Si anode with high initial Coulombic efficiency, long cycle life, and superior rate capability by integrated utilization of graphene and pitch-based carbon.

A variety of strategies have been developed to enhance the cycling stability of Si-based anodes in lithium-ion batteries. Although significant progress has been made in enhancing the cycling stability of Si-based anodes, the low initial Coulombic efficiency (ICE) remains a significant challenge to their commercial application. Herein, pitch-based carbon (C) coated Si nanoparticles (NPs) were wrapped by graphene (G) to obtain Si@C/G composite with a small specific surface area of 11.3 m2g-1, resulting in a high ICE of 91.2% at 500 mA g-1. Moreover, the integrated utilization of graphene and soft carbon derived from the low-cost petroleum pitch strongly promotes the electrical conductivity, structure stability, and reaction kinetics of Si NPs. Consequently, the synthesized Si@C/G with a Si loading of 54.7% delivers large reversible capacity (1191 mAh g-1at 500 mA g-1), long cycle life over 200 cycles (a capacity retention of 87.1%), and superior rate capability (952 mAh g-1at 1500 mA g-1). When coupled with a homemade LiNi0.8Co0.1Mn0.1O2(NCM811) cathode in a full cell, it exhibits a promising cycling stability for 200 cycles. This work presents an innovative approach for the manufacture of Si-based anode materials with commercial application.

Analysis of transverse thermal conductivity for mesophase pitch-based carbon fibers and the through-thickness heat conduction of their composites.

A quantitative analysis method for the transverse thermal conductivity (TC) of carbon fiber is developed, which consists of three steps including TC and morphology characterization of unidirectional composite laminate, fiber contour extraction, and finite element inverse analysis. Two different pitch-based carbon fibers with folded-radial and onion-skin microstructure are characterized, and the influences of fiber volume fraction and microstructure on the heat conduction of their composites are investigated. The equivalent transverse TCs of TC-HC-800 and PCF-1 carbon fibers are measured to be 9.27 and 2.87 W m-1 K-1, respectively. The through-thickness TC of unidirectional composite exhibits rapid growth with the increase in fiber volume fraction. The finite element analysis reveals that more continuous heat conduction paths are formed with the increase in fiber volume fraction. Benefited from the bigger graphitization degree, larger cross-sectional area, and bigger aspect ratio, TC-HC-800 unidirectional composite shows higher through-thickness TC than PCF-1 composite at the same fiber volume fraction.

Preparation, Microstructure and Thermal Properties of Aligned Mesophase Pitch-Based Carbon Fiber Interface Materials by an Electrostatic Flocking Method.

The mesophase pitch-based carbon fiber interface material (TIM) with a vertical array was prepared by using mesophase pitch-based short-cut fibers (MPCFs) and 3016 epoxy resin as raw materials and carbon nanotubes (CNTs) as additives through electrostatic flocking and resin pouring molding process. The microstructure and thermal properties of the interface were analyzed by using a scanning electron microscope (SEM), laser thermal conductivity and thermal infrared imaging methods. The results indicate that the plate spacing and fusing voltage have a significant impact on the orientation of the arrays formed by mesophase pitch-based carbon fibers. While the orientation of the carbon fiber array has a minimal impact on the shore hardness of TIM, it does have a direct influence on its thermal conductivity. At a flocking voltage of 20 kV and plate spacing of 12 cm, the interface material exhibited an optimal thermal conductivity of 24.47 W/(m·K), shore hardness of 42 A and carbon fiber filling rate of 6.30 wt%. By incorporating 2% carbon nanotubes (CNTs) into the epoxy matrix, the interface material achieves a thermal conductivity of 28.97 W/(m·K) at a flocking voltage of 30 kV and plate spacing of 10 cm. This represents a 52.1% increase in thermal conductivity compared to the material without TIM. The material achieves temperature uniformity within 10 s at the same heat source temperatures, which indicates a good application prospect in IC packaging and electronic heat dissipation.

