一种生物炭基柔性固态超级电容器的制备及性能研究

doi:10.11949/0438-1157.20190162

化工学报 ›› 2019, Vol. 70 ›› Issue (9): 3590-3600.DOI: 10.11949/0438-1157.20190162

• 材料化学工程与纳米技术 • 上一篇下一篇

一种生物炭基柔性固态超级电容器的制备及性能研究

禹兴海^1,²(),罗齐良¹,潘剑^2,³,韩玉琦^1,⁴,张奇峰¹

1. 河西学院柔性复合材料应用基础研究所, 甘肃张掖 734000
2. 复旦大学聚合物分子工程国家重点实验室, 上海 200438
3. 美国特拉华大学化学与生物分子工程系, 特拉华涅瓦克 19716
4. 甘肃省河西走廊特色资源利用省级重点实验室, 甘肃张掖 734000

收稿日期:2019-02-27 修回日期:2019-05-08 出版日期:2019-09-05 发布日期:2019-09-05
通讯作者: 禹兴海
作者简介:禹兴海（1977—），男，博士，教授，yuxinghai455@163.com
基金资助:
国家自然科学基金项目(21865008);甘肃省委组织部青年人才专项（陇原青年创业创新人才团队）(甘组通字2018-81);复旦大学聚合物分子工程国家重点实验室开放课题项目(K-2018-14);河西学院博士科研启动项目(HXBQ 2017-05)

Preparation and properties of flexible supercapacitor based on biochar and solid gel-electrolyte

Xinghai YU^1,²(),Qiliang LUO¹,Jian PAN^2,³,Yuqi HAN^1,⁴,Qifeng ZHANG¹

1. Institute of Flexible Composite Materials, Hexi University, Zhangye 734000, Gansu, China
2. The State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai 200438, China
3. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716, Delaware, USA
4. Key Laboratory of Hexi Corridor Resources and Utilization of Gansu, Hexi University, Zhangye 734000, Gansu, China

Received:2019-02-27 Revised:2019-05-08 Online:2019-09-05 Published:2019-09-05
Contact: Xinghai YU

摘要/Abstract

摘要：

利用固体农业废弃物玉米秸秆作为原料，经高温煅烧，KOH刻蚀获得具有较大比表面积的多孔生物炭材料，并采用粉末X射线衍射仪(XRD)、场发射扫描电镜(FE-SEM)、红外光谱(FT-IR)、拉曼光谱(Raman)以及比表面积和孔径分析仪(BET)等表征手段，研究其物理、化学结构和微观形貌。结果表明，所制备的生物炭材料具有发达的“微孔-中孔-大孔”三维贯通多级孔道结构，比表面积高达1228 m2·g^-1。将其作为电极材料，与H₂SO₄/PVA凝胶电解质可组装成为具有柔性的全固态超级电容器。利用循环伏安测试(CV)、恒电流充放电(GCD)以及交流阻抗测试(EIS)对柔性超级电容器电化学性能进行了测试。在电流密度为1.0 A·g^-1的条件下，其比容量可达125 F·g^-1。该器件具有良好的机械柔性和电化学稳定性，将其从0°弯曲至180°的过程中，比电容保持率约为93.5%；以不同弯曲角度将其连续弯折100次后，仍能保持较高的比电容。此外，在弯折角度180°、充放电电流密度为5.0 A·g^-1 的条件下经过500次循环充放电后，比电容值保持率约为95.6%，库仑效率约为94.9%。说明所制备的柔性超级电容器具有优异的充放电性能和长效循环稳定性。作为一种柔性、质轻、便携的储能装置，在可穿戴电子器件领域内具有潜在应用价值。同时该方法也为固体农业废弃物玉米秸秆的高附加值转化利用和新型绿色能源器件创新研制提供了新的技术途径。

关键词: 玉米秸秆, 生物炭, 固态凝胶电解质, 柔性, 超级电容器

Abstract:

