Preparation and Electrochemical Properties of Rigid Skeleton COS-NMC Material

Abstract

Abstract: An in-situ nitrogen-doped mesoporous carbon material (COS-NMC-x) for supercapacitors was prepared by sol-gel method using chitosan oligosac charide (COS) as carbon precursor, triblock copolymer (F127) and ethyl orthosilicate (TEOs) as templating agent. The material was characterized by means of mass spectrometer, TG-DTG, XRD, Raman spectra, N₂ adsorption/desorption, XPS, FT-IR, hydrophilic and electrochemical evaluation to study the physical and chemical properties and electrochemical performance of the material. The results show that the performance parameters (specific surface area, pore volume and nitrogen atomic number fraction) of COS-NMC-x material tend to increase first and then decrease with the increase of ultrasound time, when the ultrasound time is 15 min,the specific surface area, pore volume and nitrogen atomic number fractionof sample reach the maximum, and the contact angle is the minimum, which are 144.94 m²·g^-1, 0.19 cm³·g^-1, 7.59% and 23.16°, respectively. At the same time, the electrochemical performance of COS-NMC-x was evaluated. The results show that, at a current density of 0.5 A·g^-1, the specific capacitance of sample is 189 F·g^-1, which is much higher than other materials in the same group, indicating that the larger pore structure and nitrogen atomic number fraction are beneficial to the improvement electrochemical performance of the material. After 5 000 cycles at 10 A·g^-1, the capacitance retention rate of sample reaches 114%, exhibiting good electrochemical performance and showing great application potential in supercapacitor applications.

Key words: COS-NMC material, rigid skeleton, chitosan oligosaccharide, mesoporous carbon, electrochemistry, hydrophilicity

CLC Number:

TB383

HE Shunwu, TIAN Hongsong, LI Ying, YE Entong, ZHANG Li, LIN Qian, PAN Hongyan. Preparation and Electrochemical Properties of Rigid Skeleton COS-NMC Material[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(8): 2943-2953.

