| Citation: |
LI Ruiqing，TANG Yuegang，LUO Peng，et al. Evolutionary characteristics of microstructure of coal-based graphene fromNingxia coals: Comprehensive characterized analysis[J]. Coal Science and Technology，2025，53（5）：390−406. DOI: 10.12438/cst.2024-0281
|
The preparation and characterization of coal-based carbon materials is a hot topic. The structural characteristics of coal-based graphene not only determine the performance of the products, but also provide reference for process control during product preparation. Therefore, it is necessary to have a clear understanding of the microstructure and morphology of coal-based graphene. This study collected 8 different coal ranks coals in Ningxia, and obtained coal-based graphite through high-temperature graphitization treatment after chemical demineralization. Graphene was prepared using an improved Hummer’s redox method, and the microstructure and structural parameters of coal-based graphene were comprehensively characterized by X-ray diffraction, Raman spectroscopy, atomic force microscopy, and high-resolution transmission electron microscopy. The results indicate that the coal–based graphene products prepared from coal samples of different coal ranks in Ningxia are all few-layer graphene. Graphitization can significantly improve the order and graphitization degree of coal structure, which is beneficial for the preparation of coal-based graphene, especially for low coals. In this study, the graphitization degree of coal-based graphites are more than 0.70, and the highest is 0.99. The higher the coal rank, the larger the diameter and stacking height of the graphene prepared, the fewer defects, and the better the peeling effect. and better the stripping effect of graphene prepared. The diameter of the coal-based graphene prepared in this study ranges from 3.78 to 13.04 nm, with interlayer spacing exceeding 0.355 0 nm and a maximum of 0.366 1 nm. As the coal rank increases, the diameter of coal-based graphene increases more significantly than the stacking height, the morphology of coal-based graphene tends to develop in a flattened form in general. The caking of coals can cause an increase in the surface roughness of graphene, but it does not affect the development of the crystal form and order of graphene microcrystalline domains. As the coal rank increases, the graphene structure undergoes an evolution path of vortex type -Y-type - semi-plane type -plane type. The plane type graphene structure is the final form of coal structure evolution during the preparation of coal-based graphene, characterized by obvious peeling, curling, and stretching, which also provides the possibility for the formation of step like of graphene structures.
| [1] |
NOVOSELOV K S,GEIM A K,MOROZOV S V,et al. Electric field effect in atomically thin carbon films[J]. Science,2004,306(5696):666−669.
|
| [2] |
CHEN Q,ZHU H W. Structural characterizations of graphene[M]:Graphene. Amsterdam:Elsevier,2018:13−26.
|
| [3] |
LEE C G,WEI X D,KYSAR J W,et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene[J]. Science,2008,321(5887):385−388.
|
| [4] |
REINA A,JIA X T,HO J,et al. Large area,few-layer graphene films on arbitrary substrates by chemical vapor deposition[J]. Nano Letters,2009,9(1):30−35.
|
| [5] |
LIANG M H,LUO B,ZHI L J. Application of graphene and graphene-based materials in clean energy-related devices[J]. International Journal of Energy Research,2009,33(13):1161−1170.
|
| [6] |
HUAN X,TANG Y G,XU J J,et al. Structural characterization of graphenic material prepared from anthracites of different characteristics:A comparative analysis[J]. Fuel Processing Technology,2019,183:8−18.
|
| [7] |
郇璇. 煤基石墨烯与煤基石墨烯量子点结构影响因素研究[D]. 北京:中国矿业大学(北京),2019.
HUAN Xuan. Study on the influencing factors of coal-based graphene and coal-based graphene quantum dots structure[D]. Beijing:China University of Mining & Technology-Beijing,2019.
|
| [8] |
VIJAPUR S H,WANG D,BOTTE G G. The growth of transparent amorphous carbon thin films from coal[J]. Carbon,2013,54:22−28.
|
| [9] |
李瑞青,唐跃刚,郇璇,等. 煤基石墨烯原料与制备技术研究进展[J]. 煤田地质与勘探,2020,48(5):1−15. doi: 10.3969/j.issn.1001-1986.2020.05.001
LI Ruiqing,TANG Yuegang,HUAN Xuan,et al. Progress in the research on the raw materials and the preparation techniques of coal-based graphene[J]. Coal Geology & Exploration,2020,48(5):1−15. doi: 10.3969/j.issn.1001-1986.2020.05.001
|
| [10] |
LU L,SAHAJWALLA V,KONG C,et al. Quantitative X-ray diffraction analysis and its application to various coals[J]. Carbon,2001,39(12):1821−1833.
