Graphite Layers Research Articles

Polyoxometalate coupled polymers induced molybdenum phosphide with large surface area for efficient hydrogen evolution

Developing highly active hydrogen evolution reaction (HER) electrocatalysts possesses great significance for the green renewable energy conversion and storage. Here, through the electrostatic attraction between polyoxometalate (PMo12) and ammonium polyphosphate (APP) and the coordination with polyallylamine hydrochloride (PAH), the precursor was constructed, and then nitrogen-doped graphite carbon layer-coated MoP active particles (MoP@NC) were successfully prepared by high temperature carbonization. For HER, the overpotential of η10 for MoP@NC is 119 and 126 mV in acidic and alkaline electrolyte. Furthermore, in alkaline solution, when the current density reaches a certain degree (≥110 mA cm−2), the hydrogen production activity of the catalysts are the same as that of the industrial Pt/C catalysts, or even have a slight advantage. The synergistic interaction of active particles (MoP) and graphitic carbon layers and high specific surface area ensure the excellent activity of HER. N-doped porous carbon layers also protect MoP@NC working for 24 h. Moreover, the catalysts prepared in the same experimental environment with ammonium molybdate as metal source also showed good HER performance in acidic and alkaline environments. This study opens a general way to develop earth-rich Mo-based phosphide electrocatalysts with high activity for hydrolysis applications.

Investigation of biomimetic HAp formation on graphite

According to reports, coating implants with hydroxyapatite (HAp) promotes bone repair and combines the biological effectiveness of the material with the mechanical properties of standard metallic implants. In this contribution, bioactive nanographite particles were synthesized using a novel technique to stimulate HAp deposition using a biomimetic method. The rapid breakdown ionization (RBA) technique was used to synthesize graphite nanoparticles. The electrophoretic deposition (EPD) technique was utilized to deposit the nanoparticle on titanium substrates. Scanning electron microscope (SEM) images showed the creation of nanoparticles with a size of around 65nm. An X-ray diffraction (XRD) test confirmed the polycrystalline structure of graphite with a dominant peak (002). UV-VIS absorption and FTIR spectra confirmed the production of graphite powder. To test the bioactivity of the graphite layer, it was immersed in simulated body fluid (SBF) for 30 days. The formation of a HAp layer on graphite is depicted by an XRD pattern, and SEM images illustrate nanoclusters of this layer.

Self-assembled lignin-based flame retardant hybrids carrying Cu2+ for poly(lactic acid) composites with improved fire safety and mechanical properties

To enhance the flame retardancy and mechanical performance of PLA, a polyelectrolyte complex predicated on lignin was obtained by electrostatic mutual adsorption of ammonium polyphosphate (APP), polyethyleneimine (PEI), and copper ions as raw materials. The FT-IR spectra and EDX analysis confirmed the successful synthesis of a lignin-based flame retardant hybrid (APL-Cu2+) containing copper, phosphorus, and nitrogen elements. The combustion test results showed that the peak heat release rate and total heat release of the PLA composite containing 12 wt% APL-Cu2+ were decreased by 15.1 % and 18.2 %, respectively, as compared to those of pure PLA. The char residue morphology observation revealed that the addition of APL-Cu2+ could promote the formation of a highly dense and stable graphitized char layer, while TG-MS detected the emission of refractory gases such as ammonia gas, carbon dioxide, and water during combustion. The strong hydrogen bonding between APL-Cu2+ and the PLA matrix kept the composite maintaining good strength and toughness. The tensile strength and impact strength of PLA/6APL-Cu2+ increased by 4.73 % and 65.71 %, respectively, due to its high crystallinity and good interfacial compatibility. This work provides a feasible method to develop biobased flame retardant hybrids for PLA composites with better fire safety and improved mechanical properties.

