Shulyak Vladimir A, Morozov Nikolai S, Gracheva Alexandra V, Gritskevich Maria D, Chebotarev Sergei N, Avdeev Viktor V
Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia.
Nanomaterials (Basel). 2024 Jul 7;14(13):1162. doi: 10.3390/nano14131162.
Flexible graphite foils with varying thicknesses (S = 282 ± 5 μm, M = 494 ± 7 μm, L = 746 ± 8 μm) and an initial density of 0.70 g/cm were obtained using the nitrate method. The specific electrical and thermal conductivity of these foils were investigated. As the density increased from 0.70 g/cm to 1.75 g/cm, the specific electrical conductivity increased from 69 to 192 kS/m and the thermal conductivity increased from 109 to 326 W/(m·K) due to the rolling of graphite foils. The study showed that conductivity and anisotropy depend on the shape, orientation, and contact area of thermally expanded graphite (TEG) mesoparticles (mesostructural factor), and the crystal structure of nanocrystallites (nanostructural factor). A proposed mesostructural model explained these increases, with denser foils showing elongated, narrowed TEG particles and larger contact areas, confirmed by electron microscopy results. For graphite foils 200 and 750 μm thick, increased density led to a larger coherent scattering region, likely due to the rotation of graphite mesoparticles under mechanical action, while thinner foils (<200 μm) with densities > 1.7 g/cm showed increased plastic deformation, indicated by a sharp reduction in the coherent scattering region size. This was also evident from the decrease in misorientation angles with increasing density. Rolling reduced nanocrystallite misorientation angles along the rolling direction compared to the transverse direction (TD) (for 1.75 g/cm density ΔMA = 1.2° (), 2.6° (), and 2.4° ()), explaining the observed anisotropy in the electrical and mechanical properties of the rolled graphite foils. X-ray analysis confirmed the preferred nanocrystallite orientation and anisotropy coefficients (A) using Kearns parameters, which aligned well with experimental measurements (for L series foils calculated as: A = 1.05, A = 1.10, and A = 1.16). These calculated values corresponded well with the experimental measurements of specific electrical conductivity, where the anisotropy coefficient changed from 1.00 to 1.16 and mechanical properties varied from 0.98 to 1.13.
采用硝酸盐法制备了不同厚度(S = 282 ± 5 μm,M = 494 ± 7 μm,L = 746 ± 8 μm)且初始密度为0.70 g/cm³的柔性石墨箔。对这些箔的比电导率和热导率进行了研究。随着密度从0.70 g/cm³增加到1.75 g/cm³,由于石墨箔的轧制,比电导率从69 kS/m增加到192 kS/m,热导率从109 W/(m·K)增加到326 W/(m·K)。研究表明,电导率和各向异性取决于热膨胀石墨(TEG)介观颗粒的形状、取向和接触面积(介观结构因素)以及纳米微晶的晶体结构(纳米结构因素)。提出的介观结构模型解释了这些增加现象,密度更高的箔显示出细长、变窄的TEG颗粒和更大的接触面积,这一点得到了电子显微镜结果的证实。对于200和750 μm厚的石墨箔,密度增加导致相干散射区域增大,这可能是由于石墨介观颗粒在机械作用下发生旋转,而密度> 1.7 g/cm³的较薄箔(<200 μm)显示出塑性变形增加,这表现为相干散射区域尺寸急剧减小。这也从取向差角随密度增加而减小中明显看出。与横向(TD)相比,轧制使纳米微晶沿轧制方向的取向差角减小(对于1.75 g/cm³密度,ΔMA = 1.2°()、2.6°()和2.4°()),这解释了轧制石墨箔在电学和力学性能方面观察到的各向异性。X射线分析使用卡恩斯参数证实了纳米微晶的择优取向和各向异性系数(A),其与实验测量结果吻合良好(对于L系列箔计算为:A = 1.05、A = 1.10和A = 1.16)。这些计算值与比电导率的实验测量结果吻合良好,其中各向异性系数从1.00变化到1.16,力学性能从0.98变化到1.13。