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Sulfur-Containing Activated Carbons with Greatly Reduced Content of Bottle Neck Pores for Double-Layer Capacitors: a Case Study for Pseudocapacitance Detection

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Sulfur-Containing Activated Carbons with Greatly Reduced Content of Bottle Neck Pores for Double-Layer Capacitors: a Case Study for Pseudocapacitance Detection Sulfur-Containing Activated Carbons With Greatly Reduced Content of Bottle Neck Pores For Double-Layer Capacitors: A Case Study For Pseudocapacitance Detection a b a b *a 5 Wentian Gu, Marta Sevilla, Alexandre Magasinski, Antonio B. Fuertes, and Gleb Yushin Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x Synthesis of S-doped activated carbons (ACs) by carbonization and simultaneous activation of S-based polymers was found to be an efficient route to produce porous carbons for double layer capacitors (EDLCs) with high specific energy and power densities combined 10 with low self-discharge. Here we investigate for the first time the processing-structure-property relationships related to the formation of polythiophene-derived ACs for EDLC applications. Sulfide bridges present in the polymer precursor were found to depress the shrinkage of the smallest micropores during the carbonization process and allow for the enhanced ion transport within the produced AC electrodes. The cyclic voltammetry (CV) measurements on S-doped ACs produced at 800 and 850 ºC showed high specific capacitance (up to ~200 Fg-1) and no significant self-discharge in neutral aqueous electrolytes. More importantly, these capacitance values remained virtually -1 15 identical for a sweep rate increasing from 1 to 50 mVs . The observed capacitance retention is quite remarkable for thick electrodes of ~200 µm and large AC particle size of 10-100 µm. It indicates great potential of the proposed synthesis technology for EDLC operating at high frequencies and high currents. In the course of our systematic studies of AC performance in different electrolytes we found a strong correlation between the large pseudocapacitance and the significant self-discharge in ACs. We harness the difference between the characteristic times required to establish a double layer and that of the pseudocapacitive redox reactions and propose a simple method to 20 estimate the fraction of pseudocapacitance. The proposed method is particularly valuable in cases when CV measurements do not show clear characteristic reduction-oxidation peaks. Keywords: supercapacitor, microporous, mesoporous, carbon, graphene, nanotube, doping, leakage, self-discharge, pseudocapacitance, functional groups 9, 10 50 enhance their energy storage ability , but could also lead to 10, 11 25 1. Introduction undesirable leakage currents and device degradation with cycling and/or storage, particularly at elevated temperatures. In the field of electrical energy storage, electrochemical Unfortunately, the detection of pseudocapacitance contributions, capacitors (ECs) technology offering a combination of high required for systematic studies and material optimization, is not a specific power, and stable operation under short term high current 55 trivial task since cyclic voltammetry (CV) curves may exhibit no pulses even in the case of full discharge 1, 2 is an indispensible evident peaks. This is because the enthalpies of various ion- 30 complement to Li-ion batteries. Potential applications of ECs electrode interactions on the surface of electrode materials may range from power supplies for memories in micro-computers to exhibit a very broad distribution. In fact, even the “classical” rapid heating devices in copiers and industrial printers to power pseudocapacitance materials, such as hydrous ruthenium oxide, for on-demand lighting on roads to electrical motors in hybrid 60 may show no characteristic peaks and exhibit a rectangular shape electric vehicles and industrial equipment to power sources in 12, 13 of the CV curves. 35 lasers, to name a few. The majority of commercial ECs are Desirable properties of porous carbons for the majority of EC believed to function as electrical double layer capacitors applications include high volumetric capacity (and therefore high (EDLCs), where the energy storage is purely electrostatic and particle density and high particle packing factor), the lack of virtually no charge transfer takes place across the electrode- 65 uncontrolled side reactions with electrolyte (to achieve low self- electrolyte interface. Micro- and meso-porous carbons utilized in discharge and long cycle life), scalable low-cost synthesis and 40 EC/EDLC electrodes have shown steady developments during the consistent properties (such as pore size distribution, density, last decade and demonstrated increased specific and volumetric 3-5 6-8 impurity content and surface functionalities). While several capacitance and longer EC cycle life. The contribution of interesting methods have recently been