References

[1] 陈莹莹,宓一鸣,阮勤超,等.石墨烯的制备及应用的研究进展[J].硅酸盐通报,2015,34(3):755-763.
CHEN Y Y, MI Y M, RUAN Q C, et al. Progress on preparation of graphene and its application[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(3): 755-763 (in Chinese).
[2] LIU L, ZHANG H L, WANG G X, et al. Synthesis of mesoporous carbon nanospheres via “pyrolysis-deposition” strategy for CO₂ capture[J]. Journal of Materials Science, 2017, 52(16): 9640-9647.
[3] DU J, LIU L, HU Z P, et al. Order mesoporous carbon spheres with precise tunable large pore size by encapsulated self-activation strategy[J]. Advanced Functional Materials, 2018, 28(33): 1802332.
[4] WANG C J, WU D P, WANG H J, et al. A green and scalable route to yield porous carbon sheets from biomass for supercapacitors with high capacity[J]. Journal of Materials Chemistry A, 2018, 6(3): 1244-1254.
[5] 李璐,高长青,刘怡琳,等.氮杂化介孔碳制备方法及在超级电容器中的应用进展[J].无机盐工业,2021,53(3):24-29+77.
LI L, GAO C Q, LIU Y L, et al. Advances of preparation of nitrogen-doped mesoporous carbon and its application in super-capacitor[J]. Inorganic Chemicals Industry, 2021, 53(3): 24-29+77 (in Chinese).
[6] 潘旭晨,汤静,薛海荣,等.氮掺杂有序介孔碳-Ni纳米复合材料的制备及电化学性能[J].无机化学学报,2015,31(2):282-290.
PAN X C, TANG J, XUE H R, et al. Synthesis and electrocatalytic performance of N-doped ordered mesoporous carbon-Ni nanocomposite[J]. Chinese Journal of Inorganic Chemistry, 2015, 31(2): 282-290 (in Chinese).
[7] WANG X Q, LEE J S, ZHU Q, et al. Ammonia-treated ordered mesoporous carbons as catalytic materials for oxygen reduction reaction[J]. Chemistry of Materials, 2010, 22(7): 2178-2180.
[8] LIANG Z J, HONG Z B, XIE M Y, et al. Recent progress of mesoporous carbons applied in electrochemical catalysis[J]. New Carbon Materials, 2022, 37(1): 152-179.
[9] HUANG C H, DOONG R A. Sugarcane bagasse as the scaffold for mass production of hierarchically porous carbon monoliths by surface self-assembly[J]. Microporous and Mesoporous Materials, 2012, 147(1): 47-52.
[10] 徐玲玲,张小华,陈金华.氮掺杂介孔碳的制备及其电化学超电容性能(英文)[J].物理化学学报,2014,30(7):1274-1280.
XU L L, ZHANG X H, CHEN J H. Synthesis and electrochemical supercapacitive properties of nitrogen-doped mesoporous carbons[J]. Acta Physico-Chimica Sinica, 2014, 30(7): 1274-1280.
[11] SWIEGERS G F, HUANG J H, BRIMBLECOMBE R, et al. Homogeneous catalysts with a mechanical (“machine-like”) action[J]. Chemistry (Weinheim an Der Bergstrasse, Germany), 2009, 15(19): 4746-4759.
[12] DONG X S, LIU X W, CHEN H, et al. Hard template-assisted N, P-doped multifunctional mesoporous carbon for supercapacitors and hydrogen evolution reaction[J]. Journal of Materials Science, 2021, 56(3): 2385-2398.
[13] 孙立.纳米结构晶态碳基材料可控制备及电化学储能特性研究[D].哈尔滨:黑龙江大学,2014.
SUN L. The controllable synthesis of crystalline nanocarbon-based materials and their electrochemical performance for energy storage[D]. Harbin: Heilongjiang University, 2014 (in Chinese).
[14] LI K C, XING R E, LIU S, et al. Access to N-acetylated chitohexaose with well-defined degrees of acetylation[J]. BioMed Research International, 2017, 2017: 2486515.
[15] LIU H, BAO J G, DU Y M, et al. Effect of ultrasonic treatment on the biochemphysical properties of chitosan[J]. Carbohydrate Polymers, 2006, 64(4): 553-559.
[16] CZECHOWSKA-BISKUP R, ROKITA B, LOTFY S, et al. Degradation of chitosan and starch by 360-kHz ultrasound[J]. Carbohydrate Polymers, 2005, 60(2): 175-184.
[17] MOCHIDA I, KU C H, YOON S H, et al. Anodic performances of anisotropic carbon derived from isotropic quinoline pitch[J]. Carbon, 1999, 37(2): 323-327.
[18] PARAKNOWITSCH J P, THOMAS A, ANTONIETTI M. A detailed view on the polycondensation of ionic liquid monomers towards nitrogen doped carbon materials[J]. Journal of Materials Chemistry, 2010, 20(32): 6746.
[19] BENCHAMAS G, HUANG G L, HUANG S Y, et al. Preparation and biological activities of chitosan oligosaccharides[J]. Trends in Food Science & Technology, 2021, 107: 38-44.
[20] WANG Q, WU J, WANG W B, et al. Preparation, characterization and drug-release behaviors of crosslinked chitosan/attapulgite hybrid microspheres by a facile spray-drying technique[J]. Journal of Biomaterials and Nanobiotechnology, 2011, 2(3): 250-257.
[21] NISTICÒ R, FRANZOSO F, CESANO F, et al. Chitosan-derived iron oxide systems for magnetically guided and efficient water purification processes from polycyclic aromatic hydrocarbons[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(1): 793-801.
[22] PENG H L, ZHANG J B, ZHANG J Y, et al. Chitosan-derived mesoporous carbon with ultrahigh pore volume for amine impregnation and highly efficient CO₂ capture[J]. Chemical Engineering Journal, 2019, 359: 1159-1165.
[23] SUN Z M, XU J, WANG G F, et al. Hydrothermal fabrication of rectorite based biocomposite modified by chitosan derived carbon nanoparticles as efficient mycotoxins adsorbents[J]. Applied Clay Science, 2020, 184: 105373.
[24] BIBI S, YASIN T, HASSAN S, et al. Chitosan/CNTs green nanocomposite membrane: synthesis, swelling and polyaromatic hydrocarbons removal[J]. Materials Science and Engineering: C, 2015, 46: 359-365.
