Graphene-copper composites hold great promise for thermal and electrical management, yet their deployment is hindered by high grain boundary density, weak interfacial coupling, and limited scalability. Here we report a modular assembly strategy that transforms A3-sized single-crystalline graphene-skinned Cu(111) foils into bulk laminates with tailored interfaces and enhanced transport properties. The building blocks are synthesized via industrial-scale CVD system, combining temperature-gradient annealing with graphene epitaxial growth. Orientation-controlled stacking followed by spark plasma sintering yields dense laminates featuring only low-angle grain boundaries (<2°), preserved coherent Gr(0001)/Cu(111) interfaces, and a continuous graphene channel. The laminates achieve electrical conductivity up to 103.7% IACS and thermal conductivity exceeding 422.3 W·m^-1·K^-1, representing improvements of 5.5% and 8.2% respectively compared to commercial copper. Integrated heat spreaders exhibit substantially reduced thermal resistance (0.88 °C/W) with excellent stability. Extending this strategy to Gr/Ni(111) enables Cu-Gr-Ni heterostructures where graphene prevents intermetallic alloying. This work establishes a scalable paradigm for assembling macroscopic architectures from single-crystal, graphene-skinned building blocks for high-performance electronic packaging and multifunctional composites.

The interphase in continuous SiC fiber-reinforced ceramic matrix composites is critical to their mechanical reliability, and graphene is a promising interphase material. However, the effect of substrate surface condition on graphene growth on SiC fibers remains unclear. Here, graphene grown by chemical vapor deposition on pristine SiC fibers and pre-oxidized SiO₂/SiC fibers is systematically compared. Experiments show that pristine SiC promotes early multi-point nucleation and an outward-propagating SK-like mode, whereas the pre-oxidized surface favors conformal layer-by-layer growth, leading to a smoother FM-like morphology. First-principles calculations reveal that SiC more strongly catalyzes carbon-source cracking and generates active carbon species, while SiO₂ is more favorable for carbon diffusion and conformal growth. In addition, graphene edges, steps, and curved regions tend to act as secondary nucleation sites, inducing disordered multilayer growth at later stages. These results provide guidance for tailoring graphene interphases on SiC fibers by surface pretreatment.

Materials that can deliver in-plane heat diffusion and through-plane thermal insulation are essential for thermal management in extreme environments. However, integrating these opposing functions into a single material remains highly challenging because thermal conduction and insulation are inherently contradictory. Here, we report an anisotropic graphene-skinned welded glass fiber felt (Gr-wGFF) produced through a one-step process that couples the in-situ growth of vertically aligned graphene on glass fibers by plasma-enhanced chemical vapor deposition (PECVD) with the concurrent thermal welding of fiber junctions. This approach generates a continuous, covalently bonded thermal transport network at an ultralow graphene content (≈0.86 wt%), thereby overcoming the high percolation threshold commonly encountered in conventional composites. The resulting structure exhibits pronounced anisotropy: at an areal density of 430 g·m^-2, the Gr-wGFF achieves an in-plane thermal conductivity of 1.6 W·m^-1·K^-1 and a through-plane conductivity of 0.2 W·m^-1·K^-1, corresponding to an anisotropy ratio of 8. When embedded into phenolic resin (PR) matrix, the composite maintains high thermal anisotropy with good mechanical strength and flame retardancy. This multifunctional integration offers a solution for advanced thermal–structural applications in extreme environments.

The direct growth of graphene via chemical vapour deposition on dielectric materials is a promising approach for transfer-free applications. However, large-scale production using this technique is hindered by the slow growth on non-catalytic substrates. In this study, the growth mechanism of graphene on glass fibre is theoretically explored, assuming α-SiO₂(001) as the model substrate. C₂/C₂H (from ethylene and acetylene) and C₃/C₃H (from propane) are identified as the active species driving the growth process. C₂H and C₃ are also key for nucleation because of their excellent migration capabilities. In hydrogen-passivated surface models, C₂H demonstrates a lower energy barrier for growth. Experimental results further indicate that acetylene, ethylene, and propane are promising carbon sources for graphene synthesis. These results are valuable for understanding the synthesis of graphene-skinned glass fibre fabrics, with the potential to improve graphene production on insulating substrates.

Scalable synthesis of high-quality graphene via roll-to-roll chemical vapor deposition faces a fundamental conflict between rapid growth and crystallographic perfection. Conventional methane (CH₄)-derived growth suffers from disordered nucleation and orientation mismatch at elevated precursor pressures, limiting industrial adoption. This work resolves this challenge by employing acetylene (C₂H₂) as a carbon precursor to enable carbon dimer-mediated cyclotrimerization nucleation. First-principles calculations reveal that C₂H₂-derived carbon dimers (C₂) spontaneously assemble into hexagonal nuclei, bypassing defect-prone chain-to-ring transitions inherent to monatomic carbon pathway of CH₄. This mechanism ensures > 98% lattice orientation consistency even at nucleation densities of 10⁴ mm⁻², in stark contrast to CH₄-derived graphene. Crucially, the enhanced surface adsorption of C₂ species enables continuous nucleation during lateral growth, achieving high growth rate of 500 mm·min⁻¹ at roll-to-roll process. Leveraging dimeric carbon precursors and Cu single-crystallization technique, we demonstrate roll-to-roll production of graphene films with high crystallographic orientation across meter-scale Cu(111) foils. This precursor-specific strategy decouples nucleation density from disorder accumulation, establishing a scalable pathway for industrial graphene manufacturing.