In our present work, a typical biomass, maize straw was used as precursor to prepare porous biochar under high temperature followed with etching by KOH solution. The prepared biochar was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy (Raman). The specific surface area of as-prepared biochar was calculated by the Brunauer-Emmett-Teller (BET) method. Under the optimal conditions, the specific surface area can reach 1228 m2·g^-1. Then the as-prepared biochar was employed as electrode materials to fabricate the flexible supercapacitor cooperating with the H₂SO₄/PVA gel as electrolyte. The electrochemical capacitance properties of the obtained supercapacitors were tested by cyclic voltammetry (CV) constant current charge-discharge (CD) and AC impedance spectroscopy (EIS) measurements in a two-electrode system. The results showed that the specific capacity reaches 125 F·g^-1 when the current density is 1.0 A·g^-1. Noteworthily, the fabricated supercapacitor demonstrates the perfectly flexibility and stability that the capacitance retention kept at 93.5% under different bending angles (from 0° to 180°) at a constant current density of 1.0 A·g^-1. Furthermore, the flexible supercapacitor also exhibits a satisfied long-term stability performance of 95.6% capacitance retention and 94.9% coulombic efficiency under 180° bending angle through 500 cycles. These very attractive mechanical properties and electrochemical performances enable this flexible supercapacitor to present a great potential for wearable devices as energy storage equipment and open up new avenues to high-value materials from waste maize straw.

Key words: maize straw, biochar, solid gel electrolyte, flexibility, supercapacitor

中图分类号:

TQ 031.2

禹兴海, 罗齐良, 潘剑, 韩玉琦, 张奇峰. 一种生物炭基柔性固态超级电容器的制备及性能研究[J]. 化工学报, 2019, 70(9): 3590-3600.

Xinghai YU, Qiliang LUO, Jian PAN, Yuqi HAN, Qifeng ZHANG. Preparation and properties of flexible supercapacitor based on biochar and solid gel-electrolyte[J]. CIESC Journal, 2019, 70(9): 3590-3600.

图/表 9

图1 玉米秸秆[(a),(b)]和生物炭[(c)～(f)]的扫描电镜图片

Fig.1 SEM images of maize straw power [(a),(b)] and biochar (BC) activated by KOH [(c)—(f)]

图2 生物炭的氮气吸附-脱附等温线(a)和孔径分布曲线(b)

Fig.2 Nitrogen adsorption-desorption isotherms and pore size distribution curves of biochar

表1 不同活化条件下制备的生物炭表面积及孔结构比较

Table 1 Specific surface area and porosity parameters of biochar at different activated conditions.

Sample

(m _C∶m _KOH)

BET surface, S _BET/(m2·g^-1)

Total volume in pores,

V _Total/(cm3·g^-1)

DFT pore

size/nm

图3 生物炭的XRD谱图(a)、红外光谱图(b)和拉曼光谱图(c)

Fig.3 XRD pattern (a), FT-IR spectra (b) and Raman spectra (c) of biochar

图4 柔性超级电容器在不同扫描速率下的循环伏安曲线(a)和不同电流密度下的恒电流充放电曲线(b)

Fig.4 Cyclic voltammetry curves of assembled flexible capacitor at various sweep rates and charge/discharge curves at various current

图5 柔性超级电容器的交流阻抗谱(a)和不同电流密度下的比电容(b)

Fig.5 Electrochemical impedance spectra (a) and specific capacitance at different current density (b)

图6 柔性超级电容器在不同弯曲角度下的循环伏安曲线(a)和比电容保持率(b)

Fig.6 Cyclic voltammetry curves of flexible capacitor for different curvatures and capacitance retention at different bending angles

图7 反复机械弯曲100次后柔性超级电容器在充放电电流密度为5.0 A·g-1条件下的比容量

Fig.7 Specific capacitance of flexible capacitor under 100 bending cycles at 5.0 A·g-1 current density

图8 柔性超级电容器的循环稳定性测试(电流密度5.0 A·g-1，弯曲角度180°；插图为最后20次的充放电曲线)

Fig.8 Long-term cycling performance of flexible capacitor at current density of 5.0 A·g-1 under 180° bending angle (Inset is charge-discharge curves of the last 20 cycles)