explored for the reduction/oxidation (redox) pseudocapacitance reactions to 14-21 70 microporous carbon synthesis, such as zeolite- and/or a School of Materials Science and Engineering, Georgia Institute of mesoporous silica 22-25 templating, soft templating 26, 27, and the 45 Technology, Atlanta, GA, USA b Instituto Nacional del Carbón (CSIC), P.O. Box 73, 33080 Oviedo, use of inorganic carbide precursors for carbide-derived carbon Spain synthesis 22-24, 27-40, to mention a few, activated carbons (AC) will * Corresponding author email: [email protected] the double layer capacitance of porous carbons may potentially likely to dominate commercial EC applications due to their surface area accessible by electrolyte ions. Both too large 31, 32, 48, 52, 53 48, 53-56 75 comparable and often superior performance combined with well- and too small pores are known to offer inferior established manufacturing. 41-43 The recent advancements in AC capacitance. During AC synthesis very small pores (not synthesis from organic natural 41, 44-49 or synthetic 42, 44, 50, 51 accessible by electrolyte ions in ECs) are formed by the shrinkage precursors show rapid progress. To further advance the 85 of the material during carbonization of organic precursors at high performance of ACs one needs to fine-tune synthesis techniques temperatures. 57 80 to optimize carbon pore size distribution and to maximize the To depress the pore shrinkage of micropores and therefore This journal is © The Royal Society of Chemistry [year] [journal], [year], [vol], 00–00 | 1 better match the pore size with charge carriers in the electrolyte, shape of the carbon pores. Hasegawa et al. 58 proposed sulfonation of carbon precursor by All electrochemical measurements in this study were intensive acid treatment. Sulfur-containing functional groups 60 performed in symmetric beaker cells. Gold thin foils were used as were proposed to support the larger pores and avoid their collapse current collector. Celgard 2325 membrane was used as separator. 5 or shrinkage at high temperatures. However, acidic treatments We used a suspension of the Polytetrafluoroethylene (PTFE) offer rather poor control over the uniformity and distribution of (Aldrich, 60 wt. % in water) as a fibrous binder. The total amount S-containing functional groups in ACs. In addition, the of the binder in electrodes was kept at 15 wt. %. The electrodes pseudocapacitive reactions in EC induced by acid oxidations 65 were thoroughly dried overnight and then assembled in beaker may, in principle, lead to undesirable self-discharge and device cells. The thickness of the electrodes was controlled at around 10 10 degradation. 200µm. The following electrolyte solutions have been selected In this work, we report for the first time how the intrinsic for the study: 6M lithium chloride (LiCl), 1M hydrochloride sulfur (S) - doping of activated carbon may reduce the content of (HCl) and 0.5M sulfuric acid (H2SO4) aqueous solutions. Cyclic the smallest bottleneck micropores and enhance the rate 70 voltammetry (CV) measurements were performed using a 1250 capability of EDLC electrodes. In the course of our study we Galvanostat/Potentiostat (Solartron Instruments, USA) at -1 15 systematically investigate how synthesis conditions of S-doped different constant scan rate (1 - 500 mV s ) between -0.6V and ACs influence their pore size distribution, specific surface area, 0.6 V. The capacitance of a symmetric cell was deduced from the microstructure and chemistry. We also reveal how the physical loop area by the relation C=A/(2ΔV), where C is the cell and chemical properties of these AC affect their electrochemical 75 capacitance, A is the loop area and ΔV the potential window. With performance in different aqueous electrolytes. More importantly, the assumption that two electrodes assembled together are equal 20 by using some of such carbons, we demonstrate that simple in capacitance, the capacitance of each electrode is double the kinetic studies of cyclic voltammograms allow one to distinguish value of the whole cell. Charge-discharge measurements were between slow pseudocapacitive reactions and faster double layer performed using a SCTS supercapacitor testing system (Arbin adsorption within microporous carbon electrodes. 80 Instruments, USA) in the range of constant current densities (50 - 10000 mA g-1) between -0.6 and 0.6 V. The capacitance was 2. Experimental deduced from the charge-discharge curves by the relation C=I/(dV/dt), where C is the cell capacitance, I is the current, 25 For the synthesis of S-doped carbon, 2-thiophenemethanol dV/dt is the average slope of the discharge curve. Electrochemical (Aldrich) in CH3CN was slowly added to FeCl3 solution in 85 impedance spectra (EIS) was performed by Gamry Reference 600 CH 3CN. After kept under stirring for 15h, the mixture was Potentiostat. Nyquist plots and Bode plots are recorded for filtered and PTh was separated. The obtained
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