Spontaneous grafting of 9,10-phenanthrenequinone on porous carbon as an active electrode material in an electrochemical capacitor in an alkaline electrolyte

Comte, Annaïg Le; Chhin, Danny; Gagnon, Alexandre; Retoux, R.; Brousse, Thierry; Bélanger, Daniel

doi:10.1039/c4ta05536e

Cited by 73 publications

(82 citation statements)

References 77 publications

(140 reference statements)

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“…Carbon modification by grafting.-Carbon modification was carried out by grafting according to the procedure described in reference 35 using spontaneous reduction of in-situ generated diazonium cations. 2-amino-9,10-phenanthrenequinone (186.3 mg, 0.1 equiv.…”

Section: Methodsmentioning

confidence: 99%

“…The CV of asreceived DLC Supra 30 displays a rectangular shaped voltammogram typical of the electrical double-layer (EDL) charging, whereas for DLC Supra 30-PQ, a pseudo-capacitive contribution related to the PQ molecules strongly bonded to the surface of activated carbon takes place together with the EDL formation. 35 As a result of grafting PQ molecules, the specific capacitance increases from 82 F g −1 for DLC Supra 30 up to 194 F g −1 for DLC Supra 30-PQ. It is also interesting to note on Fig.…”

Section: Improvement Of Long Time Performance By Coupling Of Differenmentioning

confidence: 99%

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Strategies to Improve the Performance of Carbon/Carbon Capacitors in Salt Aqueous Electrolytes

Abbas

Ratajczak

Babuchowska

et al. 2015

J. Electrochem. Soc.

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105

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Strategies are presented to enhance operating potential and cycle life of AC/AC capacitors using salt aqueous electrolytes. Li 2 SO 4 (pH = 6.5) allows 99% efficiency to be exhibited at 1.6 V cell potential with low self-discharge, while in BeSO 4 (pH = 2.1) efficiency is low (81%). Li 2 SO 4 performs better due to high di-hydrogen over-potential at the negative electrode and related pH increase in AC porosity. When stainless steel current collectors are used in Li 2 SO 4 , the cell resistance suddenly increases after 12 hours floating at 1.6 V, due to corrosion of the positive collector. With nickel negative and stainless steel positive collectors, the electrode potentials are shifted by −105 mV at cell potential of 1.6 V, allowing stable cell parameters (capacitance, resistance) and reduction of corrosion products formation on positive steel collector after 120 hours floating. Phenanthrenequinone was grafted on activated carbon to get an additional faradaic contribution in buffer solutions (pH = 4.0 or 7.2). The three-electrode cell CVs show that the redox peaks of the phenanthrenequinone graft shift toward negative values when pH increases from 4 to 7. Electrical double-layer capacitors (EDLCs) based on activated carbons (AC) and traditional aqueous electrolytes, such as H 2 SO 4 and KOH, operate at low cell potential (up to ∼0.8 V), limiting their capability at industrial level. [1][2][3][4] In order to improve the energy (E = 1 2 CU 2 ), both capacitance (C) and cell potential (U) determined by the stability window of the electrolyte have to be optimized. In this context, it has been recently demonstrated that symmetric capacitors based on AC electrodes and salt aqueous electrolyte (0.5 mol L −1 Na 2 SO 4 ) exhibit excellent cyclability under galvanostatic charge/discharge up to 1.6 V. 5,6 . While using 1 mol L −1 Li 2 SO 4 and gold current collectors, excellent cycle life has been shown up to ∼1.9 V using galvanostatic charge/discharge. 7,8 Such high cell potential value is caused by a high over-potential for di-hydrogen evolution as a consequence of water reduction and OH − ions generation in the porosity of the negative AC electrode. 5,7 According to the Nernst equation (E red = −0.059 pH), the pH increase associated to OH − ions causes locally a shift of redox potential to lower values. Based on this fact, it has been recently demonstrated that the di-hydrogen evolution over-potential is higher in almost neutral electrolyte solutions (pH = 4-8) than in acidic ones, resulting in larger operating cell potential of asymmetric capacitors in the former media.9 From the foregoing, it makes sense to study in more details the influence of aqueous electrolyte pH on the electrochemical performance of AC/AC capacitors beyond only the cell potential.Besides, when shifting from gold to stainless steel current collectors in order to develop low cost AC/AC capacitors in 1 mol L −1 Li 2 SO 4 , constant capacitance and low cell resistance have been observed during potentiostatic floating at cell potential of 1.5 V, whil...

