以木材液化物为原料,利用乳液法制备树脂球,经半固化、溶解、二次固化、炭化、活化制备木质基空心炭球(HCS)。通过扫描电镜、X射线衍射、拉曼光谱仪、X射线光电子能谱、比表面及孔隙度分析仪研究了半固化时间(3min、10min、20min、30min)对木质基空心炭球表面形貌、石墨化程度、表面官能团、空隙结构的影响,并探讨了HCS的电化学性能。结果表明:随着半固化时间增加,HCS壁变厚,空腔体积变小,石墨化程度先增大后减小,表面官能团C—C键先减少后增加,C—O键先增加后减少。半固化10min时,制备HCS的比表面积高达1610m2/g,总孔容达到0.93cm3/g,在以6mol/L KOH作为电解质的三电极体系中进行测试,发现当电流密度为0.5A/g时比电容高达139.8F/g,经3000次循环测试后,其比电容保持率为77%,显示了优异的倍率性能。
Using liquefied wood as raw material,resin spheres were prepared by emulsion method,and wood-based hollow carbon sphere (HCS) were prepared by semi-curing,dissolving,secondary curing,carbonization and activation.The effects of semi-curing time (3min,10min,20min and 30min) on the surface morphology,graphitization degree,surface functional groups and void structure of the HCS were studied by SEM,XRD,raman spectrometer,XPS and specific surface and porosity analyzer.The electrochemical properties of the HCS were discussed.The results shown that with the increase of semi-curing time,the HCS wall became thicker,the cavity volume became smaller.The graphitization degree increased firstly and then decreased,the C—C bond of surface functional groups decreased firstly and then increased,and the C—O bond increased firstly and then decreased.After 10min of semi-curing,the specific surface area of the HCS was as high as 1610m2/g and the total pore volume was 0.93cm3/g.Tested in three-electrode system with 6mol/L KOH as electrolyte,it was found that the specific capacitance was as high as 139.8F/g,when the current density was 0.5A/g,and the specific capacitance retention rate was 77% after 3000 cycles of testing,which shown excellent rate performance.
[1] Shi X,Zhang S,Chen X,et al.Effect of iron oxide impregnated in hollow carbon sphere as symmetric supercapacitors[J].Journal of Alloys and Compounds,2017,726:466-473.
[2] Chen A,Wang Y,Yu Y,et al.Nitrogen-doped hollow carbon spheres for supercapacitors[J].Journal of Materials Science,2016,52(6):3153-3161.
[3] Qian X,Miao L,Jiang J,et al.Hydrangea-like N/O codoped porous carbons for high-energy supercapacitors[J].Chemical Engineering Journal,2020,388:124208.
[4] Zhang Y,Liu L,Yu Y,et al.Controlling the inner structure of carbon spheres via “Protective-Dissolution” strategy for supercapacitor[J].The Journal of Physical Chemistry C,2019,123(5):2801-2807.
[5] Yadav K,Jassal M,Agrawal A K.Highly conducting silver nanowire-polyacrylonitrile hollow fibres for flexible supercapacitors[J].International Journal of Energy Research,2019,44(2):1284-1293.
[6] Zhang G,Guan T,Wang N,et al.Small mesopore engineering of pitch-based porous carbons toward enhanced supercapacitor performance[J].Chemical Engineering Journal,2020,399:125818.
[7] 刘鑫,马晓军.氧化铌/木质活性碳纤维复合材料的结构性能表征[J].生物质化学工程,2021,55(2):16-22.
[8] Kai D,Tan M J,Chee P L,et al.Towards lignin-based functional materials in a sustainable world[J].Green Chemistry,2016,18(5):1175-1200.
[9] 邹江东,许飞,赵强,等.不同生物质活性炭的合成与电化学性能[J].成都大学学报(自然科学版),2018,37(1):88-91.
[10] 商俊博,董子航,赵广杰.木质基活性微球炭的制备与表征[J].化工新型材料,2018,46(10):200-203.
[11] Du J,Liu L,Zhang Y,et al.Rich porous dual-shell carbon spheres by dissolution-reassembly with high performance in supercapacitor[J].Journal of Energy Storage,2020,29:101375.
[12] Chen C,Zhang L,Li M,et al.Controlling morphology and particle size of hollow poly(styrene-divinylbenzene) microspheres fabricated by template-based method[J].Journal of Saudi Chemical Society,2018,22(6):644-653.
[13] Xi J,Li H,Xi J,et al.Preparation of high porosity biochar materials by template method:a review[J].Environmental Science and Pollution Research,2020,27(17):20675-20684.
[14] 马晓军,赵广杰.炭化条件对木材苯酚液化物碳纤维性能的影响[J].复合材料学报,2008(5):74-78.
[15] Qian L,Guo F,Jia X,et al.Recent development in the synthesis of agricultural and forestry biomass-derived porous carbons for supercapacitor applications:a review[J].Ionics,2020,26(8):3705-3723.
[16] Huang S,Zhang J,Li P,et al.Preparation of metal-organic framework-derived nitrogen-doped porous carbon and study of its supercapacitive performance in potassium citrate electrolyte[J].Applied Surface Science,2018,459:120-128.
[17] Amiri M,Davarani S S H,Kaverlavani S K,et al.Construction of hierarchical nanoporous CuCo2V2O8 hollow spheres as a novel electrode material for high-performance asymmetric supercapacitors[J].Applied Surface Science,2020,527:146855.
[18] Ma X,Ding C,Li D,et al.A facile approach to prepare biomass-derived activated carbon hollow fibers from wood waste as high-performance supercapacitor electrodes[J].Cellulose,2018,25(8):4743-4755.
[19] Ma L,Li J,Ma X.Improvement of electrochemical properties of activated carbon hollow fibers from liquefied wood by charcoal power[J].Materials Letters,2019,255:126544.
[20] 宋豫龙,李伟,徐州.喷雾热解制备落叶松基炭球及其电化学性能[J].林产化学与工业,2019,39(2):9-15.
[21] Feng S,Liu Z,Yu Q,et al.Monodisperse carbon sphere-constructed pomegranate-like structures for high-volumetric-capacitance supercapacitors[J].ACS Applied Materials & Interfaces,2019,11(4):4011-4016.
基金资助
国家自然科学基金(31870564)
PDF
