Kilogram-scale synthesis of ordered mesoporous carbons and their electrochemical performance

An efficient post-cure approach has been demonstrated for the kilogram-scale synthesis of high-quality ordered mesoporous carbons (OMC) by using triblock copolymer Pluronic F127 as a template, phenolic resol as a carbon precursor and polyurethane foam as a sacrificial scaffold through an organic–organic self-assembly. The effects of the concentration and the loading amount of resol on the mesostructure of the carbons are systematically investigated. The small-angle X-ray scattering, nitrogen sorption and transmission electron microscopy results reveal that the resultant OMC in kilogram-scale quantities possesses high surface area (∼690 m² g⁻¹), large pore volume (∼0.45 cm³ g⁻¹) and uniform, large pore size (∼4.5 nm) as well as thick pore walls (∼6.5 nm). The OMC exhibits good electrochemical performance of about 130 F g⁻¹ in KOH electrolyte.     

Preparation and performance of a core-shell carbon/sulfur material for lithium/sulfur battery

The core-shell carbon/sulfur material with high performance is prepared by a facile and fast deposit method in an aqueous solution. As sulfur ratio is 85% (w/w) in the composite, scanning electron microscope (SEM) and transmission electron microscope (TEM) observation show that the moniliform particles with 10 nm sulfur shells preserve the morphology of carbon cores. Tested as the cathode material in a lithium cell with binary organic electrolyte at room temperature, the composite shows excellent electrochemical performance. It exhibits a specific capacity up to 1232.5 mAh g⁻¹ at the initial discharge and its specific capacity remained above 800 mAh g⁻¹ after 50 cycles. Meanwhile, the composite also exhibits the high-rate behavior at 800 mA g⁻¹ of current density. Assuming a complete reaction to the final product, Li₂S, the utilization of the electrochemically active sulfur is about 85% at the initial cycle. Electrochemical impedance spectroscopy (EIS) is introduced to understand the impact of the microstructure of composite on electrochemistry. According to our study, a novel core-shell structural carbon/sulfur material is proposed and the key factors of the preparation are discussed.     

Ordered mesoporous carbons with controlled particle sizes as catalyst supports for direct methanol fuel cell cathodes

The ordered mesoporous carbons (OMCs) with various primary particle sizes were synthesized and the effect of the particle size of the OMC supports on their performance for the oxygen reduction reaction (ORR) in direct methanol fuel cells was investigated. The ordered mesoporous silica (OMS) templates with particle sizes of 100, 300, and 700 nm (OMS-100, -300, and -700) were synthesized by changing the synthesis pH and Na content in the silica source, sodium silicate. The OMCs with similar particle sizes and morphologies (OMC-100, -300, and -700) were faithfully replicated by using the corresponding OMSs as templates and phenanthrene as a carbon source. Structural characterizations revealed that three OMCs exhibit uniform mesopores of 4–5 nm and BET surface areas of 600–800 m² g⁻¹. The Pt nanoparticles of ca. 3 nm were supported onto these OMCs and the resulting Pt/OMC catalysts were tested for the ORR. The three OMC supported catalysts exhibited the catalyst utilization efficiencies and ORR activities of similar range, with the values of Pt/OMC-300 catalyst being slightly higher than the other two catalysts.     

Nitrogen/sulfur dual-doped mesoporous carbon with controllable morphology as a catalyst support for the methanol oxidation reaction

Ordered mesoporous carbon (OMC) was synthesized by nano-casting method using novel fluidic precursor – acrylonitrile telomer (ANT). By the penetration of mesoporous silica template with pure ANT, followed by the stabilization, carbonization and removal of the template, we obtained highly ordered mesoporous carbon rods (specific area 408 m² g⁻¹). When an acetone solution of ANT (66 and 33 wt.%) was used instead of pure ANT, carbon materials with mesopore ranging from 2 to 7 nm were obtained (specific area 843 and 1012 m² g⁻¹ respectively). Both nitrogen and sulfur atoms were doped into mesoporous carbon with 4 and 0.6 at.% using nitrogen containing monomer and sulfur containing chain transfer agent, without involving complicated synthetic technique and poisonous gaseous compounds. This method was proved to be a facile way to synthesize nitrogen and sulfur containing OMC with partially controllable pore distribution and morphology. More importantly, due to unique mesopore structure and heteroatom doping, Pt nano-particles deposited on the OMCs showed electrocatalytic activity as high as 508 mA mg⁻¹ Pt in methanol oxidation which is 1.7-fold of activity of Pt deposited on commercial Vulcan carbon black.     

