Preparation and electrochemical properties of polyaniline/(montmorillonite-cellulosenanofibers) composite electrodes
-
摘要: 采用冷冻干燥法制备蒙脱土-纳米纤维素(MTM-CNFs)复合基底材料,再通过原位聚合,无模版法构建有序纳米阵列线结构,合成了聚苯胺(PANi)三元复合电极材料。对其微观结构、合成机制、电导率及电化学性质进行了分析,研究了一维线性材料、二维片状材料与导电聚合物的复合机制及无模版法制备PANi阵列储能材料的方法。结果表明,二维MTM纳米片的加入有利于聚苯胺在基底材料上进行原位生长,形成排列有序的阵列线结构,有效提高了电极材料的比电容量。当复合基底材料中MTM和CNFs质量比为1∶9时,合成的PANi/(MTM-CNFs)三元电极材料比电容量最高,达到596 F/g,相比PANi/CNFs二元材料提高了11.5倍。随着基底材料中MTM纳米片的进一步增加和堆叠,活性物质的减少导致材料比电容量的下降,但相比二元材料,仍有明显提高。另外,MTM纳米片的加入有助于稳定复合电极材料的库伦效率,在1 000次充放电循环过程中始终保持在100%左右。Abstract: Montmorillonite-cellulosenanofibers (MTM-CNFs) substrate materials were prepared by freeze drying. Then polyaniline (PANi) was synthesized from aniline monomers by in-situ polymerization and the ordered nanowire arrays were constructed without templates. Through the research on microstructure, synthesis mechanism, electrical conductivity and electrochemical properties of PANi/(MTM-CNFs) composite electrodes, we studied the principle of compounds prepared by one-dimensional (1D) linear material, two-dimensional (2D) nanosheets and conductive polymer. Furthermore, we also studied the preparation method of the energy-storing materials with ordered arrays. The results show that the incorporation of MTM nanosheets facilitate the in-situ growing of PANi nanorod on the substrates, Forming the ordered nanowire arrays and improving the capacitance of the composite electrodes efficiently. When the mass ratio of MTM and CNFs in the substrates is 1∶9, the PANi/(MTM-CNFs) compo-sites have the highest capacitance with the value of 596 F/g, which is 11.5 times compared to PANi/CNFs composites. With the increasement and stack of nanosheets, the capacitance of composites decreases owing to the reduced active substance. However, the value of capacitance of ternary electrodes is also significantly higher than that of binary electrodes.Furthermore, the corporation of MTM nanosheet is beneficial for the stability of columbic efficiency of the composites. During the charge and discharge cycles for 1 000 times, the value of columbic efficiency is always around 100%.
-
Key words:
- polyaniline /
- substrate material /
- montmorillonite nanosheet /
- nanowire arrays /
- nanocellulose
-
表 1 复合膜中各组分含量
Table 1. Content of different components in the composites
Sample Mass fraction/wt% CNFs MTM PANi PANi/CNFs 83.3 0 16.7 PANi/(MTM-CNFs)-1 86.4 4.5 9.1 PANi/(MTM-CNFs)-2 86.3 9.6 4.1 PANi/(MTM-CNFs)-3 71.9 24 4.1 PANi/(MTM-CNFs)-4 64.7 32.4 2.9 PANi/(MTM-CNFs)-5 49 49 2 -
[1] LIANG J, JIANG C, WU W. Toward fiber-, paper-, and foam-based flexible solid-state supercapacitors: Electrode materials and device designs[J]. Nanoscale,2019,11(15):1-59. [2] LIU S, LI H, HE C. Simultaneous enhancement of electrical conductivity and seebeck coefficient in organic thermoelectric SWNT/PEDOT: PSS nano-composites[J]. Carbon,2019,149:25-32. [3] 张政, 刘洪达, 宋朝霞, 等. 聚苯胺包覆CoFe类普鲁士蓝复合材料的超电容性能[J]. 复合材料学报, 2020, 37(3):731-738.ZHANG Z, LIU H D, SONG Z X, et al. Supercapacitive performance of polyaniline coated CoFe prussian blue analogue comosite[J]. Acta materiae compositae sinica,2020,37(3):731-738(in Chinese). [4] WANG Y, TRAN H D, KANER R B. Template-free growth of aligned bundles of conducting polymer nanowires[J]. The Journal of Physical Chemistry C,2009,113(24):10346-10349. [5] YAO Q, CHEN L, ZHANG W, et al. Enhanced thermoelectric performance of single-walled carbon nanotubes/polyaniline hybrid nanocomposites[J]. ACS Nano,2010,4(4):2445-2451. [6] MI H, ZHOU J, CUI Q, et al. Chemically