Crystalline-topologies engineering of bio-spore-derived hard carbon for efficient low-potential potassium ion storage

Clarifying the relationship between crystalline topologies of hard carbon and electrochemical K+ storage behaviors is essential to develop low-cost anode for K+ battery. Herein, bio-mass derived hard carbons with various crystalline topologies were synthesized for the first time by one-step pyrolysis of spores of sorghum smut fungus as new precursors. The crystalline-structures of spore-derived hard carbons including graphitic-like layer number, spacing and curvature can be effectively modulated by pyrolysis temperatures, leading to significant difference between correspondingly as-synthesized hard carbons for K+ storage. The hard carbon obtained at 1400 °C presents a unique crystalline structure with fewer graphite stacking layers down to 2, achieving the excellent K+ storage performance, in which, it presents a high capacity of 495.0 mAh/g with a significant plateau capacity of 368.9 mAh/g (< 0.5 V), a good rate performance of 175.0 mAh g-1 at 500 mA g-1 and stable cycling performance (125.0 mAh g-1 at 500 mA g-1 over 600 cycles), outperforming the most of reported hard carbons derived from various precursors. Meanwhile, the DFT calculation further clarifies that the crystalline topologies of hard carbon play a critical role for efficient K+ storage. In particular, there is an interesting discovery that the number of graphite stacking layers can significantly affect the migration and diffusion of K+, in which, the fewer the number of graphite stacking layers, the lower the energy barrier of K+ diffusion between graphite layers. These results in the work provide new insights for the understanding of K+ storage behavior in hard carbon.

Study on electrochemical lithiation stress model of graphite-carbon fiber bilayer electrode

Graphite–carbon fiber bilayer electrodes (GCBEs), as part of composite structural batteries, are capable of both energy storage and load bearing without the requirement of an extra structure. However, carbon fiber (CF) as a current collector exists lithiation stress, the stress of this bilayer electrode structure is still unclear. In this study, the relationship between the potential and deflection deformation of GCBEs at various thickness ratios is experimentally recorded using an in situ electrochemical cell device. The GCBE bends and recovers with a decrease and increase in potential, respectively. In addition, a cantilever stress model is established to depict the effect of the Li+ concentration difference and thickness ratio on the GCBE lithiation deflection and stress distribution. The results show that the concentration difference and thickness ratio are positively correlated with the deflection and stress, and the stress is discontinuous at the interlayer interface of the electrode. Finite element simulation shows that the Li+ concentration in the graphite layer is approximately three times more than CFs. Compared to the commercial graphite-copper bilayer electrode, the GCBE is experimentally proven to better suppress lithiation deformation. Meanwhile, the influence of solid electrolyte interphase (SEI) is considered by a simplified strain transfer model.

Nanodiamond‐Assisted High Performance Lithium and Sodium Ions Co‐Storage

While lithium resources are scarce for high energy‐dense lithium‐ion batteries (LIBs), sodium‐ion batteries (SIBs), serving as an alternative, inherently suffer from low capacity and the high‐cost use of non‐graphite anodes. Combining Li‐ and Na‐ions within a single battery system is expected to mitigate the shortcomings of both systems while leveraging their respective advantages. In this study, we developed and assembled a nanodiamonds (NDs)‐assisted co‐Li/Na‐ion battery (ND–LSIB). This innovative battery system comprised a commercial graphite anode, an ND‐modified polypropylene (DPP) separator, a hybrid lithium/sodium‐based electrolyte, and a cathode. It is theoretically and experimentally demonstrated that the ND/Li co‐insertion can serve as an ion‐drill opening graphite layers and reconstructing graphite anodes into few‐layered graphene with expanding interlayer space, achieving highly efficient Li/Na storage and the theoretical maximum of LiC6 for Li storage in graphite. In addition, ND is helpful for creating a LiF‐/NaF‐rich hybrid solid electrolyte interface with improved ionic mobility, mechanical strength, and reversibility. Consequently, ND–LSIBs have higher specific capacities ~1.4 times the theoretical value of LIBs and show long‐term cycling stability. This study proposes and realizes the concept of Li/Na co‐storage in one ion battery with compatible high‐performance, cost‐effectiveness, and industrial prospects.

Shielding Mn3+ Disproportionation with Graphitic Carbon-Interlayered Manganese Oxide Cathodes for Enhanced Aqueous Energy Storage System.

