Supercapacitor-Type Behavior of Carbon Composite and Replica Obtained from Hybrid Layered Double Hydroxide Active Container

Abstract

An original concept based on carbon replica method and adapted on organic/inorganic (O/I) hybrid layered double hydroxide (LDH) assembly is used to impart resulting carbon composites and replicas with interesting electrochemical properties. Thanks to the isomorphous cation substitution possible within the LDH layers, a series of O/I materials are prepared using the emulsifier 2-acrylamido-2-methyl-1-propanesulfonate acid (AMPS) as a source of carbon and Zn2Al, Co2Al0.5Fe0.5 and Ni2Al as the LDH framework container. The process of carbonization and acid leaching is characterized by in situ X-ray diffractometry, Raman spectroscopy, and the pore formation of the resulting carbon replica by nitrogen adsorption. According to the carbonization/acid-leaching procedure, the electrochemical behavior is characterized in various aqueous electrolytes, using four salts, including 1.0 M NaNO3, 0.5 M Na2SO4, 1 M Na2SO3, and 6 M KOH by means of cyclic voltammetry, galvanostatic mode, and complex impedance spectroscopy. Here, the key facet is the combination of the capacitive behavior of carbon, the pseudo-capacitive response coming from its functionalized surface, as well as redox reactions resulting from the inorganic particles present in the carbon composite and acting as a pore former during the acid leaching. From an optimized potential window of 1.2 V in 1 M Na2SO3, an electric energy of 11.0 W h/kg associated with a power density of 87.75 kW/kg is retrieved at a current density of 10 mA/g for carbon replica obtained from Co2Al0.5Fe0.5/AMPS, and this is determined to be stable at moderate regime without significant capacitance fading. Meanwhile, a corresponding carbon composite, i.e., before acid leaching, presents over an optimized potential window of 1.8 V, a capacitance per surface unit of 92.6 μF/cm2 at slow scan rate, largely because of the pseudo-capacitance effect, and a reversible redox reaction of 43 mAh/g is obtained at the C/3 regime in galvanostatic mode. Finally, preliminary tests in an asymmetric capacitor give some hints on the versatility of the new innovative approach using electrochemically active template, which creates the carbon part with suitable (pseudo)-capacitive properties, as well as being electronically conductive embedding inorganic redox centers.

Sulfur-doped mesoporous carbon from surfactant-intercalated layered double hydroxide precursor as high-performance anode nanomaterials for both Li-ion and Na-ion batteries

“…The other type of carbonaceous nanostructures was obtained by direct thermal carbonization of anions intercalated between interlayer galleries at moderate or high temperatures, including zero-dimensional nano-onion [10]/nano-ring [11], two-dimensional graphene [12], and three-dimensional mesoporous carbon materials [13]. Leroux and Dubois reported a series of progressions of diverse mesoporous carbon nanostructures through carbonization of different intercalated anions [13][14][15][16], such as poly(vinylbenzene-4-sulfonate) and 3-sulfopropyl-methacrylic acid. Coronado et al prepared two distinctly different nanocarbons from a sebacate-intercalated NiFe-LDH precursor [12], involving carbon nano-onion obtained at 400°C and graphene formed at 900°C.…”

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

“…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].…”

Two‐Dimensional Hybrid Materials: Transferring Technology from Biology to Society

“…Aside from the hybridization and the mixing with electrical percolates, another concept consists of producing an intimate mixture from a 2D LDH hybrid assembly by carbonization where the collapse of the inorganic moiety may play the role of porous agent for the carbon replica after acid leaching or may remain partly to supply an additional pseudocapacity. [51] A single layer of nanosheets is of interest in the oxygen evolution reaction, a key reaction in water splitting. [52] More active sites and improved electronic conductivity were demonstrated for Ni/Fe and Ni/Co LDH nanosheets, outperforming a commercial iridium dioxide catalyst in both activity and stability.…”