Differential scanning calorimetry analysis of an enhanced LiNi0.8Co0.2O2 cathode with single wall carbon nanotube conductive additives

The replacement of traditional conductive carbon additives with single wall carbon nanotubes (SWCNTs) in lithium metal oxide cathode composites has been shown to enhance thermal stability as well as power capability and electrode energy density. The dispersion of 1 wt% high purity laser-produced SWCNTs in a LiNi_0.8Co_0.2O₂ electrode created an improved percolation network over an equivalent composite electrode using 4 wt% Super C65 carbon black; evidenced by additive connectivity in SEM images and an order of magnitude increase in electrode electrical conductivity. The cathode with 1 wt% SWCNT additives showed comparable active material capacity (185–188 mAh g⁻¹), at a low rate, and Coulombic efficiency to the cathode composite with 4 wt% Super C65. At increased cycling rates, the cathode with SWCNT additives had higher capacity retention with more than three times the capacity at 10C (16.4 mA cm⁻²). The thermal stability of the electrodes was evaluated by differential scanning calorimetry after charging to 4.3 V and float charging for 12 h. A 40% reduction of the cathode exothermic energy released was measured when using 1 wt% SWCNTs as the additive. Thus, the results demonstrate that replacing traditional conductive carbon additives with a lower weight loading of SWCNTs is a simple way to improve the thermal transport, safety, power, and energy characteristics of cathode composites for lithium ion batteries.     

Sucrose derived microporous–mesoporous carbon for advanced lithium–sulfur batteries

A microporous–mesoporous carbon has been successfully prepared via carbonization of sucrose followed by heat treatment process. The obtained porous carbon possesses abundant micropores and mesopores, which can effectively increase the sulfur loading. The composite exhibited a remarkable initial capacity of 1185 mAh g^?1 at 0.2 A g^?1 and maintained at 488 mAh g^?1 after 200 cycles, when employed for lithium?sulfur batteries. Moreover, the composite displayed enhanced rate capabilities of 1124, 914 and 572 mAh g^?1 at 0.2, 0.5 and 1.0 A g^?1. The outstanding electrochemical capabilities and facile low?cost preparation make the new microporous–mesoporous carbon as an excellent candidate for lithium sulfur batteries.     

In situ immobilization of cobalt phthalocyanine on the mesoporous carbon ceramic SiO2/C prepared by the sol–gel process. Evaluation as an electrochemical sensor for oxalic acid

The mesoporous carbon ceramics SiO₂/20 wt% C (S_BET = 160 m² g⁻¹) and SiO₂/50 wt% C (S_BET = 170 m² g⁻¹), where C is graphite, were prepared by the sol–gel method. Scanning electron microscopy images and the respective element mapping showed that, within the magnification used, no phase segregation was detectable. The materials containing 20 and 50 wt% of C presented electric conductivities of 9.2 × 10⁻⁵ and 0.49 S cm⁻¹, respectively. These materials were used as matrices to support cobalt phthalocyanine (CoPc), prepared in situ on their surfaces, to assure homogeneous dispersion of the electroactive complex in the pores of both matrices. The surface densities of cobalt phthalocyanine on both matrix surfaces were 0.014 mol cm⁻² and 0.015 mol cm⁻² for materials containing 20 and 50 wt% of C, respectively. Pressed disk electrodes made with SiO₂/50 wt% C/CoPc and SiO₂/20 wt% C/CoPc were tested as sensors for oxalic acid. The electrode was chemically very stable and presented very high sensitivity for this analyte, with a limit of detection, LOD = 5.8 × 10⁻⁷ mol L⁻¹.     

Exploration on sulfur/acid treatment of sepiolite composite positive electrode material for lithium-sulfur battery

High energy density battery system is endowed with more complex Lithium sulfur cathode whose electrochemical redox reaction and phase transition occurred due to multi electron participation. The different mole ratios of sepiolite mixed with sulfur were synthesized by acid cum thermal treatment method. The morphological analysis illustrates that the sepiolite powder is composed of micro fibrous bundles in the range of 1 μm to 10 μm. The sorption isotherms indicate that the sieved sepiolite (Sp) and different mole ratio (4, 6 and 8) of sepiolite/sulfur shows a type-IV isotherm of mesoporous material. The S/SvSp (sulfur/sieved sepiolite) composite cathode exhibits an initial discharge capacity of 1066 mAh g^?1 and attains a stable capacity of 596 mAh g^?1 during 40 cycles with 97% of efficiency. All the results correlated with the better electrochemical behaviour of electrode and it satisfies the needs of high energy density storage application.     