Multilayer graphene films demonstrate superior electrical and thermal conductivity, mechanical properties, and barrier performance compared to monolayer, thereby exhibiting greater potential for industrial applications. However, the synthesis of multilayer graphene films continues to face critical challenges, primarily including uncontrollable layer numbers, incomplete understanding of growth mechanisms, and poor reproducibility and scalability in mass production. This study introduces the “fractional layer” concept and corresponding mathematical model to precisely quantify graphene layers for the first time. Using this metric, we systematically established growth principles and process windows for layer-controlled graphene synthesis on copper substrates and elucidated the multilayer growth mechanism governed by modulating the lateral growth and vertical growth kinetics. Based on this theoretical framework, the continuous preparation of 2.3-layer graphene films was achieved via industrial scale roll-to-roll chemical vapor deposition equipment, exhibiting exceptional macroscopic uniformity and demonstrating significant potential for applications in transparent, flexible electrothermal heaters. Our work will establish a solid material foundation for the industrial application of multilayer graphene films and offer novel insights into the layer-controlled synthesis of other two-dimensional materials.

Direct growth of graphene on dielectric or insulating materials via chemical vapor deposition (CVD) offers a novel, transfer-free approach for various applications. However, challenges remain in growing graphene on non-catalytic substrates. In particular, the low growth rate of graphene remains a significant barrier to its large-scale production. In this study, propane (C₃H₈) was used as the carbon source to prepare graphene on commercial alumina fiber fabric (AFF) via CVD, resulting in the synthesis of a novel material: graphene-skinned alumina fiber fabric (GAFF). Through comparative analysis of the graphene growth behaviors using C₃H₈ and traditional carbon sources (CH₄ and C₂H₄) on AFF, the growth mechanism of C₃H₈ was elucidated. The pyrolysis of C₃H₈ generates the unique carbon species C₃H, which exhibits distinct advantages in terms of migration, nucleation, and growth on AFF. Graphene nucleation density using C₃H₈ was found to be 160 times higher than that of CH₄ and 50 times higher than C₂H₄. The resulting GAFF exhibits a wide tunable electrical conductivity range (1 to 7000 Ω·sq⁻¹), high tensile strength (> 170 MPa), lightweight properties, flexibility, and a hierarchical macrostructure. These characteristics make GAFF a promising candidate for various applications, including electromagnetic interference (EMI) shielding.

Direct chemical vapor deposition (CVD) growth of graphene on dielectric/insulating materials promises transfer-free applications of graphene. However, growing graphene on non-catalytic substrates faces significant challenges, particularly due to its limited growth rate, restricting large-scale production and potential applications. Here, we develop graphene-skinned glass fiber fabric (GGFF) by growing graphene CVD on commercial glass fiber fabric (GFF). This study utilizes propane as a carbon source to prepare GGFF rapidly. The active carbon source (C₂H) derived from propane plays a significant role in facilitating the rapid growth of graphene films. It accelerated growth rates (~ 50 times faster), and reduced growth temperature (~ 100 °C lower) compared to the conventional carbon source methane. Additionally, propane consistently maintains a higher graphene growth rate than methane at equivalent growth temperatures. The lightweight flexibility, excellent thermal radiation properties, and energy efficiency of GGFF make it an outstanding material for infrared radiation drying.

Chemical vapor deposition (CVD) has shown great promise for the large-scale production of high-quality graphene films for industrial applications. Atomic-scale theoretical studies can help experiments to deeply understand the graphene growth mechanism, and serve as theoretical guides for further experimental designs. Here, by using density functional theory calculations, ab-initio molecular dynamics simulations, and microkinetic analysis, we systematically investigated the kinetics of hydrogen constrained graphene growth on Cu substrate. The results reveal that the actual hydrogen-rich environment of CVD results in CH as the dominating carbon species and graphene H-terminated edges. CH participated island sp² nucleation avoids chain cyclization process, thereby improving the nucleation and preventing the formation of non-hexameric ring defects. The graphene growth is not simply C-atomic activity, rather, involves three main processes: CH species attachment at the growth edge, leading to a localized sp³ hybridized carbon at the connecting site; excess H transfer from the sp³ carbon to the newly attached CH; and finally dehydrogenation to achieve the sp² reconstruction of the newly grown edge. The threshold reaction barriers for the growth of graphene zigzag (ZZ) and armchair (AC) edges were calculated as 2.46 and 2.16 eV, respectively, thus the AC edge grows faster than the ZZ one. Our theory successfully explained why the circumference of a graphene island grown on Cu substrates is generally dominated by ZZ edges, which is a commonly observed phenomenon in experiments. In addition, the growth rate of graphene on Cu substrates is calculated and matches well with existing experimental observations.

Transition metal catalyzed chemical vapor deposition (CVD) is considered as the most promising approach to synthesize high-quality graphene films, and low-temperature growth of defect-free graphene films is long-term challenged because of the high energy barrier for precursor dissociation and graphitization. Reducing the growth temperature can also bring advantages on wrinkle-free graphene films owing to the minimized thermal expansion coefficient mismatch. This work focuses on density functional theory (DFT) calculations of the carbon source precursor with hydroxyl group, especially CH₃OH, on low-temperature CVD growth of graphene on Cu and CuNi substrate. We calculated all the possible cleavage paths for CH₃OH on transition metal substrates. The results show that, firstly, the cleavage barriers of CH₃OH on transition metal substrates are slightly lower than those of CH₄, and once CO appears, it is difficult to break the C–O bond. Secondly, the CO promotes a better formation and retention of perfect rings in the early stage of graphene nucleation and reduces the edge growth barriers. Thirdly, these deoxidation barriers of CO are reduced after CO participates in graphene edge growth. This paper provides a strategy for the low-temperature growth of wrinkles-free graphene on transition metal substrates using CH₃OH.