite materials
FIGURE 12 AFM images of electrochemically deposited WO,., films in different forms: from nanowire to small aggregated spherical nanoparticles: (a,b) nucleation of WO, nanowires on edges of atomic steps of HOPG at the deposition potential: (a) —0.3 V, (b) —0.4 V versus Ag/AgCl; (c,d) large WO; particles deposited at Eyey: (Cc) —0.3 V, (d) —0.4 V, and annealed at 300°C; (e,f) small WO, nanoparticles obtained by deposition at Eye, = -0.5 V, average nanoparticle diameter: 27 + 4 nm (reprinted from Ref. [151] with permission. Copyright 2008 American Chemical Society
FIGURE 12 AFM images of electrochemically deposited WO,., films in different forms: from nanowire to small aggregated spherical nanoparticles: (a,b) nucleation of WO, nanowires on edges of atomic steps of HOPG at the deposition potential: (a) —0.3 V, (b) —0.4 V versus Ag/AgCl; (c,d) large WO; particles deposited at Eyey: (Cc) —0.3 V, (d) —0.4 V, and annealed at 300°C; (e,f) small WO, nanoparticles obtained by deposition at Eye, = -0.5 V, average nanoparticle diameter: 27 + 4 nm (reprinted from Ref. [151] with permission. Copyright 2008 American Chemical Society
FIGURE 13 _ Raman spectra of oxidized and reduced WO3.x.(1/3)H,0O: (1) oxidized form, (2,3) reduced form; the isotopic Raman shift for Ht and Dt is also indicated. Reproduced with permission from Ref. [145]. Copyright 1998, the Electrochemical Society
FIGURE 13 _ Raman spectra of oxidized and reduced WO3.x.(1/3)H,0O: (1) oxidized form, (2,3) reduced form; the isotopic Raman shift for Ht and Dt is also indicated. Reproduced with permission from Ref. [145]. Copyright 1998, the Electrochemical Society
*Thin-film micro-porous graphene uniformly coated with MnO, nanoparticles. **For asymmetric supercapacitor with high-area GF and wGF/Mn0O, electrodes. AC, activated carbon; EG, exfoliated graphene; GNS, graphene nanosheet; wGF, micro-graphene foam; nf, nanoflakes; vaCNT, vertically aligned carbon nanotube: TABLE 4 Electrochemical properties reported recently for MnO,-grafted porous graphene paper supercapacitor electrodes in differer aqueous electrolytes
*Thin-film micro-porous graphene uniformly coated with MnO, nanoparticles. **For asymmetric supercapacitor with high-area GF and wGF/Mn0O, electrodes. AC, activated carbon; EG, exfoliated graphene; GNS, graphene nanosheet; wGF, micro-graphene foam; nf, nanoflakes; vaCNT, vertically aligned carbon nanotube: TABLE 4 Electrochemical properties reported recently for MnO,-grafted porous graphene paper supercapacitor electrodes in differer aqueous electrolytes
TABLE 5 Metal-organic-framework (MOF) materials developed recently for supercapacitor applications Abbreviations. C-CNTs, carboxylated multi-walled carbon nanotubes; GO, graphene oxide; HITP, 2,3,6,7,10,11-hexaiminotriphenylene; LDH, layered double hydroxides; n.s., not specified.
TABLE 5 Metal-organic-framework (MOF) materials developed recently for supercapacitor applications Abbreviations. C-CNTs, carboxylated multi-walled carbon nanotubes; GO, graphene oxide; HITP, 2,3,6,7,10,11-hexaiminotriphenylene; LDH, layered double hydroxides; n.s., not specified.
Abbreviations: AgNW, silver nanowires; C, carbon nanoforms; CDC, carbide-derived porous carbon; DC-MSP-direct current magnetron sputtering; EG, exfoliated graphene; FAT, freezing-and-thawing; Gr, graphite; HQ, hydroquinone; NGO, nanosized graphene oxide; n.s., not specified; PAni, polyaniline; PEDOT, poly(3,4- ethylenedioxythiophene); PG-PSS, printable graphene-based planar sandwich supercapacitor; pw, potential window; Qdots, quantum dots; v, potential scan rate. [TABLE 6 _ Flexible micro-supercapacitors (FMSCs) and their properties
Abbreviations: AgNW, silver nanowires; C, carbon nanoforms; CDC, carbide-derived porous carbon; DC-MSP-direct current magnetron sputtering; EG, exfoliated graphene; FAT, freezing-and-thawing; Gr, graphite; HQ, hydroquinone; NGO, nanosized graphene oxide; n.s., not specified; PAni, polyaniline; PEDOT, poly(3,4- ethylenedioxythiophene); PG-PSS, printable graphene-based planar sandwich supercapacitor; pw, potential window; Qdots, quantum dots; v, potential scan rate. [TABLE 6 _ Flexible micro-supercapacitors (FMSCs) and their properties
FIGURE 14 _ One pot synthesis and characteristics of nitrogen-doped reduced graphene (NRG) nanosheets with dispersed ZnFe,0, nanoparticles. Top panel: schematic illustration of the preparation of ZnFe,0,/NRG composite. Lower panel: (a) galvanostatic charge-discharge curves of ZnFe,0, NPs, NRG and ZnFe,0,/NRG; (b) galvanostatic charge—-discharge curves of ZnFe,O,/NRG composite tested at different discharge currents; (c) current density-dependent specific capacitance of ZnFe,O, NPs, NRG and ZnFe,0,/NRG; (d) Nyquist plots of the EIS for ZnFe,0, NPs, NRG and ZnFe,0,/NRG. Adopted from Ref. [263]