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Section: Methodsmentioning

confidence: 99%

Section: Improvement Of Long Time Performance By Coupling Of Differenmentioning

confidence: 99%

Strategies to Improve the Performance of Carbon/Carbon Capacitors in Salt Aqueous Electrolytes

Abbas

Ratajczak

Babuchowska

et al. 2015

J. Electrochem. Soc.

Self Cite

105

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“…The current was normalized to the CDC film footprint surface area and thickness. Both CV curves exhibit a quasi-rectangular shape within a 1.1 V potential window, typical from capacitive signature of carbon material in KOH electrolyte [21]. Furthermore, small oxidation and reduction waves are observed at À0.18 V vs NHE and À0.37 V vs NHE, respectively, after modification.…”

Section: Chemical Grafting Of Aqmentioning

confidence: 82%

“…Delamar and coworkers were the first to take advantage of the electrochemical reduction of diazonium cations to modify carbon electrodes [17,18]. Precursor solutions for such electrochemical grafting can be prepared either from dissolution of diazonium derivatives in acetonitrile [19], or by in situ generation of diazonium salts from the parent aniline [20,21]. Both methods have been used to graft various aryl radicals on a large variety of substrates such as high surface area carbons, metals or semi-conductors [22][23][24][25].…”

Section: Introductionmentioning

confidence: 99%

Anthraquinone modification of microporous carbide derived carbon films for on-chip micro-supercapacitors applications

Brousse

Martin²,

Brisse

et al. 2017

Electrochimica Acta

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OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao. A B S T R A C TThe modification of carbide derived carbon (CDC) thin film electrodes with anthraquinone (AQ) molecules was demonstrated by using pulsed chronoamperometry, in 0.1 M NEt 4 BF 4 /ACN solution of AQ diazonium derivative. The functionalization of CDC electrodes was only possible when a critical pore size is reached: only 2 nm pore diameter CDC can be grafted with AQ moieties, smaller pore size leading to a poorly functionalized electrode. High AQ surface coverage of 0.88 Â 10 À10 mol.cm À2 was determined using 2 nm pore size CDC. Despite a decrease in double layer capacitance value of about 10%, the total capacitance of the AQ-modified on-chip CDC electrodes was twice larger than that of pristine CDC film, leading to high total capacitance value of 44 mF.cm À2 (338 F.cm À3). The cyclability of the AQ-modified onchip CDC electrode was also investigated. The faradic contribution of AQ grafted molecules progressively decreased during cycling and only 39% of the normalized capacity remained after 500 cycles; this decrease has been assigned to electrostatic repulsion of dianionic AQ confined in narrow micropores in the alkaline media.

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“…The covalent attachment of electroactive molecules such as quinone for example, on the surface of activated carbon has shown drastic improvement of charge storage. [37][38][39][40][41][42][43][44][45] Very recently, Downard and coworkers demonstrated the possibility to covalently bind aryl group to MnO 2 nanorods from diazonium-based grafting, 46 assuming that such strategy can be used to improve electrochemical behavior of manganese dioxide based electrodes.In this work, the chemical bridging between MnO 2 and carbon particles by diazonium chemistry is presented. The intimate contact between the two materials through a covalent bond can improve the …”

mentioning

confidence: 99%

Electrochemical Performance of Carbon/MnO₂Nanocomposites Prepared via Molecular Bridging as Supercapacitor Electrode Materials