Manganese dioxide (MnO2) materials have recently garnered attention as prospective high-capacity cathodes, owing to their theoretical two-electron redox reaction in charge storage processes. However, their practical application in aqueous energy storage systems faces a formidable challenge: the disproportionation of Mn3+ ions, leading to a significant reduction in their capacity. To address this limitation, the study presents a novel graphitic carbon interlayer-engineered manganese oxide (CI-MnOx) characterized by an open structure and abundant defects. This innovative material serves several essential functions for efficient aqueous energy storage. First, a graphitic carbon layer coats the MnOx molecular interlayer, effectively inhibiting Mn3+ disproportionation and substantially enhancing electrode conductivity. Second, the phase variation within MnOx generates numerous crystal defects, vacancies, and active sites, optimizing electron-transfer capability. Third, the flexible carbon layer acts as a buffer, mitigating the volume expansion of MnOx during extended cycling. The synergistic effects of these features result in the CI-MnOx exhibiting an impressive high capacity of 272 mAh g-1 (1224 F g-1) at 0.25 A g-1. Notably, the CI-MnOx demonstrates zero capacity loss after 90000 cycles (≈3011h), an uncommon longevity for manganese oxide materials. Spectral characterizations reveal reversible cation intercalation and conversion reactions with multielectron transfer in a LiCl electrolyte.

Hierarchical Porous N-Doped Carbon Particles Derived from ZIF-8 as Highly Efficient H2S Selective Oxidation Catalysts.

In the selective oxidation of H2S, the catalytic activity over N-doped carbon-based catalysts is significantly influenced by the accessibility of active sites and the mass transfer rates of reactant molecules (e.g., H2S and O2) as well as generated sulfur monomers. Therefore, it is crucial for enhancing the initial performance via the controlled synthesis of carbon-based catalysts with highly exposed active sites and unique porous structures. Herein, we reported on an efficient strategy to synthesize nanosized N-doped carbon particles with hierarchical porous structures by directly pyrolyzing an oversaturated NaCl-encapsulated ZIF-8 precursor mixture. The introduction of NaCl not only serves as a pollution-free template to promote the formation of graphitic carbon layers but also acts as an intercalating agent to guide the derivation of hierarchical porous structures, as well as enhances the amount of active nitrogen species in the catalysts. As a result, the as-prepared H-NC800 catalyst shows excellent H2S selective oxidation performance (sulfur formation rate is 794 gsulfur·kgcat-1·h-1), good stability (>80 h), and antiwater vapor properties. The characterization results and DFT calculations indicate the crucial role of pyridinic N in the adsorbing and activating reactant molecules (H2S, O2). Furthermore, nanoscale N-doped carbon particles accelerated the rapid transport of generated sulfur monomers under a hierarchical porous structure. This investigation introduces a distinctive strategy for synthesizing ZIF-8-derived N-doped carbon nanosized with a hierarchical porous structure, while its efficient and stable H2S selective oxidation performance highlights significant potential for practical implementation in the industrial desulfurization process.

The construction of iron-based catalysts encapsulated by graphite for CO2 hydrogenation to light olefins

Developing efficient catalytic materials and unveiling the active factors are significant for selective hydrogenation of CO2 to light olefins (C2–4=). Herein, Fe3O4-FeCx nanoparticles coated by graphite without other doped elements were synthesized successfully. The optimal catalyst exhibited CO2 conversion of 48.0%, C2–4= space–time yield of 29.0 mmol·g−1·h−1, and a stability of 100 h (3.0 MPa, 320 °C, and GHSV = 12000 mL·g−1·h−1). The core–shell structure derived from the strong interaction between the phenolic hydroxyl group of resin and iron ions, as well as the encapsulation of the copolymer P123. The characterization results revealed that the size of core–shell particles and thickness of graphite layers could be regulated by P123, which affected the conversion of CO2 and products distribution significantly. Moreover, the combined results of quasi in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) and Raman spectra suggested small particle size and thin graphite shell strengthen the adsorption and conversion of CO2, playing an important role in the formation of light olefins. This work proposes a simple and feasible synthesis strategy to construct Fe3O4-FeCx particles encapsulated by graphite shell, which provides insights into catalysts design and the reaction mechanism of CO2 conversion to light olefins.