FIGURE 14 _ One pot synthesis and characteristics of nitrogen-doped reduced graphene (NRG) nanosheets with dispersed ZnFe,0, nanoparticles. Top panel: schematic illustration of the preparation of ZnFe,0,/NRG composite. Lower panel: (a) galvanostatic charge-discharge curves of ZnFe,0, NPs, NRG and ZnFe,0,/NRG; (b) galvanostatic charge—-discharge curves of ZnFe,O,/NRG composite tested at different discharge currents; (c) current density-dependent specific capacitance of ZnFe,O, NPs, NRG and ZnFe,0,/NRG; (d) Nyquist plots of the EIS for ZnFe,0, NPs, NRG and ZnFe,0,/NRG. Adopted from Ref. [263]
FIGURE 15 _ Characteristics of a strain sensor driven by a micro-supercapacitor (SS-MSC): (a) SEM image of a AgNW network on PDMS before stretching (0%) and for a 30% stretching (inset). (b) The relative change in resistance (AR/RO) versus strain curves of the AgNW SS taken for various stretching states from 0 to 30%. (Inset) I-V curves of the sensor for strain from 0 to 30%. (c) Photograph of wrist bending with a skin-attached SS-MSC patch. (d) Current change of the AgNW SS with wrist motion, where red and blue arrows correspond to bending and straightening, respectively. The top and bottom graphs are obtained from the SS driven by an externally applied constant voltage of 0.8 V and by the in-circuit MSC, respectively. (e) Photograph of the integrated system attached to the skin of the wrist. (f) Resistance change of the AgNW SS with the wrist pulse. The top and bottom graphs are obtained for the SS driven by an externally applied constant voltage of 0.8 V and by the in-circuit MSC, respectively (adopted with permission from Ref. [265])
FIGURE 15 _ Characteristics of a strain sensor driven by a micro-supercapacitor (SS-MSC): (a) SEM image of a AgNW network on PDMS before stretching (0%) and for a 30% stretching (inset). (b) The relative change in resistance (AR/RO) versus strain curves of the AgNW SS taken for various stretching states from 0 to 30%. (Inset) I-V curves of the sensor for strain from 0 to 30%. (c) Photograph of wrist bending with a skin-attached SS-MSC patch. (d) Current change of the AgNW SS with wrist motion, where red and blue arrows correspond to bending and straightening, respectively. The top and bottom graphs are obtained from the SS driven by an externally applied constant voltage of 0.8 V and by the in-circuit MSC, respectively. (e) Photograph of the integrated system attached to the skin of the wrist. (f) Resistance change of the AgNW SS with the wrist pulse. The top and bottom graphs are obtained for the SS driven by an externally applied constant voltage of 0.8 V and by the in-circuit MSC, respectively (adopted with permission from Ref. [265])
FIGURE 16 (a) Schematic illustration and (b) photograph of a transparent and stretchable micro-supercapacitor (MSC) integrated wit an Ag NW strain sensor (SS). The scale bar corresponds to 5 cm. Cross-sectional view of (c) the MSC and (d) SS. (e) Molecular structures of the components of the stretchable ionic electrolyte [BMIM] [TFSI]/PMMA. (f) Transmittance spectrum of (red) [BMIM]|[TFSI]/PMMA, (green) the fractal MSC and (orange) the Ag NW SS. Reprinted with permission from Ref. [265]
FIGURE 16 (a) Schematic illustration and (b) photograph of a transparent and stretchable micro-supercapacitor (MSC) integrated wit an Ag NW strain sensor (SS). The scale bar corresponds to 5 cm. Cross-sectional view of (c) the MSC and (d) SS. (e) Molecular structures of the components of the stretchable ionic electrolyte [BMIM] [TFSI]/PMMA. (f) Transmittance spectrum of (red) [BMIM]|[TFSI]/PMMA, (green) the fractal MSC and (orange) the Ag NW SS. Reprinted with permission from Ref. [265]
FIGURE 17 _ Device architecture of LbL self-assembled multilayer MXene-based electrochemical random-access memory (ECRAM) for artificial neural network (ANN) design: (a) LbL assembly (right panel) and principles of RAM memory operation (left panel). (b) Fast pulsed operation of 10-layer (MXene/TAPA),, ECRAM using +1 V 4 us write pulses, followed by 1 us write-read delay and 0.1 V 10 s readout. Reprinted with permission from Ref. [280]
FIGURE 17 _ Device architecture of LbL self-assembled multilayer MXene-based electrochemical random-access memory (ECRAM) for artificial neural network (ANN) design: (a) LbL assembly (right panel) and principles of RAM memory operation (left panel). (b) Fast pulsed operation of 10-layer (MXene/TAPA),, ECRAM using +1 V 4 us write pulses, followed by 1 us write-read delay and 0.1 V 10 s readout. Reprinted with permission from Ref. [280]

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