patterned polyaniline arrays located on pyrolytic graphene for supercapacitors[J]. Carbon,2014,80:799-807. doi: 10.1016/j.carbon.2014.09.036 [7] HUI N, CHAI F, LIN P, et al. Electrodeposited conducting polyaniline nanowire arrays aligned on carbon nanotubes network for high performance supercapacitors and sensors[J]. Electrochimica Acta,2016,199:234-241. doi: 10.1016/j.electacta.2016.03.115 [8] XIE A, ZHOU X, ZHOU W, et al. Fabrication of Pt/porous PANI using attapulgite as template for electro-oxidation of glycerol[J]. Electrochimica Acta,2016,189:215-223. doi: 10.1016/j.electacta.2015.12.104 [9] XING J, TAO P, WU Z, et al. Nanocellulose-graphene composites: A promising nanomaterial for flexible supercapacitors[J]. Carbohydrate Polymers,2019,207:447-459. doi: 10.1016/j.carbpol.2018.12.010 [10] GUO R, ZHANG L, LU Y, et al. Research progress of nanocellulose for electrochemical energy storage: A review[J]. Journal of Energy Chemistry,2020,51:342-361. doi: 10.1016/j.jechem.2020.04.029 [11] 卿彦, 易佳楠, 吴义强, 等. 纳米纤维素储能研究进展[J]. 林业科学, 2018, 54(3):134-143.QING Y, YI J N, WU Y Q, et al. Advances in application of biamass nanocellulose to green-energy storage[J]. Scientia Silvae Sinicae,2018,54(3):134-143(in Chinese). [12] YUE L, XIE Y, ZHENG Y, et al. Sulfonated bacterial cellulose/polyaniline composite membrane for use as gel polymer electrolyte[J]. Composites Science and Technology,2017,145:122-131. doi: 10.1016/j.compscitech.2017.04.002 [13] HUANG Z, LI L, WANG Y, et al. Polyaniline-graphene nanocomposites towards high-performance supercapacitors: A review[J]. Composites Communications,2018,8:83-91. doi: 10.1016/j.coco.2017.11.005 [14] LIAO J, NI W, WANG C, et al. Layer-structured niobium oxides and their analogues for advanced hybrid capacitors[J]. Chemical Engineering Journal,2019,391:123489. doi: 10.1016/j.cej.2019.123489 [15] WU Q, CHEN M, WANG S, et al. Preparation of sandwich-like ternary hierarchical nanosheets manganese dioxide/polyaniline/reduced graphene oxide as electrode material for supercapacitor[J]. Chemical Engineering Journal,2016,304:29-38. doi: 10.1016/j.cej.2016.06.060 [16] AYDINLI A, YUKSEL R, UNALAN H E. Vertically aligned carbon nanotube-Polyaniline nanocomposite supercapacitor electrodes[J]. International Journal of Hydrogen Energy,2018,43(40):18617-18625. doi: 10.1016/j.ijhydene.2018.05.126 [17] BILLINGHAM N C, CALVERT P D. Electrically conducting polymers-A polymer science viewpoint[J]. Advances in Polymer Science,1989:1-104. [18] LI R, CHEN Z, LI J, et al. Effective synthesis to control the growth of polyaniline nanofibers by interfacial polymerization[J]. Synthetic Metals,2013,171:39-44. doi: 10.1016/j.synthmet.2013.02.020 [19] MUJAWAR S H, AMBADE S B, BATTUMUR T, et al. Electropolymerization of polyaniline on titanium oxide nanotubes for supercapacitor application[J]. Electrochimica Acta,2011,56(12):4462-4466. doi: 10.1016/j.electacta.2011.02.043 [20] HE Y, WANG X, HUANG H, et al. In-situ electropolymerization of porous conducting polyaniline fibrous network for solid-state supercapacitor[J]. Applied Surface Science,2019,469:446-455. [21] CHIOU N R, LU C, GUAN J, et al. Growth and alignment of polyaniline nanofibres with superhydrophobic, superhydrophilic and other properties[J]. Nature Nanotechnology,2007,2(6):354-357. doi: 10.1038/nnano.2007.147 [22] TANG L, YANG Z, DUAN F, et al. Fabrication of graphene sheets/polyaniline nanofibers composite for enhanced supercapacitor properties[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2017,520:184-192.