参考文献 46

1	Zhang Q F , Uchaker E , Candelaria S L , et al . Nanomaterials for energy conversion and storage[J]. Chem. Soc. Rev., 2013, 42(7): 3127-3171.
2	刘明贤, 缪灵, 陆文静, 等 . 多孔碳材料的设计合成及其在能源存储与转换领域中的应用[J]. 科学通报, 2017, 62(6): 590-605.
	Liu M X , Miao L , Lu W J , et al . Porous carbon materials: design, synthesis and applications in energy storage and conversion devices[J]. Chin. Sci. Bull., 2017, 62(6): 590-605.
3	Chen X L , Qiu L B , Peng H S , et al . Novel electric double-layer capacitor with a coaxial fiber structure[J]. Adv. Mater., 2013, 25(44): 6436-6441.
4	Beidaghi M , Gogotsi Y . Capacitive energy storage in micro-scale devices: recent advances in design and fabrication of micro-supercapacitors[J]. Energy & Environ. Sci., 2014, 7(3): 867-884.
5	Bae J , Song M K , Park Y J , et al . Fiber supercapacitors made of nanowire-fiber hybrid structures for wearable/flexible energy storage[J]. Angew. Chem. Int. Ed., 2011, 50(7): 1683-1687.
6	Yan J , Qian W , Tong W , et al . Recent advances in design and fabrication of electrochemical supercapacitors with high energy densities[J]. Adv. Energy. Mater., 2014, 4(4): 1300816.
7	Cheng Y W , Zhang H B , Lu S T , et al . Flexible asymmetric supercapacitors with high energy and high power density in aqueous electrolytes[J]. Nanoscale, 2013, 5(3): 1067-1073.
8	Kötz R , Carlen M . Principles and applications of electrochemical capacitors[J]. Electrochimica Acta, 2000, 45: 2483-2498.
9	Wang Y G , Song Y F , Xia Y Y . Electrochemical capacitors: mechanism, materials, systems, characterization and applications[J]. Chem. Soc. Rev., 2016, 45(21): 5925-5950.
10	Conway B E , Pell W G . Double-layer and pseudocapacitance types of electrochemical capacitors and their applications to the development of hybrid devices[J]. J.Solid.State.Electr., 2003, 7(9): 637-644.
11	Sharma P , Bhatti T S . A review on electrochemical double-layer capacitors[J]. Energy. Convers. Manage, 2010, 51(12): 2901-2912.
12	Lu Q , Chen J G , Xiao J Q . Nanostructured electrodes for high-performance pseudocapacitors[J]. Angew. Chem. Int. Ed., 2013, 52(7): 1882-1889.
13	Liu Q , Nayfeh M H , Yau S T . Brushed-on flexible supercapacitor sheets using a nanocomposite of polyaniline and carbon nanotubes[J]. J.Power. Sources, 2010, 195(21): 7480-7483.
14	Lv T , Yao Y , Li N , et al ．Wearable fiber-shaped energy conversion and storage devices based on aligned carbon nanotubes[J]. Nano Today, 2016, 11(5): 644-660.
15	Meng C Z , Liu C H , Chen L Z , et al . Highly flexible and all-solid-state paper-like polymer supercapacitors[J]. Nano Lett., 2010, 10(40): 25-4031.
16	李宁, 陈涛 . 石墨烯基电极材料在柔性全固态超级电容器中的研究进展[J]. 应用化学, 2018, 35(3): 259-271.
	Li N , Chen T . Recent progress on graphene-based flexible all-solid-state supercapacitors[J]. J. Chin. Appl. Chem., 2018, 35 (3): 259-271.
17	彭旭, 李典奇, 谢毅, 等 . 二维石墨烯和准二维类石墨烯在全固态柔性超级电容器中的应用[J]. 科学通报, 2013, 58(Z2): 2886-2894.
	Peng X , Li D Q , Xie Y , et al . Two-dimensional graphene/quasi-two-dimensional graphene analogues for flexible supercapacitor in all-solid-state[J]. Chin. Sci. Bull., 2013, 58(Z2): 2886-2894.
18	朱红艳, 赵建国, 庞明俊, 等 . 石墨烯/δ-MnO₂复合材料的制备及其超级电容器性能[J]. 化工学报, 2017, 68(12): 4824-4832.
	Zhu H Y , Zhao J G , Pang M J , et al . Preparation of graphene/δ-MnO₂ composites and supercapacitor performance[J]. CIESC Journal, 2017, 68(12): 4824-4832.
19	Cui Y , Chai J , Du H , et al . Facile and reliable in situ polymerization of poly(ethyl cyanoacrylate)-based polymer electrolytes toward flexible lithium batteries[J]. ACS Appl. Mater. Interfaces, 2017, 9(10): 8737-8741.
20	Cheng X , Jian P , Yang Z , et al . Gel polymer electrolytes for electrochemical energy storage[J]. Adv. Energy Mater., 2018, 8(7): 1702184.
21	Arya A , Sharma A L . Polymer electrolytes for lithium ion batteries: a critical study[J]. Ionics, 2017, 23(3): 497-540.
22	Dagousset L , Pognon G , Nguyen G T M , et al . Self-standing gel polymer electrolyte for improving supercapacitor thermal and electrochemical stability[J]. J. Power. Sources, 2018, 391(1): 86-93.
23	Wang Y , Xia Y . Recent progress in supercapacitors: from materials design to system construction[J]. Adv. Mater., 2013, 25(37): 5336-5342.