The Microstructure and Thermal Conductive Behavior of Three-Dimensional Carbon/Carbon Composites with Ultrahigh Thermal Conductivity.

Carbon-based composite materials, denoted as C/C composites and possessing high thermal conductivity, were synthesized utilizing a three-dimensional (3D) preform methodology. This involved the orthogonal weaving of mesophase pitch-based fibers in an X (Y) direction derived from low-temperature carbonization, and commercial PAN-based carbon fibers in a Z direction. The 3D preforms were saturated with mesophase pitch in their raw state through a hot-pressing process, which was executed under relatively low pressure at a predetermined temperature. Further densification was achieved by successive stages of mesophase pitch impregnation (MPI), followed by impregnation with coal pitch under high pressure (IPI). The microstructure and thermal conductivity of the C/C composites were systematically examined using a suite of analytical techniques, including Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and PLM, amongst others. The findings suggest that the volumetric fraction of fibers and the directional alignment of the mesophase pitch molecules can be enhanced via hot pressing. The high graphitization degree of the mesophase pitch matrix results in an increased microcrystalline size and thus improved thermal conductivity of the C/C composite. Conversely, the orientation of the medium-temperature coal pitch matrix is relatively low, which compensates for the structural inadequacies of the composite material, albeit contributing minimally to the thermal conductivity of the resultant C/C composites. Following several stages of impregnation with mesophase pitch and subsequent impregnation with medium-temperature coal pitch, the 3D C/C composites yielded a density of 1.83 and 2.02 g/cm3. The thermal conductivity in the X (Y) direction was found to be 358 and 400 W/(m·K), respectively.

The Recent Progress of Pitch Nanoengineering to Obtain the Carbon Anode for High-Performance Sodium Ion Batteries.

As an anode material for sodium ion batteries (SIBs), carbon materials have attracted people's interest because of their abundant resources, good structural stability and low cost. Among most carbon precursors, pitch is viewed as a promising one because of a higher carbon content, good oxidation reversibility and low cost. However, the pitch-based carbon obtained with direct pyrolysis of pitch displays a high degree of graphitization and small layer spacing, which is unfavorable for the storage of sodium ions. In recent years, with the aid of the development of the nanoengineering process, the storage of sodium ions with pitch-based carbon has been drastically improved. This review article summarizes the recent progress of pitch nanoengineering to obtain the carbon anode for high-performance SIBs, including porous structure adjustment, heteroatom doping, co-carbonization and pre-oxidation. In addition, the merits and demerits of a variety of nanoengineering processes are discussed, and future research directions of pitch-based carbon are prospected.

Preparation and Adsorption Properties of Graphene-Modified, Pitch-Based Carbon Foam Composites.

In view of the good adsorption properties of graphene and carbon foam, they were combined to achieve the optimal matching of microstructures. Taking mesophase pitch as a raw material, pitch-based carbon foam was prepared by the self-foaming method. Graphene gel was prepared as the second phase to composite with the carbon foam matrix; graphene-modified, pitch-based carbon foam composites were finally obtained. Graphene gel was dispersed in the rich pore structure of carbon foam to improve its agglomeration and the porosity, and the active sites of the composite were further increased; the adsorption properties and mechanical properties of the composites were also significantly improved. The microstructure and morphology of the composites were studied by SEM, XRD and Raman spectroscopy; the compressive property and porosity were also tested. Methylene blue (MB) solution was used to simulate a dye solution for the adsorption test, and the influence of the composite properties and MB solution on the adsorption property was studied. Results showed that the compressive strength of the composite was 13.5 MPa, increased by 53.41%, and the porosity was 58.14%, increased by 24.15%, when compared to raw carbon foam. When the mass of the adsorbent was 150 mg, the initial concentration of the MB solution was 5 mg/L, and the pH value of the MB solution was 11; the graphene-modified carbon foam composites showed the best adsorption effect, with an adsorption rate of 96.3% and an adsorption capacity of 144.45 mg/g. Compared with the raw carbon foam, the adsorption rate and adsorption capacity of the composites were increased by 158.18% and 93.50%, respectively.