|
| [11] |
RODRIGUES S,SUÁREZ-RUIZ I,MARQUES M,et al. Microstructural evolution of high temperature treated anthracites of different rank[J]. International Journal of Coal Geology,2011,87(3-4):204−211.
|
| [12] |
TAKAGI H,MARUYAMA K,YOSHIZAWA N,et al. XRD analysis of carbon stacking structure in coal during heat treatment[J]. Fuel,2004,83(17-18):2427−2433.
|
| [13] |
ZHANG S,LIU Q F,ZHANG H,et al. Structural order evaluation and structural evolution of coal derived natural graphite during graphitization[J]. Carbon,2020,157:714−723.
|
| [14] |
ZHANG H,LI K,SUN J M,et al. The structural evolution and mutation of graphite derived from coal under the influence of natural igneous plutonic intrusion[J]. Fuel,2022,322:124066.
|
| [15] |
OBERLIN A,TERRIERE G. Graphitization studies of anthracites by high resolution electron microscopy[J]. Carbon,1975,13(5):367−376.
|
| [16] |
MARSH H,MENENDEZ R. Carbons from pyrolysis of pitches,coals,and their blends[J]. Fuel Processing Technology,1988,20:269−296.
|
| [17] |
王绍清,王小令,沙吉顿,等. 煤石墨化:结构和差异性演化[J]. 煤炭学报,2022,47(12):4300−4312.
WANG Shaoqing,WANG Xiaoling,SHA Jidun,et al. Coal graphitization:Structures and their differential evolution[J]. Journal of China Coal Society,2022,47(12):4300−4312.
|
| [18] |
李阔,刘钦甫,宋波涛,等. 湖南新化煤系石墨结构演化及其热反应行为[J]. 煤田地质与勘探,2020,48(1):42−47,54. doi: 10.3969/j.issn.1001-1986.2020.01.006
LI Kuo,LIU Qinfu,SONG Botao,et al. Investigation on structural evolution and thermal reaction of coal-based graphite from Xinhua County,Hunan Province[J]. Coal Geology & Exploration,2020,48(1):42−47,54. doi: 10.3969/j.issn.1001-1986.2020.01.006
|
| [19] |
CHE Y J,SHI K M,CUI Z H,et al. Conversion of low temperature coal tar into high value-added chemicals based on the coupling process of fast pyrolysis and catalytic cracking[J]. Energy,2023,264:126169.
|
| [20] |
张小梅,王绍清,陈昊,李雪琦,张一岫. 低煤级煤的石墨化研究:芳香结构演化特征[J]. 煤炭学报,2022,47(7):2768−2778.
ZHANG Xiaomei,WANG Shaoqing,CHEN Hao,LI Xueqi,ZHANG Yixiu. An investigation on the graphitization of low rank coal:Evolutional characteristics of aromatic structure[J]. Journal of China Coal Society,2022,47(7):2768−2778.
|
| [21] |
王路,董业绩,张鹤,等. 煤成石墨化作用的影响因素及其实验验证[J]. 矿业科学学报,2018,3(1):9−19.
WANG Lu,DONG Yeji,ZHANG He,et al. Factors affecting graphitization of coal and the experimental validation[J]. Journal of Mining Science and Technology,2018,3(1):9−19.
|
| [22] |
LUO P,TANG Y G,LI R Q,et al. The pretreatment of hydrous pyrolysis on the synthetic graphitization of coal:Insights into temperature,pressure,and water[J]. Fuel,2024,358:130119.
|
| [23] |
LI R,TANG Y,CHE Q,et al. Effects of Coal rank and macerals on the structure characteristics of coal-based graphene materials from anthracite in Qinshui Coalfield [J]. Minerals 2022,12:588.
|
| [24] |
ZHOU Q,ZHAO Z B,ZHANG Y T,et al. Graphene sheets from graphitized anthracite coal:Preparation,decoration,and application[J]. Energy & Fuels,2012,26(8):5186−5192.
|
| [25] |
唐跃刚,徐靖杰,郇璇,等. 云南小发路无烟煤基石墨烯制备与谱学表征[J]. 煤炭学报,2020,45(2):740−748.