24	Hsu Y K , Chen Y C , Lin Y G , et al . High-cell-voltage supercapacitor of carbon nanotube/carbon cloth operating in neutral aqueous solution[J]. J. Mate. Chem., 2012, 22(8): 3383-3390.
25	Cui X , Lv R , Sagar R U R , et al . Reduced graphene oxide/carbon nanotube hybrid film as high performance negative electrode for supercapacitor[J]. Electrochimica Acta, 2015, 169: 342-350.
26	胡立鹃, 吴峰, 彭善枝, 等 . 生物质活性炭的制备及应用进展[J]. 化学通报, 2016, 79(3): 205-212.
	Hu L J , Wu F , Peng S Z , et al . Recent progress in preparation and utilization of biomass-based activated carbons[J]. Chem. Bull., 2016, 79(3): 205-212.
27	Goldfarb J L , Dou G , Salari M , et al . Biomass-based fuels and activated carbon electrode materials: an integrated approach to green energy systems[J]. ACS Sustain. Chem. Eng., 2017, 5(4): 3046-3054.
28	Gu X , Wang Y , Chao L , et al . Microporous bamboo biochar for lithium-sulfur batteries[J]. Nano Res., 2015, 8(1): 129-139.
29	Liu Y , Shi Z , Gao Y , et al . Biomass-swelling assisted synthesis of hierarchical porous carbon fibers for supercapacitor electrodes[J]. ACS Appl. Mater. Interfaces, 2016, 8(42): 28283-28290.
30	Hou J H , Cao C B , Ma J H , et al . Hierarchical porous nitrogen-doped carbon nanosheets derived from silk for ultrahigh-capacity battery anodes and supercapacitors[J]. ACS Nano, 2015, 9(3): 2556-2564.
31	Yu P F , Liang Y R , Liu Y L , et al . Rational synthesis of highly porous carbon from waste bagasse for advanced supercapacitor application[J]. ACS Sustain. Chem. Eng., 2018, 6(11): 15325-15332.
32	Fu P , Hu S , Sun L S , et al . Structural evolution of maize stalk particles during pyrolysis[J]. Bioresource Technol., 2009, 100(5): 4877-4883.
33	Jia M , Fang W , Xin J , et al . Metal ion-oxytetracycline interactions on maize straw biochar pyrolyzed at different temperatures[J]. Chem. Eng. J., 2016, 304(15): 934-940.
34	Yang G , Yun S Z , Min Q , et al . Chemical activation of carbon nano-onions for high-rate supercapacitor electrodes[J]. Carbon, 2013, 51: 52-58.
35	Wang J , Kaskel S . KOH activation of carbon-based materials for energy storage[J]. J. Mate. Chem., 2012, 22(45): 23710-23725.
36	Zhu H , Jia Z , Chen Y , et al . Tin anode for sodium-ion batteries using natural wood fiber as a mechanical buffer and electrolyte reservoir[J]. Nano Lett., 2013, 13(7): 3093-3100.
37	Liang Q H , Ye L , Huang Z H , et al . A honeycomb-like porous carbon derived from pomelo peel for use in high-performance supercapacitors[J]. Nanoscale, 2014, 6(22): 13831-13837.
38	Gong Y , Li D , Luo C , et al . Highly porous graphitic biomass carbon as advanced electrode materials for supercapacitors[J]. Green Chem., 2017, 17(19): 4132-4140.
39	Hao C , Liu D , Shen Z , et al . Functional biomass carbons with hierarchical porous structure for supercapacitor electrode materials[J]. Electrochimica Acta, 2015, 180: 241-251.
40	Qu J Y , Geng C , Lv S Y , et al . Nitrogen, oxygen and phosphorus decorated porous carbons derived from shrimp shells for supercapacitors[J]. Electrochimica Acta, 2015, 176: 982-988.
41	Gao S Y , Chen Y L , Fan H , et al . Large scale production of biomass-derived N-doped porous carbon spheres for oxygen reduction and supercapacitors[J]. J. Mater. Chem. A, 2014, 2(10): 3317-3324.
42	Xu H H , Hu X L , Sun Y M , et al . Flexible fiber-shaped supercapacitors based on hierarchically nanostructured composite electrodes[J]. Nano Research, 2015, 8(4): 1148-1158.
43	Chen S , Zhu J W , Wu X , et al . Graphene oxide-MnO₂nanocomposites for supercapacitors[J]. ACS Nano, 2010, 4(5): 6212-6218.
44	Tiruye G A , Muñoz-Torrero D , Thomas B , et al . Functional porous carbon nanospheres from sustainable precursors for high performance supercapacitors[J]. J.Mater. Chem. A, 2017, 5(31): 16263-16272.
45	Ma H Y , Li C , Zhang M , et al . Graphene oxide induced hydrothermal carbonization of egg proteins for high-performance supercapacitors[J]. J.
	Mate . Chem. A , 2017, 5(32): 17040-17047.
46	Wu C H , Deng S X , Wang H , et al . Preparation of novel three-dimensional NiO/ultrathin derived graphene hybrid for supercapacitor applications[J]. ACS Appl. Mate. Interfaces, 2014, 6(2): 1106-1112.

