Block-Copolymer assisted synthesis of hierarchical carbon monoliths suitable as supercapacitor electrodes

Carriazo, Daniel; Picó, Fernando; Gutiérrez, Marı́a C.; Rubio, F.; Rojo, J. M.; Monte, Francisco del

doi:10.1039/b915903g

Cited by 120 publications

(74 citation statements)

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“…In general, the M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 4 carbon monoliths are isotropic materials; however, some monoliths are anisotropic and show carbon walls and channels, both aligned along a specific direction of the monolith [21]. The main drawback of the carbon monoliths is their low density, typically lower than 0.5-0.6 g cm -3 [2,[20][21][22][23][24][25][26][27][28][29][30][31][32]. Consequently, their volumetric capacitance is usually low, below 100 F cm -3 in aqueous electrolytes and below 50 F cm -3 in organic ones.…”

Section: Introductionmentioning

confidence: 99%

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The contribution of sulfate ions and protons to the specific capacitance of microporous carbon monoliths

Barranco

García-Gómez

Kunowsky

et al. 2014

Journal of Power Sources

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The monoliths studied in this work show large specific surface areas (up to 1600 m 2 g -1 ), high densities (up to 1.17 g cm -3) and high electrical conductivities (up to 9.5 S cm -1 ). They are microporous carbons with pore sizes up to 1.3 nm but most of them below 0.75 nm. They also show oxygen functionalities. The electrochemical behavior of the monoliths is studied in three-electrode cells with aqueous H 2 SO 4 solution as electrolyte. This work deals with the contribution of the sulfate ions and protons to the specific capacitance of carbon monoliths having different surface areas and different contents of oxygen groups. Protons contribute with a pseudocapacitance (up to 152 F g ); both capacitances increase as the surface area increases. The preference of protons to be electroadsorbed at the double layer and the broader voltage window of these ions account for their higher contribution (70 %) to the double layer capacitance.

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Section: Introductionmentioning

confidence: 99%

“…as an entire piece of carbon [6,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. Cells having carbon monoliths as electrodes have a number of advantages over those comprising compacted powder pellets made from powder carbon.…”

Section: Introductionmentioning

confidence: 99%

The contribution of sulfate ions and protons to the specific capacitance of microporous carbon monoliths

Barranco

García-Gómez

Kunowsky

et al. 2014

Journal of Power Sources

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“…Porous nanostructures have received great attention because of their wide-ranging applications, such as in lithium-ion batteries [1][2][3], ion exchange membranes [4], catalysis supports [5][6][7][8], solar cells [9], and supercapacitor electrodes [10][11][12][13][14] due to their high surface area and enhanced interaction with the environment [15]. In the case of charge storage applications, transition metal oxide nanostructures are attractive candidates by virtue of their excellent pseudocapacitive behavior and high electrical conductivity [16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of porous NiO nanocrystals with controllable surface area and their application as supercapacitor electrodes

et al. 2010

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We report a facile way to grow various porous NiO nanostructures including nanoslices, nanoplates, and nanocolumns, which show a structure-dependence in their specific charge capacitances. The formation of controllable porosity is due to the dehydration and re-crystallization of β-Ni(OH) 2 nanoplates synthesized by a hydrothermal process. Thermogravimetric analysis shows that the decomposition temperature of the β-Ni(OH) 2 nanostructures is related to their morphology. In electrochemical tests, the porous NiO nanostructures show stable cycling performance with retention of specific capacitance over 1000 cycles. Interestingly, the formation of nanocolumns by the stacking of β-Ni(OH) 2 nanoslices/plates favors the creation of small pores in the NiO nanocrystals obtained after annealing, and the surface area is over five times larger than that of NiO nanoslices and nanoplates. Consequently, the specific capacitance of the porous NiO nanocolumns (390 F/g) is significantly higher than that of the nanoslices (176 F/g) or nanoplates (285 F/g) at a discharge current of 5 A/g. This approach provides a clear illustration of the process-structure-property relationship in nanocrystal synthesis and potentially offers strategies to enhance the performance of supercapacitor electrodes.

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“…IL based syntheses of carbon materials have been established in manifold ways in recent years of research. [1][2][3][4][5][6][7][21][22][23][39][40][41][42][43][44][45][46][47][48] Especially liquid salts with dicyanamide anions are a powerful precursor for N-doped carbons, [1][2][3][4][5][6][7] and for advanced co-doping with S. 27 Herein we present a modified IL route using phosphonium additives, paving the way towards P-and N-co-doped carbonsa class of materials only rarely reported in the literature so far. 36 BMP-dca with 40 mol% of tetrabutyl-phosphonium-bromide (TBuPBr) as a phosphorus source was therefore carbonised at 1000 1C in a constant flow of inert gas (see ESI † for details).…”

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confidence: 99%

Nitrogen- and phosphorus-co-doped carbons with tunable enhanced surface areas promoted by the doping additives

et al. 2013

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Herein we present a modified IL route using phosphonium additives, paving the way towards P-and N-co-doped carbonsa class of materials only rarely reported in the literature so far. 36BMP-dca with 40 mol% of tetrabutyl-phosphonium-bromide (TBuPBr) as a phosphorus source was therefore carbonised at 1000 1C in a constant flow of inert gas (see ESI † for details). The black solid product is a carbonaceous material exhibiting a local graphitic order that is limited in its extension. This can be derived from the powder X-ray diffraction (PXRD) patterns showing broadened, but intense, (002) and (100) reflexes typical for a stacking motif in turbostratic-like carbons (compare Fig. S1, ESI †). The black product was also characterised by means of elemental combustion analysis (EA) and inductively coupled plasma optical emission spectrometry (ICP-OES) to determine the degree of heteroatom-doping: 4.1 wt% of N-doping (EA) and 5.7 wt% of P-doping (ICP-OES) are revealed. The material is thus successfully dually doped; especially the remarkably high degree of P-doping compared to other approaches 36-38 is noteworthy and points out the advantages of the method. To also prove the homogeneity of the material, elemental mapping based on energy dispersive X-ray spectroscopy (EDX) and wavelength dispersive X-ray spectroscopy (WDX) was performed. The data are provided in the ESI † (Fig. S2-S5, ESI †), showing clearly that the dopants are spread homogeneously throughout the material. Significant local concentration maxima cannot be found. The binding environments of both N and P could be elucidated by X-ray photoelectron spectroscopy (XPS), and the detailed N1s and P2p scans are depicted in Fig. 1. The results for nitrogen are as expected according to our previous studies:1,2,27,46 three deconvolved contributions appear at 398.13 eV, 400.88 eV and 402.80 eV that can be assigned to pyridinic and pyrollic nitrogen species, quaternary graphitic nitrogen and minor oxidised nitrogen binding motifs (due to oxidative processes on the surface of the materials), respectively. 16,34,49,50 The N doping thus occurs with N atoms firmly bound to the carbon backbone. To clearly assign the P2p XPS scan to certain chemical environments is however more difficult. Fig. 1 Deconvolved XPS scans of the N1s and P2p orbitals of the material.

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Block-Copolymer assisted synthesis of hierarchical carbon monoliths suitable as supercapacitor electrodes

Cited by 120 publications

References 59 publications

The contribution of sulfate ions and protons to the specific capacitance of microporous carbon monoliths

The contribution of sulfate ions and protons to the specific capacitance of microporous carbon monoliths

Synthesis of porous NiO nanocrystals with controllable surface area and their application as supercapacitor electrodes

Nitrogen- and phosphorus-co-doped carbons with tunable enhanced surface areas promoted by the doping additives

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