Boron-doped polyhedral graphite catalyzed by h-BN via structural induction for lithium storage

Artificial graphite is extensively used in power lithium-ion batteries for its exceptional stability and high-rate performance. However, the commercial high-temperature graphitization process is conducted at temperatures up to 3000 °C to enhance the degree of graphitization, resulting in significant electricity consumption and lengthy production cycles. This study aimed to lower graphitization temperatures and shorten times by using h-BN as a catalyst. Employing anthracite coal as the precursor and catalyzing with BN at 2800 °C for just 2 h, we achieved a remarkable graphitization degree of 93.3 %, compared to 83.5 % without BN. This indicates BN's effectiveness in accelerating graphite phase formation. Interestingly, the resultant graphite exhibited polyhedral morphology and incorporated boron doping. As edges increased, lithium-ion diffusion pathways and boron doping enhanced stability within the graphite layers, imparting high rate capability and robust cycle performance. The material delivered reversible specific capacities of 369.6 and 226 mA h g−1 at current densities of 0.1 and 3C, and maintained capacity retentions of 95 % and 92 % after 500 cycles at 0.5C and 1C. These results substantiate the potential for large-scale production of artificial graphite from anthracite coal using BN catalysis and underscore its promise as a superior anode material for lithium-ion batteries.

Cobalt-catalyzed soft-hard carbon composite anodes for enhanced sodium-ion storage

Hard carbon is expected to be a high-capacity anode material for sodium-ion batteries (SIBs). However, its Na+ storage performance, especially the low discharge capacity, remains a great challenge. Herein, the soft-hard carbon composite anodes with high degree of graphitization were synthesized via low-temperature pyrolysis (at only 900 °C) of Cobalt-catalyzed perylene tetracarboxylic dianhydride (PTCDA-Co) and cotton, with subsequent removal of cobalt. The composite resulting from a 2:3 mass ratio of soft to hard carbon exhibits a good discharge capacity of 355.81 mAh g−1 at a current density of 50 mA g−1 and an enhanced initial Coulombic efficiency (ICE) of 81.41%. The enhanced electrochemical storage performance of cotton is attributed to the introduction of PTCDA-Co, which creates low-defect graphitic layer, hierarchical porous channels, and carbon shielding coating on hard carbon.

Relationships Between Macrostructure and Microstructure in Lamellar Graphite Iron Castings

AbstractSpherical sheet steel molds filled with gray iron melts of varying chemical compositions and metallurgical conditions were air-cooled until solid, followed directly by austempering to preserve the austenite grain structure. The castings were studied using a combination of cooling curves and quantitative metallography, in order to clarify control of the austenite grain structure and its impact on the local microstructure. A novel method utilizing fast Fourier transform provided visual overview of macroscopic trends in the scale of the flake graphite structure. Castings inoculated with Sr-containing ferrosilicon featured finer eutectic cell structure but coarser equiaxed structure of austenite, emphasizing that melt treatments applied to control the graphite structure may have unintended effects on the austenite grain structure. In most non-inoculated castings, the microstructure was banded, with alternating layers of coarse and fine flake graphite with distance from the casting surface. The extent of the columnar zone of austenite grains showed no correlation with the graphite structure nor the volume fraction of dendrites. The volume-to-surface ratio of dendrites was more uniform in the columnar zone, but increased toward the center in the equiaxed zone. The casting with the highest carbon equivalent (4.34), featured zones containing finer dendrites and graphite. These zones appear to be gaps in the early solidification structure which filled later by secondary dendritic growth from surrounding austenite. This highlights that high carbon equivalent may lead to poor dendrite coherency which can make the microstructure less uniform and less predictable.