[1]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[2]	李靖, 沈聪浩, 郭大亮, 李静, 沙力争, 童欣. 木质素基碳纤维复合材料在储能元件中的应用研究进展[J]. 化工学报, 2023, 74(6): 2322-2334.
[3]	杨琴, 秦传鉴, 李明梓, 杨文晶, 赵卫杰, 刘虎. 用于柔性传感的双形状记忆MXene基水凝胶的制备及性能研究[J]. 化工学报, 2023, 74(6): 2699-2707.
[4]	吴学红, 栾林林, 陈亚南, 赵敏, 吕财, 刘勇. 可降解柔性相变薄膜的制备及其热性能[J]. 化工学报, 2023, 74(4): 1818-1826.
[5]	徐东, 田杜, 陈龙, 张禹, 尤庆亮, 胡成龙, 陈韶云, 陈建. 聚苯胺/二氧化锰/聚吡咯复合纳米球的制备及其电化学储能性[J]. 化工学报, 2023, 74(3): 1379-1389.
[6]	姜家豪, 黄笑乐, 任纪云, 朱正荣, 邓磊, 车得福. 生物炭吸附溶液中Pb²⁺的定性及定量研究[J]. 化工学报, 2023, 74(2): 830-842.
[7]	陈健鑫, 朱瑞杰, 盛楠, 朱春宇, 饶中浩. 纤维素基生物质多孔炭的制备及其超级电容器性能研究[J]. 化工学报, 2022, 73(9): 4194-4206.
[8]	顾仁杰, 张加威, 靳雪阳, 文利雄. 微撞击流反应器制备镍钴复合氢氧化物超级电容器材料及其性能研究[J]. 化工学报, 2022, 73(8): 3749-3757.
[9]	刘学安, 汤丽怡, 覃健, 唐大江, 童张法, 曲慧颖. 热解Ni/Co-ZIF-8制备碳纳米管桥连多孔碳及其在超级电容器中的应用[J]. 化工学报, 2022, 73(7): 3287-3297.
[10]	赵希强, 张健, 孙爽, 王文龙, 毛岩鹏, 孙静, 刘景龙, 宋占龙. 生物质炭改性微球去除化工废水中无机磷的性能研究[J]. 化工学报, 2022, 73(5): 2158-2173.
[11]	陈冠益, 童图军, 李瑞, 王燕杉, 颜蓓蓓, 李宁, 侯立安. 热解时间对污泥生物炭活化过硫酸盐的影响研究[J]. 化工学报, 2022, 73(5): 2111-2119.
[12]	黄其, 章晓敏, 宓霄凌, 周楷, 钟英杰. 三角槽道低 Reynolds 数脉动流与柔性壁耦合特性研究[J]. 化工学报, 2022, 73(5): 1964-1973.
[13]	王学良, 刘美红, 熊忠汾, 李鑫. 考虑表面粗糙度的柔性箔柱面气膜密封紊流特性分析[J]. 化工学报, 2022, 73(4): 1683-1694.
[14]	周云龙, 林东尧, 叶校源, 孙博. 常见离子对玉米秸秆为牺牲剂的光催化制氢影响[J]. 化工学报, 2022, 73(2): 722-729.
[15]	秦坤, 李佳乐, 王章鸿, 张会岩. 富Ca香菇菌渣基生物炭对含磷废水处理性能的研究[J]. 化工学报, 2022, 73(11): 5263-5274.

一种生物炭基柔性固态超级电容器的制备及性能研究

Preparation and properties of flexible supercapacitor based on biochar and solid gel-electrolyte

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 46

相关文章 15

编辑推荐

Metrics

本文评价