Reduced graphene oxide wrapped sulfur nanocomposite as cathode material for lithium sulfur battery

Sulfur has been investigated as an active electrode material for secondary batteries due to theoretically specific capacity compared to the lithium-ion battery. In the present study, reduced graphene oxide (RGO) sheets wrapped Sulfur nanocomposite (S-RGO) synthesized by hydrothermal method and confirmed the wrapping of RGO sheets on Sulfur nanoparticles by various analytical techniques. The synthesized S-RGO nanocomposite demonstrated improved interaction of sulfur nanoparticles with RGO which is confirmed through XPS analysis. The synthesized S-RGO resulted in significantly improved reversible specific capacity and higher rate capability (823 mAh/g at 0.1C, 400 mAh/g at 1C) with 77 wt% of sulfur loading amount on the cathode of the Li–S battery. Therefore, the present study opens up new insights into sustainable development in the field of Li–S battery energy storage applications.     

Hollow C/Co9S8 hybrid polyhedra-modified carbon nanofibers as sulfur hosts for promising Li–S batteries

Lithium-sulfur (Li–S) batteries hold great expectations as next-generation advanced capacity storage devices due to their higher theoretical energy density and low cost. Even so, polysulfide shuttles, insulation, and volume expansion of sulfur impede its commercial progress. To suppress these problems, we used electrospinning and self-templating to construct C/Co₉S₈ hybrid polyhedra-modified carbon nanofibers (denoted as C/Co₉S₈–C@S fibers) as sulfur hosts. The quasi-metallic polar Co₉S₈ strongly bonds and locks polysulfides, and the hollow polyhedra provide sulfur storage space. Moreover, the overall nanofiber forms an interconnected conductive network to assist the transmission of Li⁺/e⁻ and restrain the escape of the sulfur phase to a certain extent. Compared with C/Co₉S₈ polyhedra and carbon nanofibers, the C/Co₉S₈–C@S fiber delivers excellent adsorption characteristics for polysulfides. As a Li–S battery cathode, the C/Co₉S₈–C@S fiber (sulfur content: 87.20 wt%) exhibits an initial specific capacity of 1013.7 mAh g⁻¹ at 0.1 C, displaying a stable capacity of 694.9 mAh g⁻¹ after 150 cycles. Additionally, it shows a high specific capacity of 894.7 mAh g⁻¹ at 1C with a capacity decay of ~0.116% per cycle over 500 cycles.     

A wormhole-structured mesoporous carbon with superior adsorption for dyes

A series of large-pore mesoporous carbon materials with a three-dimensional wormhole framework structure were synthesized by nanocasting using mesoporous silica as a hard template. Samples of hard-template mesoporous silica with pore diameters from 3.08 to 6.43 nm, pore volumes from 0.59 to 1.02 cm³ g⁻¹ and surface areas from 832 to 579 m² g⁻¹ were prepared from tetraethyl orthosilicate as the silica source and ionic liquid 1-butyl-3-methylimidazolium bromide as structure-directing agent through hydrothermal treatment at different temperatures (110–150 °C) followed by calcining at 550 °C. Subsequently, carbon materials with large pore diameters (2.76–6.70 nm), pore volumes (0.74–2.10 cm³ g⁻¹) and high surface areas (1074–1276 m² g⁻¹) were synthesized using the various mesoporous silicas synthesized at the different hydrothermal temperatures as a hard-template. The carbon material obtained at a hydrothermal temperature of 150 °C possesses outstanding adsorbility for amaranth and methylene blue dyes.     

Application of gelatin as a binder for the sulfur cathode in lithium-sulfur batteries

Gelatin, a natural biological macromolecule, was successfully used as a new binder in place of poly(ethylene oxide) (PEO) in the fabrication of the sulfur cathode in lithium-sulfur batteries. The structure and electrochemical performance of the two types of sulfur cathodes, with gelatin and PEO as binders, respectively, were compared in 1 M LiClO₄ DME/DOL (V/V = 1/1) electrolyte. The results showed that the gelatin binder had multifunctional effects on the sulfur cathode: it not only functioned as a highly adhesive agent and an effective dispersion agent for the cathode materials, but also an electrochemically stable binder. The gelatin binder-sulfur cathode achieved a high initial capacity of 1132 mAh g⁻¹, and remained at a reversible capacity of 408 mAh g⁻¹ after 50 cycles, all of which were better than with the PEO binder-sulfur cathode under the same conditions.     

