Improved electro-grafting of nitropyrene onto onion-like carbon via in situ electrochemical reduction and polymerization: tailoring redox energy density of the supercapacitor positive electrode

Herein, we report a improved method for the physical grafting of 1-nitropyrene (Pyr-NO2) onto highly graphitized carbon onion. This is achieved through a lowering of the onset potential of the pyrene polymerization via in situ reduction of the NO2 group. The additional redox activity pertaining to the reduced NO2 enables exceeding the faradaic capacity which is associated with the p-doping of the grafted pyrene backbone, as observed for pyrene, 1-aminopyrene, and unreduced Pyr-NO2. Theoretical calculations demonstrate the charge transfer and binding enthalpy capabilities of Pyr-NO2, which are significantly higher than those of the other two species, and which allow for improved p-stacking on the carbon surface. Upon 20 wt % grafting of Pyr-NO2, the capacity of the electrode jumps from 20 mAh g-1 electrode to 38 mAh g-1 electrode, which corresponds to 110 mAh g-1 per mass of Pyr-NO2 and the average potential is increased by 200 mV. Very interestingly, this high performance is also coupled with outstanding retention with respect to both the initial capacity for more than 4000 cycles, as well as the power characteristics, demonstrating the considerable advantages of employing the present in situ grafting technique

Interest of molecular functionalization for electrochemical storage

International audienceDespite great interests in electrochemical energy storage systems for numerous applications, considerable challenges remain to be overcome. Among the various approaches to improving the stability, safety, performance, and cost of these systems, molecular functionalization has recently been proved an attractive method that allows the tuning of material surface reactivity while retaining the properties of the bulk material. For this purpose, the reduction of aryldiazonium salt, which is a versatile method, is considered suitable; it forms robust covalent bonds with the material surface, however, with the formation of multilayer structures and sp3 defects (for carbon substrate) that can be detrimental to the electronic conductivity. Alternatively, non-covalent molecular functionalization based on π–π interactions using aromatic ring units has been proposed. In this review, the various advances in molecular functionalization concerning the current limitations in lithium-ion batteries and electrochemical capacitors are discussed. According to the targeted applications and required properties, both covalent and non-covalent functionalization methods have proved to be very efficient and versatile. Fundamental aspects to achieve a better understanding of the functionalization reactions as well as molecular layer properties and their effects on the electrochemical performance are also discussed. Finally, perspectives are proposed for future implementation of molecular functionalization in the field of electrochemical storage

In Situ Polymerization Process: An Essential Design Tool for Lithium Polymer Batteries

Polymer electrolytes (PEs), a type of solid-state electrolytes (SSEs), have been in contention for nearly half a century to replace organic liquid electrolytes (LEs) that are used in state-of-the-art lithium-ion batteries (LIBs). They are envisaged to accelerate the industrial-scale production of safe, energy-dense, flexible, and thin lithium polymer batteries (LPBs). LPBs are expected to be widely employed for electric propulsion and other futuristic applications, such as flexible electronics and the Internet of Things (IoT). Even though several polymer architectures and chemistries have been attempted so far, PEs that can outperform LEs remain a real challenge. Apart from inadequate Li+-ion transport properties, challenges concerning the integration of PEs and the engineering of compatible, robust, and durable interfaces and interphases at both the electrodes of LPBs must be appropriately addressed. Recently, the in situ polymerization process has been widely employed as a robust fabrication tool for surpassing the intricacies related to the integration of PEs in LPBs. Hence, in this review, we focus on the in situ polymerization processes that employ various polymerization methods (e.g., free-radical polymerization, ionic polymerization, electropolymerization, condensation polymerization, etc.), functional monomers and oligomers (e.g., acrylate, methacrylate, allyl and vinyl ethers, epoxides, etc.), and PE integration strategies for the fabrication of lithium (ion and metal) polymer batteries (LIPBs and LMPBs). Additionally, this review also evaluates the approaches that have been developed until now to implement the in situ processing of LPBs from large-sized pouch cells to flexible-/printable-batteries and even microbatteries

3D Polyaniline Porous Layer Anchored Pillared Graphene Sheets: Enhanced Interface Joined with High Conductivity for Better Charge Storage Applications

Here, we report synthesis of a 3-dimensional (3D) porous polyaniline (PANI) anchored on pillared graphene (G-PANI-PA) as an efficient charge storage material for supercapacitor applications. Benzoic acid (BA) anchored graphene, having spatially separated graphene layers (G-Bz-COOH), was used as a structure controlling support whereas 3D PANI growth has been achieved by a simple chemical oxidation of aniline in the presence of phytic acid (PA). The BA groups on G-Bz-COOH play a critical role in preventing the restacking of graphene to achieve a high surface area of 472 m²/g compared to reduced graphene oxide (RGO, 290 m²/g). The carboxylic acid (−COOH) group controls the rate of polymerization to achieve a compact polymer structure with micropores whereas the chelating nature of PA plays a crucial role to achieve the 3D growth pattern of PANI. This type of controlled interplay helps G-PANI-PA to achieve a high conductivity of 3.74 S/cm all the while maintaining a high surface area of 330 m²/g compared to PANI-PA (0.4 S/cm and 60 m²/g). G-PANI-PA thus conceives the characteristics required for facile charge mobility during fast charge–discharge cycles, which results in a high specific capacitance of 652 F/g for the composite. Owing to the high surface area along with high conductivity, G-PANI-PA displays a stable specific capacitance of 547 F/g even with a high mass loading of 3 mg/cm², an enhanced areal capacitance of 1.52 F/cm², and a volumetric capacitance of 122 F/cm³. The reduced charge-transfer resistance (RCT) of 0.67 Ω displayed by G-PANI-PA compared to pure PANI (0.79 Ω) stands out as valid evidence of the improved charge mobility achieved by the system by growing the 3D PANI layer along the spatially separated layers of the graphene sheets. The low RCT helps the system to display capacitance retention as high as 65% even under a high current dragging condition of 10 A/g. High charge/discharge rates and good cycling stability are the other highlights of the supercapacitor system derived from this composite material

Peculiar Li-storage mechanism at graphene edges in turbostratic carbon black and their application in high energy Li-ion capacitor

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Cascade‐Type Prelithiation Approach for Li‐Ion Capacitors

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From waste paper basket to solid state and Li-HEC ultracapacitor electrodes : a value added journey for shredded office paper

Hydrothermal processing followed by controlled pyrolysis of used white office paper (a globally collectable shredded paper waste) are performed to obtain high surface area carbon with hierarchical pore size distribution. The BET specific surface area of such carbon is 2341 m2 g−1. The interconnected macroporous structure along with the concurrent presence of mesopores and micropores makes the material ideal for ultracapacitor application. Such waste paper derived carbon (WPC) shows remarkable performance in all solid-state supercapacitor fabricated with ionic liquid-polymer gel electrolyte. At room temperature, the material exhibits a power density of 19 000 W kg−1 with an energy capability of 31 Wh kg−1. The Li-ion electrochemical capacitor constructed using WPC as cathode also shows an excellent energy storage capacity of 61 Wh kg−1