Synergistic Effects of Hybrid Carbonaceous Fillers of Carbon Fibers and Reduced Graphene Oxides on Enhanced Heat-Dissipation Capability of Polymer Composites.

In this study, we investigated the synergistic effects of thermally conductive hybrid carbonaceous fillers of mesophase pitch-based carbon fibers (MPCFs) and reduced graphene oxides (rGOs) on the thermal conductivity of polymer matrix composites. Micro-sized MPCFs with different lengths (50 µm, 200 µm, and 6 mm) and nano-sized rGOs were used as the thermally conductive fillers used for the preparation of the heat-dissipation polymer composites. For all MPCF fillers with a different length, the thermal conductivity values of the MPCF/epoxy composites were proportional to the MPCF length and loading amount (0-50 wt%) of MPCFs. For an MPCF:rGO weight ratio of 49:1 (total loading amount of 50 wt%), the thermal conductivity values of MPCF-rGO/epoxy composites loaded with MPCFs of 50 µm, 200 µm, and 6 mm increased from 5.56 to 7.98 W/mK (approximately 44% increase), from 7.36 to 9.80 W/mK (approximately 33% increase), and from 11.53 to 12.58 W/mK (approximately 9% increase) compared to the MPCF/epoxy composites, respectively, indicating the synergistic effect on the thermal conductivity enhancement. The rGOs in the MPCF-rGO/epoxy composites acted as thermal bridges between neighboring MPCFs, resulting in the formation of effective heat transfer pathways. In contrast, the MPCF-rGO/epoxy composites with MPCF:rGO weight ratios of 48:2 and 47:3 decreased the synergistic effect more significantly compared to rGO content of 1 wt%, which is associated with the agglomeration of rGO nanoparticles. The synergistic effect was inversely proportional to the MPCF length. A theoretical approach, the modified Mori-Tanaka model, was used to estimate the thermal conductivity values of the MPCF-rGO/epoxy composites, which were in agreement with the experimentally measured values for MPCF-rGO/epoxy composites loaded with short MPCF lengths of 50 and 200 µm.

Functional Properties of a Pitch-Based Carbon Fiber-Mortar Composite as a Thin Overlay for Concrete Pavement.

This experimental study investigated the utility of a pitch-based carbon fiber-mortar composite, which could replace polyacrylonitrile carbon fiber, as a thin overlay for concrete pavement. The objective was to explore the utility of the low-cost carbon fiber, which was produced via a melt-blown method, i.e., blowing at high pressure after melting the pitch residue following crude oil purification. The mechanical properties, durability, and thermal properties of the pitch-based carbon fiber were explored to maximize strength, durability, functionality, and economy by using micro-sized fibers that are closer in size to the constituents of cementitious materials. Melt-blown pitch-based carbon fiber has low individual fiber strength but generally excellent thermal conductivity. Thermal conductivity tests were conducted on mortar panels (560 mm × 560 mm; thickness = 25, 40 or 60 mm) containing 0, 0.4, 0.5 or 0.6 wt % pitch-based carbon fiber. The absolute thermal conductivity tended to improve with higher wt % of pitch-based carbon fiber, in the range of 9~11 W/°C. However, thermal conductivity tended to be lower under the 0.6 wt % condition, possibly due to the effect of dispersion. Compressive strength degradation was tested over 350 cycles of freezing and thawing: the strength of the 0.4, 0.5 or 0.6 wt % samples was 91, 89, and 82%, respectively, relative to the control specimen (0 wt %). Thus, all specimens had a compressive strength of 80% or more after 350 cycles compared to the control specimen. To test the adhesion performance for new thin overlays and old concrete surfaces, concrete cylinders (100 × 200 mm; thickness = 10 mm) were cut at an angle of 46 degrees, and the pitch-based carbon fiber-mortar composite was used to bond the various sections. The bond strength of the test specimens was more than twice that of the reference specimen.