High-loading polysulfide/cement cathode for the manufacture of dynamically and statically stable lean-electrolyte lithium–sulfur batteries

In order to design lithium-sulfur cells for practical viability in the high-density energy storage, the exploitation of the effective contribution of the large amount of active-material mass to the high specific capacity at a lean-electrolyte condition must be considered. However, this is limited by the insulating nature of solid-state sulfur/sulfide, and the diffusion loss of the liquid-state polysulfides. In this study, Portland cement is adopted as a reinforcement material to design a high-loading polysulfide/cement cathode with sulfur loading and content of 8.64 mg cm⁻² and 60 wt%, respectively. The nonporous cement exhibits a high polysulfide-trapping capability and low electrolyte consumption, which enable the high-sulfur-loading cathode to achieve record low electrolyte-to-sulfur ratios of 7–3 μL mg⁻¹, with high gravimetric capacity and areal capacity of the cathode (i.e., 768 mA h g⁻¹ and 11.06 mA h cm⁻², respectively) and dynamically/statically electrochemical stability with 90% capacity retention after 100 cycles and a 1-month rest.     

Improved specific capacity of sulfur/starch‐based activated carbon spheres composites by polyaniline‐based carbon encapsulation strategy

Lithium‐sulfur battery is one of the most promising electrochemical energy storage systems because of its high theoretical specific capacity and energy density. When carbon materials are used for immobilizing sulfur, the technical challenge is designing their framework to relieve the shuttle effect of polysulfides intermediates and the volume change of sulfur, and to improve the conductivity of sulfur. Herein, polyaniline‐based carbon (PANI‐C) coated corn starch‐based activated carbon spheres (ACS@PANI‐C) was prepared and used as hosts of sulfur, which can effectively combine the advantages of physical entrapment and chemical binding interactions of sulfur species. The results of electrochemical performance test indicate that S/ACS@PANI‐C composites exhibit much better electrochemical performance than S/ACS composites. Its reversible capacities at 320, 480, 800 and 1600 mA g^?1 are 687, 582, 504 and 393 mAh g^?1, respectively. The improved electrochemical performance can be attributed to the PANI‐C which can also act as a flexible cushion to accommodate volume changes of sulfur cathode as well as a barrier to trap soluble polysulfide intermediates during the charge–discharge process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46544.     

Lithium–sulfur batteries with activated carbons derived from olive stones

A lithium–sulfur battery, using activated carbon obtained from olive stones as the sulfur host, is reported. The microporous texture allows large amounts of sulfur to be infiltrated into the host (sulfur loading 80%). The resulting composite material possesses a high capacity, about 670 mA h g⁻¹, excellent capacity retention on cycling and good rate capability. We believe that activated carbons derived from biomass could be an alternative source for the preparation of the cathode for Li–S batteries.     

Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Sulfolane (also referred to as tetramethylene sulfone, TMS) containing LiPF₆ and vinylene carbonate (VC) was tested as a non-flammable electrolyte for a graphite |LiFePO₄ lithium-ion battery. Charging/discharging capacity of the LiFePO₄ electrode was ca. 150 mAh g⁻¹ (VC content 5 wt%). The capacity of the graphite electrode after 10 cycles establishes at the level of ca. 350 mAh g⁻¹ (C/10 rate). In the case of the full graphite |1 M LiPF₆ + TMS + VC 10 wt% |LiFePO₄ cell, both charging and discharging capacity (referred to cathode mass) stabilized at a value of ca. 120 mAh g⁻¹. Exchange current density for Li⁺ reduction on metallic lithium, estimated from electrochemical impedance spectroscopy (EIS) experiments, was j_o(Li/Li⁺) = 8.15 × 10⁻⁴ A cm⁻². Moreover, EIS suggests formation of the solid electrolyte interface (SEI) on lithium, lithiated graphite and LiFePO₄ electrodes, protecting them from further corrosion in contact with the liquid electrolyte. Scanning electron microscopy (SEM) images of pristine electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of SEI formation. No graphite exfoliation was observed. The main decomposition peak of the LiPF₆ + TMS + VC electrolyte (TG/DTA experiment) was present at ca. 275 °C. The LiFePO₄(solid) + 1 M LiPF₆ + TMS + 10 wt% VC system shows a flash point of ca. 150 °C. This was much higher in comparison to that characteristic of a classical LiFePO₄ (solid) + 1 M LiPF₆ + 50 wt% EC + 50 wt% DMC system (T_f ≈ 37 °C).     

