Synthesis of MnO2/PPy composite materials by miniemulsion polymerization and its electrochemical performances

doi:10.16085/j.issn.1000-6613.2018-0832

Chemical Industry and Engineering Progress ›› 2019, Vol. 38 ›› Issue (02): 979-986.DOI: 10.16085/j.issn.1000-6613.2018-0832

• Materials science and technology • Previous Articles Next Articles

Synthesis of MnO₂/PPy composite materials by miniemulsion polymerization and its electrochemical performances

Fangnan LIANG(),Zhiwei LIU,Ning ZHANG,Youzhi LIU()

1. Shanxi Province Key Laboratory of Higee-Oriented Chemical Engineering, North University of China, Taiyuan 030051, Shanxi, China

Received:2018-04-23 Revised:2018-11-07 Online:2019-02-05 Published:2019-02-05
Contact: Youzhi LIU

细乳液法制备MnO₂/PPy复合材料及其电化学性能

梁芳楠(),刘志伟,张宁,刘有智()

1. 中北大学超重力化工过程山西省重点实验室，山西太原 030051

通讯作者: 刘有智
作者简介:<named-content content-type="corresp-name">梁芳楠</named-content>（1990—），女，博士研究生，研究方向为化工过程强化。E-mail：<email>lfnzch@126.com</email>。|刘有智，教授，博士生导师，研究方向为超重力化工过程与技术。E-mail：<email>lyzzhongxin@126.com</email>。
基金资助:
山西省研究生教育创新项目(2017BY113);国家自然科学基金(21706245)

Abstract

Abstract:

The MnO₂/PPy composite materials were prepared by miniemulsion method (W/O) with Py and KMnO₄ as raw materials, which obtained spherical floral structure. The impinging stream-rotating packed bed (IS-RPB) was selected as an emulsion equipment to prepare miniemulsion. The concentration of p-toluenesulfonic acid, concentration of potassium permanganate and reaction time on the specific capacitance of MnO₂/PPy composite materials were studied. And the electrochemical performances were investigated also. The results showed that the optimum conditions of synthesis MnO₂/PPy composite materials by miniemulsion polymerization were concentration of p-toluenesulfonic acid of 0.84mol/L, concentration of potassium permanganate of 0.094mol/L and reaction time of 3.5h. Under the suitable operating conditions, the specific surface area of MnO₂/PPy composite materials was 177.1m²/g and the specific capacitance was 231.9F/g at 0.5A/g. The specific capacitance and cycle stability of MnO₂/PPy electrode were enhanced due to synergistic effect between MnO₂ and PPy.

Key words: miniemulsion, manganese bioxide/polypyrrole, impinging stream-rotating packed bed, electrochemical performances, specific capacitance

摘要：

以吡咯(Py)、高锰酸钾(KMnO₄)等为原料，撞击流-旋转填料床(IS-RPB)为乳化设备，通过细乳液法(W/O)制备了类球形花状结构的MnO₂/PPy复合材料。研究了对甲苯磺酸浓度、高锰酸钾浓度和反应时间对MnO₂/PPy复合材料比容量的影响，并对其电化学性能进行了考察。研究结果表明，细乳液法制备MnO₂/PPy复合材料适宜条件为对甲苯磺酸浓度0.84mol/L、高锰酸钾浓度0.094mol/L及反应时间3.5h。该条件下制备的MnO₂/PPy复合材料比表面积为177.1m²/g，比容量在0.5A/g时达到231.9F/g。同时，也表明MnO₂与PPy的协同作用有效提高了MnO₂/PPy的比容量和循环稳定性。

关键词: 细乳液, 二氧化锰/聚吡咯, 撞击流-旋转填料床, 电化学性能, 比容量

CLC Number:

TQ050.4

Fangnan LIANG, Zhiwei LIU, Ning ZHANG, Youzhi LIU. Synthesis of MnO₂/PPy composite materials by miniemulsion polymerization and its electrochemical performances[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 979-986.

梁芳楠, 刘志伟, 张宁, 刘有智. 细乳液法制备MnO₂/PPy复合材料及其电化学性能[J]. 化工进展, 2019, 38(02): 979-986.