Ramirez-Castro

Crosnier

Athouël

et al. 2015

J. Electrochem. Soc.

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The chemical binding of amorphous manganese oxide and carbon particles was achieved with the diazonium chemistry. The synthesis was performed in two steps, with a first step consisting in the surface functionnalization of carbon particles with aminophenyl groups and the subsequent attachment of amorphous manganese oxide particles through generated phenyl groups. The bond between carbon and MnO 2 particles is believed to occur between the carbon from the phenyl groups attached to carbon particles, and the oxygen atoms from the manganese oxide lattice. The capacitance of the carbon/MnO 2 grafted nanocomposite electrode is doubled compared to a simple mixture of its two components. The constant increment in the study and development of energy storage devices such as electrochemical capacitors (ECs) is related to an ever-growing demand of energy of the society. Electrochemical capacitors can be classified by their energy storage mechanisms in two main systems: 1) electrical double layer capacitance which arises from the charge separation at the electrode/electrolyte interface 1 and 2) pseudocapacitive charge storage phenomena where fast and reversible reactions take place.2 At this time, carbon is the commonly used electrode material for electrical double layer capacitor (EDLC) 3 while transition metal oxides and some conductive metal nitrides have demonstrated good performance as pseudocapacitive electrodes. 4 In terms of pseudocapacitive materials, manganese oxide (MnO 2 ) has proved to be one of the most promising materials due to its high energy density, low cost, environmental friendliness and natural abundance. 5 The initial studies describing the use of MnO 2 as an electrode material for ECs were performed by Lee and Goodenough. 6 They reported that amorphous or poorly crystallized MnO 2 powders incorporated into composite electrodes exhibited a capacitor-like electrochemical response in neutral KCl electrolyte, and delivered a specific capacitance of 200 F/g for "bulk" electrodes. Since this initial report, the interest in MnO 2 for ECs applications has grown steadily.Despite its electrochemical performance, the use of MnO 2 is still limited to moderate power applications due to its poor intrinsic electrical conductivity (10 −5 to 10 −6 S.cm −1 ). 7 Up to now, one of the most viable approaches to circumvent this major drawback is the use of a conductive additive such as carbon for improving the percolation through the electrode. For example, carbon black has been used just in a simple mixture with manganese oxide. 28 From all these studies it is clear that an intimate mixture of the carbon additive and manganese dioxide leads to improved power capability, but there is no clear trend to tell which carbon additive leads to the best electrode. However, carbon black is already widely used in ECs technology and thus it should be desirable to focus on this type of carbon when designing MnO 2 based electrode.In this study, we designed a new approach for the preparation of carbon/metal oxide composite electrod...

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Spontaneous grafting of 9,10-phenanthrenequinone on porous carbon as an active electrode material in an electrochemical capacitor in an alkaline electrolyte

Abstract: Spontaneous grafting of 9,10-phenanthrenequinone (PQ) on Black Pearls carbon by reduction of the corresponding in situ generated diazonium cations has been successfully achieved.

Cited by 73 publications

References 77 publications

Strategies to Improve the Performance of Carbon/Carbon Capacitors in Salt Aqueous Electrolytes

Strategies to Improve the Performance of Carbon/Carbon Capacitors in Salt Aqueous Electrolytes

Anthraquinone modification of microporous carbide derived carbon films for on-chip micro-supercapacitors applications

Electrochemical Performance of Carbon/MnO₂Nanocomposites Prepared via Molecular Bridging as Supercapacitor Electrode Materials

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Spontaneous grafting of 9,10-phenanthrenequinone on porous carbon as an active electrode material in an electrochemical capacitor in an alkaline electrolyte

Abstract: Spontaneous grafting of 9,10-phenanthrenequinone (PQ) on Black Pearls carbon by reduction of the corresponding in situ generated diazonium cations has been successfully achieved.

Cited by 73 publications

References 77 publications

Strategies to Improve the Performance of Carbon/Carbon Capacitors in Salt Aqueous Electrolytes

Strategies to Improve the Performance of Carbon/Carbon Capacitors in Salt Aqueous Electrolytes

Anthraquinone modification of microporous carbide derived carbon films for on-chip micro-supercapacitors applications

Electrochemical Performance of Carbon/MnO2Nanocomposites Prepared via Molecular Bridging as Supercapacitor Electrode Materials

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Product

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Electrochemical Performance of Carbon/MnO₂Nanocomposites Prepared via Molecular Bridging as Supercapacitor Electrode Materials