鉴于碳材料容量低、循环稳定差,提出了利用有机-无机杂化的概念来制备碳基复合材料,并将其用做锂离子电池负极材料。首先以亚磷酸三乙酯为原料制备磷酰氯,然后借助炭黑表面的羟基与羧基进行接枝反应,制备出有机磷修饰炭黑原料,并利用红外光谱、氮气吸脱附测试对材料进行了表面官能团及结构表征,利用恒流充放电与循环伏安测试对其储锂性能和动力学特性进行了表征。结果表明:有机磷官能团修饰到炭黑表面,与原料炭黑相比,磷修饰炭黑的首圈可逆容量由301mAh/g提升至950mAh/g,首圈库仑效率由54%提升至80%,动力学分析表明,有机磷官能团的引入明显增强了电极材料储锂过程中的电容特性。
In view of the low capacity and poor cyclic stability of carbon materials,the strategy of organic-inorganic hybridization is developed to produce carbon-based composite materials for the anode of Li-ion batteries (LIBs).The organophosphorus modifications on the surface of carbon black were successfully performed.The structures of organophosphorus groups on the surface were verified by FT-IR measurements.The Li storage capacity and kinetic properties were characterized by the galvanostaic charge/discharge and cyclic voltammetry tests.Compared with raw carbon black (CB),the initial capacity was enhanced from 301mAh/g to 950mAh/g,and the coulombic efficiency was increased from 54% to 80%.Kinetics analysis revealed that the Li+ storage was capacitive dominating process via introducing organophosphorus functional groups on the surface of CB.
[1] 严旭明,冯光炷,黄雪.锂离子电池负极材料的制备及应用进展[J].化工新料,2019,47(7):22-25.
[2] Nasir Mahmood,Tang T Y,Hou Y L.Nanostructured anode materials for lithium ion batteries:progress,challenge and perspective[J].Advanced Energy Materials,2016,6(17):1600374.
[3] Jin Y,Zhu B,Zhu J,et al.Challenges and recent progress in the development of Si anodes for lithium-ion battery[J].Advanced Energy Materials,2017,7(23):1700715.
[4] Huang J,Lin Y,Ji M,et al.Nitrogen-doped porous carbon derived from foam polystyrene as an anode material for lithium-ion batteries[J].Applied Surface Science,2019,504:144398.
[5] Wang Q,Yang J,Zhou X,et al.N,S Co-doped hierarchical porous carbon from antibiotic bacteria residues as anode materials for lithium ion batteries[J].Journal of the Electrochemical Society,2019,166(4):A704-A710.
[6] Piedboeuf M,Job N,Aqil A,et al.Understanding the influence of surface oxygen groups on the electrochemical behavior of porous carbons as anodes for lithium-ion batteries[J].ACS Applied Materials & Interfaces,2020,12(32):36054-36065.
[7] Chen W,Chen C,Xiong X,et al.Coordination of surface-induced reaction and intercalation:toward a high-performance carbon anode for sodium-ion batteries[J].Advanced Science,2017,4:1600500.
[8] Xie C P,Wang N,Huang C S,et al.Tuning the properties of graphdiyne by introducing electronwithdrawing/donating groups[J].Angewandte Chemie International Edition,2020,59(32):13542-13546.
[9] Li Y,Wu C,Lu J,et al.Insights into the Na+ storage mechanism of phosphorus functionalized hard carbon as ultrahigh capacity anodes[J].Advanced Energy Materials,2018,8(18):1702781.
[10] Boehm H P,Diehl E,Heck W,et al.Surface oxides of carbon[J].AngewandteChemie International Edition,1964,3(10):669-677.
[11] 刘波,王博.磷酰氯合成方法研究进展[J].化学工程与装备,2010(12):133-134.
[12] Kasyan O,Swierczynski D,Kalchenko V,et al.Upper rim substituted thiacalix[4]arenes[J].Tetrahedron Letters,2003,44:7167-7170.
[13] 刘志广.仪器分析[M].北京:高等教育出版社,2007,285-289.
[14] Puziy A M,Poddubnaya O I,Martínez-Alonso A,et al.Surface chemistry of phosphorus-containing carbons of lignocellulosic origin[J].Carbon,2005,43(14):2857-2868.
[15] Fang G,Wu Z,Zhou J,et al.Observation of pseudocapacitive effect and fast ion diffusion in bimetallic sulfides as an advanced sodium-ion battery anode[J].Advanced Energy Materials,2018,8(19):1703155.
[16] Wang J,Polleux J,Lim J,et al.Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanoparticles[J].The Journal of Physical Chemistry C,2007,111(40):14925-14931.
基金资助
深圳职业技术学院博士后启动基金资助项目(6020330007K)
PDF