Effect of carbon coating on low temperature electrochemical performance of LiFePO4/C by using polystyrene sphere as carbon source

Carbon perfectly coated LiFePO₄ cathode materials are synthesized by carbon-thermal reduction method using polystyrene (PS) spheres as carbon source. The PS spheres with diameters of 150–300 nm used for the pyrolysis reaction not only inhibit the particle growth but also lead to uniform distribution of carbon coating on the surface of LiFePO₄ particles. Rate capability and cycling stability of LiFePO₄/C with the carbon contents ranging from 1.4 wt% to 3.7 wt% are investigated at −20 °C. The LiFePO₄/C with 3.0 wt% C exhibits excellent electrochemical capability at low temperature, which delivers 147 mAh g⁻¹ at 0.1 C. After 100 cycles at a charge–discharge rate of 1 C, there is still 100% of initial capacity retained for the LiFePO₄/C electrode at −20 °C. According to the transmission electron microscope analysis and cyclic voltammetry measurement, this can be attributed to the good carbon coating morphology and optimal carbon coating thickness.     

Sulfur–carbon composite electrode for all-solid-state Li/S battery with Li2S–P2S5 solid electrolyte

All-solid-state Li/S batteries with Li₂S–P₂S₅ glass–ceramic electrolytes were fabricated and their electrochemical performance was examined. Sulfur–carbon composite electrodes were prepared by grinding with a mortar and milling with a planetary ball-mill apparatus. Milling of a mixture of sulfur, acetylene black and the Li₂S–P₂S₅ glass–ceramic electrolyte resulted in the amorphization of sulfur and a reduction in the particle size of the mixture. The charge–discharge properties of all-solid-state cells with the composite electrode were investigated at temperatures from −20 °C to 80 °C. The cells retained a reversible capacity higher than 850 mAh g⁻¹ for 200 cycles under 1.3 mA cm⁻² (333 mA g⁻¹) at 25 °C. The cell performance was influenced by the crystallinity of sulfur and the particle size of the electrode material, whereby improved contact among the electrode components achieved by milling contributed to enhancement of the capacity of an all-solid-state Li/S cell.     

Gradually anchoring sulfur into in-situ doped carbon substrate as cathode for Li–S batteries with excellent wide-temperature performance

Carbon spheres, prepared by hydrothermally treating fresh potato starch, is employed as the sulfur host to configure a high-performance cathode substrate candidate for Li–S batteries. As confirmed by experimental results, both the improved the rate and cycle performances of Li–S batteries cathode with gradient sulfur immobilization, are mainly attributed to the confining, adsorption and conduction multi-functions of as-prepared carbon spheres toward polysulfides. Specifically, on starting the discharging/charging cycles, the active material α-S₈ is irreversibly converted to polysulfides and then transformed between β-S₈ and polysulfides during the next charge/discharge cycles. After initialization at 0.1C for 3 cycles, the initial reversible discharge capacities of the Li–S batteries cathode with optimized sulfur amount are 1072.5, 831.3, 780.4, 726.8, 714.3, 702.7 mAh g^?1_sulfur at 0.1, 0.5, 1, 2, 3 and 4 C, which is superior to those of the most previously reported reports. Besides that, as-designed potato-derived carbon based composite cathodes exhibits remarkable rate performance and cycling stability even at wide temperature ranging from ?40 to 60 °C, which evidently supports the dominant role of as-prepared 3D carbon spheres in boosting the cathode performance for Li–S batteries.     

The preparation of nano-sulfur/MWCNTs and its electrochemical performance

In this work, a novel nano-sulfur/MWCNTs composite with modified multi-wall carbon nano-tubes (MWCNTs) as sulfur-fixed matrix for Li/S battery is reported. Based on different solubility of sulfur in different solvents, nano-sulfur/MWCNTs composite was prepared by solvents exchange method. The composite was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modified MWCNTs are considered that not only acts as a conducting material, but also a matrix for sulfur. The electrochemical performance of the nano-sulfur/MWCNTs composite was tested. The results indicated that nano-sulfur/MWCNTs composite had the specific capacity of 1380 mAh g⁻¹, 1326 mAh g⁻¹ and 1210 mAh g⁻¹ in the initial cycle at 100 mA g⁻¹, 200 mA g⁻¹ and 300 mAh g⁻¹ discharge rates respectively, and remained a reversible capacity of 1020 mAh g⁻¹, 870 mAh g⁻¹ and 810 mAh g⁻¹ after 30 cycles. The electrochemical performances confirm that the modified MWCNTs as sulfur-fixed matrix show better ability than any other carbon in cathode of Li/S batteries that had been reported.