Alginic acid derivatives/DOPO modified epoxy resins: Excellent flame retardancy, mechanical properties, chemical resistance

An alginic acid derivative AA@MEL with flame retardant effect in both gas and condensed phases was synthesized by the neutralization reaction of alginic acid (AA) and melamine (MEL). Modified EP obtained the UL-94 V-0 rating and limiting oxygen index (LOI) of 33.8 % when the total addition of AA@MEL and 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO) in the epoxy resin was only 4 wt% and the phosphorus content was only 0.29 %. Compared with pure EP, the total heat release (THR) and total smoke production (TSP) of flame-retardant EP were reduced by 42 % and 60 %, respectively, and the quality of the char residue was improved by forming higher graphitization layer. The flame retardancy mechanism was proposed through the pyrolysis products analyses and the characterization of the condensed phase. Meanwhile, the appropriate amount of AA@MEL/DOPO can enhance the tensile property, flexural property and impact strength of EP materials. It was closely related to the -COOH/-OH in AA@MEL and the P-H bond and rigid structure of DOPO. In addition, the modified EP has good chemical resistance, which ensures long-lasting flame retardant and mechanical properties. The AA@MEL/DOPO system exhibits low cost, low loading, high flame-retardant efficiency and environmental friendliness for industrial needs, which is promising for industrial applications.

A Gradient Composite Structure Enables a Stable Microsized Silicon Suboxide-Based Anode for a High-Performance Lithium-Ion Battery.

The practical application of microsized anodes is hindered by severe volume changes and fast capacity fading. Herein, we propose a gradient composite strategy and fabricate a silicon suboxide-based composite anode (d-SiO@SiOx/C@C) consisting of a disproportionated microsized SiO inner core, a homogeneous composite SiOx/C interlayer (x ≈ 1.5), and a highly graphitized carbon outer layer. The robust SiOx/C interlayer can realize a gradient abatement of stress and simultaneously connect the inner SiO core and carbon outer layer through covalent bonds. As a result, d-SiO@SiOx/C@C delivers a specific capacity of 1023 mAh/g after 300 cycles at 1 A/g with a retention of >90% and an average Coulombic efficiency of >99.7%. A full cell assembled with a LiNi0.8Co0.15Al0.05O2 cathode displays a remarkable specific energy density of 569 Wh/kg based on total active materials as well as excellent cycling stability. Our strategy provides a promising alternative for designing structurally and electrochemically stable microsized anodes with high capacity.

Improving the mechanical properties and thermal conductivity of mesophase-pitch-based carbon fibers by controlling the temperature in industrial spinning equipment

Mesophase-pitch-based carbon fibers (MPCFs) were prepared using industrial equipment with a constant extrusion rate of pitch while controlling the spinning temperature. The influence of spinning temperature on their microstructures, mechanical properties and thermal conductivities was investigated. SEM images of the fractured surface of MPCFs show that the graphite layers have a radiating structure at all spinning temperatures, but change from the fine-and-folded to the large-and-flat morphology when increasing the spinning temperature from 309 to 320 oC. At the same time the thermal conductivity and tensile strength of the MPCFs respectively increase from 704 W·m−1·K−1 and 2.16 GPa at 309 oC to 1 078 W·m−1·K−1 and 3.23 GPa at 320 oC. The lower viscosity and the weaker die-swell effect of mesophase pitch at the outlets of the spinnerets at the higher spinning temperature contribute to the improved orientation of mesophase pitch molecules in the pitch fibers, which improves the crystallite size and orientation of the MPCFs.

In Situ Chemical Modulation of Graphitization Degree of Carbon Fibers and Its Potassium Storage Mechanism.

Graphite is considered to be the most auspicious anode candidate for potassium ion batteries. However, the inferior rate performances and cycling stability restrict its practical applications. Few studies have investigated the modulating the graphitization degree of graphitic materials. Herein, a nitrogen-doped carbon-coated carbon fiber composite with tunable graphitization (CNF@NC) through etching growth, in-situ oxidative polymerization, and subsequent carbonization process is reported. The prepared CNF@NC with abundant electrochemical active sites and a rapid K+/electron transfer pathway, can effectively shorten the K+ transfer distance and promote the rapid insertion/removal of K+. Amorphous domains and short-range curved graphite layers can provide ample mitigation spaces for K+ storage, alleviating the volume expansion of the highly graphitized CNF during repeated K+ insertion/de-intercalation. As expected, the CNF@NC-5 electrode presents a high initial coulombic efficiency (ICE) of 69.3%, an unprecedented reversible volumetric capacity of 510.2 mA h cm-3 at 0.1 A g-1 after 100 cycles with the mass-capacity of 294.9 mA h g-1. The K+ storage mechanism and reaction kinetic analysis are studied by combining in-situ analysis and first-principles calculation. It manifests that the K+ storage mechanism in CNF@NC-5 is an adsorption-insertion-insertion mechanism (i.e., the "1+2" model). The solid electrolyte interphase (SEI) film forming is also detected.