TANG Yuegang,XU Jingjie,HUAN Xuan,et al. Preparation and spectroscopic characterization of coal-based graphene from anthracite in Xiaofalu,Yunnan,China[J]. Journal of China Coal Society,2020,45(2):740−748.
|
| [26] |
LAN C Y,TANG Y G,HUAN X,et al. Effects of minerals in anthracite on the formation of coal-based graphene[J]. ChemistrySelect,2019,4(19):5937−5944.
|
| [27] |
LUO P,TANG Y G,LI R Q,et al. Effects of minerals type and content on the synthetic graphitization of coal:Insights from the mixture of minerals and anthracite with varied rank[J]. Minerals,2023,13(8):1024.
|
| [28] |
MA P L,TANG Y G,LI R Q,et al. Preparation and characteristic analysis of graphene based on coal macerals of different rank[J]. Fuel,2024,357:130004.
|
| [29] |
WANG L,ZHANG H,LI Y. On the difference of characterization and supercapacitive performance of graphene nanosheets from precursors of inertinite- and vitrinite-rich coal[J]. Journal of Alloys and Compounds,2020,815:152502.
|
| [30] |
唐跃刚,车启立,李瑞青,等. 黔西与湖南寒婆坳地区煤制石墨烯结构的演化特征[J]. 煤炭学报,2023,48(1):357−372.
TANG Yuegang,CHE Qili,LI Ruiqing,et al. Evolutionary characteristics of coal based graphene structure in West Guizhou and Hanpo’ao,Hunan[J]. Journal of China Coal Society,2023,48(1):357−372.
|
| [31] |
唐跃刚,李瑞青,樊江涛,等. 宁夏碱沟山脱灰无烟煤石墨烯量子点制备与谱学特征[J]. 煤炭学报,2022,47(12):4278−4289.
TANG Yuegang,LI Ruiqing,FAN Jiangtao,et al. Preparation and spectroscopic characteristics of coal-based graphene quantum dots from demineralized anthracite in Jiangoushan,Ningxia[J]. Journal of China Coal Society,2022,47(12):4278−4289.
|
| [32] |
樊江涛,唐跃刚,宋晓夏,等. 接触变质作用对煤基石墨烯量子点的影响研究[J]. 地质论评,2022,68(6):2277−2289.
FAN Jiangtao,TANG Yuegang,SONG Xiaoxia,et al. Effect of contact metamorphism on coal-based graphene quantum dots[J]. Geological Review,2022,68(6):2277−2289.
|
| [33] |
TANG Y G,HUAN X,LAN C Y,et al. Effects of coal rank and high organic sulfur on the structure and optical properties of coal-based graphene quantum dots[J]. Acta Geologica Sinica - English Edition,2018,92(3):1218−1230.
|
| [34] |
CHEN C,TANG Y G,GUO X. Comparison of structural characteristics of high-organic-sulfur and low-organic-sulfur coal of various ranks based on FTIR and Raman spectroscopy[J]. Fuel,2022,310:122362.
|
| [35] |
朱川,白向飞,涂华,等. 我国典型特低灰煤深度脱灰影响因素[J]. 洁净煤技术,2018,24(6):27−31.
ZHU Chuan,BAI Xiangfei,TU Hua,et al. Deep de-ashing influencing factors of typical ultra-low ash coal in China[J]. Clean Coal Technology,2018,24(6):27−31.
|
| [36] |
HUMMERS W S Jr,OFFEMAN R E. Preparation of graphitic oxide[J]. Journal of the American Chemical Society,1958,80(6):1339.
|
| [37] |
曹代勇,魏迎春,李阳,等. 煤系石墨鉴别指标厘定及分类分级体系构建[J]. 煤炭学报,2021,46(6):1833−1846.
CAO Daiyong,WEI Yingchun,LI Yang,et al. Determination of identification index and construction of classification and classification system of coal measures graphite[J]. Journal of China Coal Society,2021,46(6):1833−1846.
|
| [38] |
SEEHRA M S,PAVLOVIC A S. X-Ray diffraction,thermal expansion,electrical conductivity,and optical microscopy studies of coal-based graphites[J]. Carbon,1993,31(4):557−564.
|
| [39] |
LIEVENS C,CI D H,BAI Y,et al. A study of slow pyrolysis of one low rank coal via pyrolysis–GC/MS[J]. Fuel Processing Technology,2013,116:85−93.
|
| [40] |
SONIBARE O O,HAEGER T,FOLEY S F. Structural characterization of Nigerian coals by X-ray diffraction,Raman and FTIR spectroscopy[J]. Energy,2010,35(12):5347−5353.