[25] SHCHERBAN N, FILONENKO S, YAREMOV P, et al. Boron-doped nanoporous carbons as promising materials for supercapacitors and hydrogen storage[J]. Journal of Materials Science, 2017, 52(3): 1523-1533.
[26] 何易.石墨烯基柔性电极的制备及其透明超级电容器的性能研究[D].天津:河北工业大学,2020.
HE Y. Preparation of flexible graphene-based electrode and researches on the performance of transparent capacitors[D]. Tianjin: Hebei University of Technology, 2020 (in Chinese).
[27] KAUFMAN J H, METIN S, SAPERSTEIN D D. Symmetry breaking in nitrogen-doped amorphous carbon: infrared observation of the Raman-active G and D bands[J]. Physical Review B, 1989, 39(18): 13053-13060.
[28] SCHWAN J, ULRICH S, BATORI V, et al. Raman spectroscopy on amorphous carbon films[J]. Journal of Applied Physics, 1996, 80(1): 440-447.
[29] LI Y G, ZHOU W, WANG H L, et al. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes[J]. Nature Nanotechnology, 2012, 7(6): 394-400.
[30] MCKEOWN N B, BUDD P M, MSAYIB K J, et al. Polymers of intrinsic microporosity (PIMs): bridging the void between microporous and polymeric materials[J]. Chemistry-A European Journal, 2005, 11(9): 2610-2620.
[31] MA Y, MA C, SHENG J, et al. Nitrogen-doped hierarchical porous carbon with high surface area derived from graphene oxide/pitch oxide composite for supercapacitors[J]. Journal of Colloid and Interface Science, 2016, 461: 96-103.
[32] 王媛媛,陈爱兵,张向京,等.软模板法合成介孔碳材料的研究与展望[J].化工新型材料,2013,41(6):15-17.
WANG Y Y, CHEN A B, ZHANG X J, et al. Research and prospect of ordered mesoporous carbon materials synthesized by soft template method[J]. New Chemical Materials, 2013, 41(6): 15-17 (in Chinese).
[33] THOMMES M, KANEKO K, NEIMARK A V, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)[J]. Pure and Applied Chemistry, 2015, 87(9/10): 1051-1069.
[34] MOHOD A V, GOGATE P R. Ultrasonic degradation of polymers: effect of operating parameters and intensification using additives for carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA)[J]. Ultrasonics Sonochemistry, 2011, 18(3): 727-734.
[35] GUO Y G, HU Y S, SIGLE W, et al. Superior electrode performance of nanostructured mesoporous TiO₂ (anatase) through efficient hierarchical mixed conducting networks[J]. Advanced Materials, 2007, 19(16): 2087-2091.
[36] BABARAO R, DAI S, JIANG D E. Nitrogen-doped mesoporous carbon for carbon capture: a molecular simulation study[J]. The Journal of Physical Chemistry C, 2012, 116(12): 7106-7110.
[37] MO Y H, DU J, LV H J, et al. N-doped mesoporous carbon nanosheets for supercapacitors with high performance[J]. Diamond and Related Materials, 2021, 111: 108206.
[38] SEVILLA M, FUERTES A B. Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides[J]. Chemistry-A European Journal, 2009, 15(16): 4195-4203.
[39] 许亮,杨梅,葛书生,等.氧化钴/氮掺杂介孔碳球的制备及其电化学性能研究[J].功能材料,2016,47(7):7168-7172.
XU L, YANG M, GE S S, et al. Synthesis and electrochemical performance of cobalt oxide/nitrogen-doped mesoporous composite carbon sphere[J]. Journal of Functional Materials, 2016, 47(7): 7168-7172 (in Chinese).
[40] TAN J B, HE X B, YIN F X, et al. β-Mo₂C/N, P-co-doped carbon as highly efficient catalyst for hydrogen evolution reaction[J]. Journal of Materials Science, 2019, 54(6): 4589-4600.
[41] WIENER C G, QIANG Z, XIA Y F, et al. Impact of surface wettability on dynamics of supercooled water confined in nitrogen-doped ordered mesoporous carbon[J]. Physical Chemistry Chemical Physics, 2018, 20(44): 28019-28025.
[42] KWON T, NISHIHARA H, ITOI H, et al. Enhancement mechanism of electrochemical capacitance in nitrogen-/boron-doped carbons with uniform straight nanochannels[J]. Langmuir, 2009, 25(19): 11961-11968.
[43] XIONG W, LIU M X, GAN L H, et al. Preparation of nitrogen-doped macro-/mesoporous carbon foams as electrode material for supercapacitors[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2012, 411: 34-39.
[44] DU J, LIU L, YU Y F, et al. N-doping carbon sheet and core-shell mesoporous carbon sphere composite for high-performance supercapacitor[J]. Journal of Industrial and Engineering Chemistry, 2019, 76: 450-456.
[45] SONG F X, CHEN Q L, LI Y, et al. High energy density supercapacitors based on porous mSiO₂@Ni₃S₂/NiS₂ promoted with boron nitride and carbon[J]. Chemical Engineering Journal, 2020, 390: 124561.
[46] XIN X P, KANG H Q, FENG J G, et al. A novel sol-gel strategy for N, P dual-doped mesoporous carbon with high specific capacitance and energy density for advanced supercapacitors[J]. Chemical Engineering Journal, 2020, 393: 124710.
[47] 刘双宇,巩学海,徐丽,等.介孔碳/石墨烯复合材料的制备及在超级电容器中的应用[J].硅酸盐学报,2017,45(2):312-316.
LIU S Y, GONG X H, XU L, et al. Mesoporous carbon/graphene composite material and its application as supercapacitor[J]. Journal of the Chinese Ceramic Society, 2017, 45(2): 312-316 (in Chinese).
[48] SUN F, QU Z B, GAO J H, et al. In situ doping boron atoms into porous carbon nanoparticles with increased oxygen graft enhances both affinity and durability toward electrolyte for greatly improved supercapacitive performance[J]. Advanced Functional Materials, 2018, 28(41): 1804190.
[49] CHEN L, WEN Z Y, CHEN L N, et al. Nitrogen and sulfur co-doped porous carbon fibers film for flexible symmetric all-solid-state supercapacitors[J]. Carbon, 2020, 158: 456-464.