Stiffness and mechanical manipulation of blisters grown on electrochemically intercalated graphite

Electrochemical anion intercalation of highly oriented pyrolytic graphite in mineral acids (such as sulfuric, perchloric, etc.) represents a model system to study (i) the intercalation process of chemical compounds in stratified crystals; (ii) the evolution of gases at the surface and inside the sample and (iii) the evolution of swollen regions of graphite, called blisters. Although the explanation of the blister evolution mechanism can be dated back to the nineties of the last century, many chemical and physical properties have been explored only very recently. In particular, the mechanical properties of blisters on graphite are not widely discussed in the literature. Here, we employ in-situ atomic force microscopy (AFM) to characterize the blister stiffness. The same AFM tip is used to move mechanically the blister on the basal plane or even cut it. As a consequence of this operation, the entrapped gases (namely, CO, CO2 and O2) can deflate and the swollen graphite layers lay down to recompose the graphite basal plane.

In Situ Defect Engineering in Carbon by Atomic Self-Activation to Boost the Accessible Low-Voltage Insertion for Advanced Potassium-Ion Full-Cells.

Enhancing the low-potential capacity of anode materials is significant in boosting the operating voltage of full-cells and constructing high energy-density energy storage devices. Graphitic carbons exhibit outstanding low-potential potassium storage performance, but show a low K+ diffusion kinetics. Herein, in&nbsp;situ defect engineering in graphitic nanocarbon is achieved by an atomic self-activation strategy to boost the accessible low-voltage insertion. Graphitic carbon layers grow on nanoscale-nickel to form the graphitic nanosphere with short-range ordered microcrystalline due to nickel graphitization catalyst. Meanwhile, the widely distributed K+ in the precursor induces the activation of surrounding carbon atoms to in situ generate carbon vacancies as channels. The graphite microcrystals with defect channels realize reversible K+ intercalation at low-potential and accessible ion diffusion kinetics, contributing to high reversible capacity (209mAhg-1 at 0.05Ag-1 under 0.8V) and rate capacity (103.2mAhg-1 at 1Ag-1). The full-cell with Prussian blue cathode and graphitic nanocarbon anode maintains an obvious working platform at ca. 3.0V. This work provides a strategy for the in situ design of carbon anode materials and gives insights into the potassium storage mechanism at low-potential for high-performance full-cells.

Core-shell diamond-graphene needles with silicon-vacancy color centers

Color centers in diamond nanostructures open new horizons in biomedicine, offering a biocompatible material platform for sensing temperature, pH, and magnetic field. Covering of the color centers enriched diamonds with graphene shell can essentially extend their application potential. Specifically, under irradiation with ultrashort laser pulses, the highly absorptive graphene shell can be used for excitation of a shock acoustic wave which can be used for cancer cell destruction or drug photoactivation through the Joule heating. In this study, we present a novel method for creating diamond-graphite core-shell structures. Through precise control of the growth of the graphitic layer on Single Crystal Diamond Needles (SCDNs) via vacuum annealing at 900°C for 30 minutes, we preserved 57% of the light emission from silicon-vacancy (SiV-) centers while maintaining their spectral peaks. Contrary to our expectations of reduced SiV- luminescence due to the presence of the graphitic shell, we observed that the initial high brightness of SiV- in the diamond needles persisted. This enabled us to detect SiV- luminescence spectrally, even within the core-shell structures. Our results underscore the tunability of these structures’ properties through temperature and duration control, suggesting promising prospects for their application in advanced biomedical tools with sensing capabilities.

Surface phenomena in graphite and obtaining graphene from it

The article offers an overview of our latest theoretical work on graphite and graphene. A model is proposed for determining the thickness of the surface layer of graphite, from which the strength of graphite and graphene can be calculated and the length of nanocracks in the surface layer of these materials can be determined.