|
| [41] |
OKOLO G N,NEOMAGUS H W J P,EVERSON R C,et al. Chemical–structural properties of South African bituminous coals:Insights from wide angle XRD–carbon fraction analysis,ATR–FTIR,solid state 13C NMR,and HRTEM techniques[J]. Fuel,2015,158:779−792.
|
| [42] |
HUANG D B,CHUAN X Y,CAO X. Spectroscopy characterization of anthracite oxide[J]. Guang Pu,2016,36(11):3698−3703.
|
| [43] |
王绍清,陈昊,王小令. 热变煤的变质演化纳米特性及其类石墨结构特征[J]. 煤炭学报,2023,48(2):846−854.
WANG Shaoqing,CHEN Hao,WANG Xiaoling. Nano properties of metamorphic evolution of thermally altered coal and its graphite-like structural characteristics[J]. Journal of China Coal Society,2023,48(2):846−854.
|
| [44] |
TAKAGI H,MARUYAMA K,YOSHIZAWA N,et al. XRD analysis of carbon stacking structure in coal during heat treatment[J]. Fuel,2004,83(17−18):2427−2433.
|
| [45] |
ZHANG Y T,LI K K,LIU G Y,et al. Synthesis and photocatalytic CO2 reduction activity of a coal-based graphene assembly[J]. Carbon,2016,104:261.
|
| [46] |
VLAHOV A. XRD graphitization degrees:A review of the published data and new calculations,correlations,and applications[J]. Geologica Balcanica,2021,50(1):11−35.
|
| [47] |
YEN T F,ERDMAN J G,POLLACK S S. Investigation of the structure of petroleum asphaltenes by X-ray diffraction[J]. Analytical Chemistry,1961,33:1587−1594.
|
| [48] |
STANKOVICH S,DIKIN D A,PINER R D,et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon,2007,45(7):1558−1565.
|
| [49] |
PIMENTA M A,DRESSELHAUS G,DRESSELHAUS M S,et al. Studying disorder in graphite-based systems by Raman spectroscopy[J]. Physical Chemistry Chemical Physics,2007,9(11):1276−1290.
|
| [50] |
李美芬,曾凡桂,齐福辉,等. 不同煤级煤的Raman谱特征及与XRD结构参数的关系[J]. 光谱学与光谱分析,2009,29(9):2446−2449.
LI Meifen,ZENG Fangui,QI Fuhui,et al. Raman spectroscopic characteristics of different rank coals and the relation with XRD structural parameters[J]. Spectroscopy and Spectral Analysis,2009,29(9):2446−2449.
|
| [51] |
SHENG C D. Char structure characterised by Raman spectroscopy and its correlations with combustion reactivity[J]. Fuel,2007,86(15):2316−2324.
|
| [52] |
王绍清,沙吉顿,张浩,等. 热接触变质煤制备石墨烯:化学结构演化[J]. 煤炭科学技术,2021,49(2):238−244.
WANG Shaoqing,SHA Jidun,ZHANG Hao,et al. Graphene produced by thermally-altered coal:Chemical structure evolution[J]. Coal Science and Technology,2021,49(2):238−244.
|
| [53] |
LI K,RIMMER S M,PRESSWOOD S M,et al. Raman spectroscopy of intruded coals from the Illinois basin:Correlation with rank and estimated alteration temperature[J]. International Journal of Coal Geology,2020,219:103369.
|
| [54] |
HAUQUIER F,ALAMARGUY D,VIEL P,et al. Conductive-probe AFM characterization of graphene sheets bonded to gold surfaces[J]. Applied Surface Science,2012,258(7):2920−2926.
|
| [55] |
CONG C X,LI K,ZHANG X X,et al. Visualization of arrangements of carbon atoms in graphene layers by Raman mapping and atomic-resolution TEM[J]. Scientific Reports,2013,3:1195.
|
| [56] |
CEMIN F,JIMENEZ M J M,LEIDENS L M,et al. A thermodynamic study on phase formation and thermal stability of AlSiTaTiZr high-entropy alloy thin films[J]. Journal of Alloys and Compounds,2020,838:155580.
|
| [57] |
LI R Q,TANG Y G,CHE Q L,et al. Study on the microstructure of the symbiosis of coal-based graphene and coal-based graphene quantum dots:Preparation and characterization[J]. Nanotechnology,2022,33(45):455702.
|
Supported by: Beijing Renhe Information Technology Co., Ltd. 
DownLoad: