聚苯胺/(蒙脱土-纳米纤维素)三元复合电极材料的制备及电化学性能

王宝霞; 李大纲; 汪钟凯

doi:10.13801/j.cnki.fhclxb.20200807.001

聚苯胺/(蒙脱土-纳米纤维素)三元复合电极材料的制备及电化学性能

doi: 10.13801/j.cnki.fhclxb.20200807.001

王宝霞^{1, 3, ,},
李大纲^2,,
汪钟凯^3,

1.
安徽农业大学　轻纺工程与艺术学院，合肥 230036
2.
南京林业大学　材料科学与工程学院，南京 210037
3.
安徽农业大学　生物质分子工程中心，合肥 230036

基金项目: 安徽省高校自然科学研究项目(KJ2019A0179)；安徽农业大学引进与稳定人才项目(wd2018-01)

详细信息

通讯作者:
王宝霞，博士，副教授，硕士生导师，研究方向为生物质基功能复合材料　E-mail：wangbaoxia@ahau.edu.cn

中图分类号: TB332；TM53
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出版历程
- 收稿日期: 2020-05-28
- 录用日期: 2020-07-29
- 网络出版日期: 2020-08-10
- 刊出日期: 2021-04-08

Preparation and electrochemical properties of polyaniline/(montmorillonite-cellulosenanofibers) composite electrodes

WANG Baoxia^{1, 3
, ,},
LI Dagang^2
,,
WANG Zhongkai^3
,

1.
College of Light Textile Engineering and Art, Anhui Agricultural University, Hefei 230036, China
2.
College of Material Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
3.
Biomass Molecular Engineering Center, Anhui Agricultural University, Hefei 230036, China

摘要

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。
- 聚苯胺 /
- 复合基底材料 /
- 蒙脱土纳米片 /
- 阵列结构 /
- 纳米纤维素
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%.
- polyaniline /
- substrate material /
- montmorillonite nanosheet /
- nanowire arrays /
- nanocellulose

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图 1 苯胺聚合过程中溶液颜色变化。

Figure 1. Color changes of solution during the polymerization of aniline

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图 2 纳米蒙脱土(MTM)的TEM图像 (a) 和纤维素纳米纤丝(CNFs)的SEM图像 (b)

Figure 2. TEN image of montmorillonite (MTM) nanosheet (a) and SEM image of cellulose nano fibers (CNFs) (b)

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图 3 纯聚苯胺(PANi)粉末 (a) 和PANi/CNFs (b)、PANi/(MTM-CNFs)-2 (c) 的SEM图像

Figure 3. SEM images of polyaniline (PANi) powder (a) ，PANi/CNFs (b) and PANi/(MTM-CNFs)-2 (c) film

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图 4 复合膜PANi/CNFs (a) 和PANi/(MTM-CNFs)-2 (b) 的SEM图像

Figure 4. SEM images of fracture surface of PANi/CNFs (a) and PANi/(MTM-CNFs)-2 (b)

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图 5 PANi在MTM-CNFs复合膜上的聚合机制

Figure 5. Schematic illustration of nucleation and growth mechanism of PANi on MTM-CNFs composite films

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图 6 不同MTM含量时复合膜的电导率

Figure 6. Conductivity of films with different MTM contents

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图 7 复合材料PANi/CNFs (a) 和PANi/(MTM-CNFs)-2 (b)在不同扫描速率时的循环伏安曲线

Figure 7. Cyclic voltammetry curves of PANi/CNFs (a) and PANi/(MTM-CNFs)-2 (b) at different scan rates

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图 8 PANi/CNFs-1和PANi/(MTM-CNFs)-2在不同扫描速率时的比电容量

Figure 8. Specific capacitance of PANi/CNFs and PANi/(MTM-CNFs)-2 versus CV curves at different scan rates

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图 9 复合材料PANi/CNFs (a) 和PANi/(MTM-CNFs)-2 (b)在0~0.8V电位窗口时的恒电流充放电曲线

Figure 9. Galvanostatic charge-discharge curves of PANi/CNFs (a) and PANi/(MTM-CNFs)-2 (b) at 0-0.8V potential window

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图 10 PANi/CNFs和PANi/(MTM-CNFs)-2在不同电流密度时的比电容量

Figure 10. Specific capacitance of PANi/CNFs and PANi/(MTM-CNFs)-2 versus charge-discharge current density

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图 11 1 mol/L H₂SO₄水溶液电解质中PANi/CNFs和PANi/(MTM-CNFs)-2的交流阻抗

Figure 11. Nyquist plots of PANi/CNFs and PANi/(MTM-CNFs)-2 in 1 mol/L H₂SO₄ aqueous electrolyte

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图 12 PANi/CNFs和PANi/(MTM-CNFs)-2经1 000次循环测试结果分析

Figure 12. Analysis result of charge-discharge cycle of PANi/CNFs and PANi/(MTM-CNFs)-2 at a current density of 1 A/g after 1 000 times

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图 13 不同MTM含量时PANi/(MTM-CNFs)复合材料的比电容量

Figure 13. Specific capacitance of PANi/(MTM-CNFs) nanocomposites of different MTM contents

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表 1 复合膜中各组分含量

Table 1. Content of different components in the composites

Sample	Mass fraction/wt%
Sample	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

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参考文献(22)

[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.