Figures/Tables 10

References 30

1	SHARMA R K , RASTOGI A C , DESU S B . Manganese oxide embedded polypyrrole nanocomposites for electrochemical supercapacitor[J]. Electrochimica Acta, 2008, 53(26): 7690-7695.
2	DING K Q , CHENG F M . Cyclic voltammetrically prepared MnO₂-PPy composite material and its electrocatalysis towards oxygen reduction reaction (ORR)[J]. Synthetic Metals, 2009, 159: 2122-2127.
3	JI J Y , ZHANG X Y , LIU J Y , et al . Assembly of polypyrrole nanotube@MnO₂ composites with an improved electrochemical capacitance[J]. Materials Science and Engineering B, 2015, 198: 51-56.
4	GAN J K , LIM Y S, HUANG N M , et al . Effect of pH on morphology and supercapacitive properties of manganese oxide/polypyrrole nanocomposite[J]. Applied Surface Science, 2015, 357: 479-486.
5	YUAN L Y , WAN C Y , ZHAO L L . Facial in-situ synthesis of mno₂/PPy composite for supercapacitor[J]. International Journal of Electrochemical Science, 2015, 10: 9456-9465.
6	ASUA J M . Miniemulsion polymerization[J]. Progress in Polymer Science, 2002, 27(7): 1283-1346.
7	ASUA J M . Challenges for industrialization of miniemulsion polymerization[J]. Progress in Polymer Science, 2014, 39(10): 1797-1826.
8	FRICKE M , VOIGT A , VEIT P , et al . Miniemulsion-based process for controlling the size and shape of zinc oxide nanoparticles[J]. Industrial & Engineering Chemistry Research, 2015, 54(42): 10293-10300.
9	BARKADE S S , PINJARI D V , SINGH A K , et al . Ultrasound assisted miniemulsion polymerization for preparation of polypyrrole-zinc oxide (PPy/ZnO) functional latex for liquefied petroleum gas sensing[J]. Industrial & Engineering Chemistry Research, 2013, 52: 7704-7712.
10	SHI A M , LI D , WANG L J , et al . Preparation of starch-based nanoparticles through high-pressure homogenization and miniemulsion cross-linking: influence of various process parameters on particle size and stability[J]. Carbohydrate Polymers, 2011, 83: 1604-1610.
11	GONG T , YANG D , HU J G . Preparation of monodispersed hybrid nanospheres with high magnetite content from uniform Fe₃O₄ clusters[J]. Colloids and Surfaces A: Physicoche. Eng. Aspects, 2009, 339: 232-239.
12	ZHANG Y Q , LI M , YANG L L , et al . Facilely prepared polypyrrole-graphene oxide-sodium dodecylbenzene sulfonate nanocomposites by in situ emulsion polymerization for high-performance supercapacitor electrodes[J]. Journal of Solid State Electrochemistry, 2014, 18: 2139-2147.
13	FUKUI Y , FUJIMOTO K . Bio-inspired nanoreactor based on a miniemulsion system to create organic-inorganic hybrid nanoparticles and nanofilms[J]. Journal of Materials Chemistry and Physics, 2012, 22: 3493-3499.
14	FAN H L , ZHOU S F , GAO J ，et al ．Continuous preparation of Fe₃O₄ nanoparticles through impinging stream-rotating packed bed reactor and their electrochemistry detection toward heavy metal ions[J]. Journal of Alloys and Compounds, 2016, 671: 354-359．
15	FAN H L , ZHOU S F , QI G S , et al . Continuous preparation of Fe₃O₄ nanoparticles using impinging stream-rotating packed bed reactor and magnetic property thereof[J]. Journal of Alloys and Compounds, 2016, 662: 497-504.
16	JIAO W Z , QIN Y J , LUO S , et al ．Simultaneous formation of nanoscale zero-valent iron and degradation of nitrobenzene in wastewater in an impinging stream-rotating packed bed reactor[J]. Chemical Engineering Journal, 2017, 321: 564-571.
17	JIAO W Z , LIU Y Z , QI G S . A new impinging stream-rotating packed bed reactor for improvement of micromixing iodide and iodate[J].Chemical Engineering Journal, 2010, 157(1): 168-173．
18	LIU Y Z , JIAO W Z , QI G S . Preparation and properties of methanol-diesel oil emulsified fuel under high-gravity environment[J]. Renewable Energy, 2011, 36: 1463-1468.
19	张莉, 张文莉, 倪良 . 乳液法制备单分散纳米二氧化锰[J]. 化工新型材料, 2006, 34(6): 33-35.
	ZHANG L , ZHANG W L , NI L . Preparation of mono-dispersed nanometer manganese dioxide by using W/O emulsion as template[J]. NEW Chemical Materials, 2006, 34(6): 33-35.
20	林幼贞 . 掺杂聚吡咯及复合材料用作超级电容器电极材料的研究[D]. 厦门: 华侨大学, 2012.
	LIN Y Z . Study on the doped PPy and composite materials as electrode
	material of supercapacitor[D]. Xiamen: Huaqiao University, 2012.
21	李倩倩, 黄健涵, 刘素琴, 等 . 对甲苯磺酸掺杂聚吡咯的合成、表征及其对金属镁的防腐蚀性能研究[J]. 化学学报, 2008, 66(5): 571-575.
	LI Q Q , HUANG J H , LIU S Q , et al . Synthesis and characterization of polypyrrole doped by p-tolyl sulfonic acid and its anticorrosion property for magnesium[J]. Acta Chemica Sinica, 2008, 66(5): 571-575.
22	WANG J G , KANG F Y , WEI B Q . Engineering of MnO₂-based nanocomposites for high-performance supercapacitors[J]. Progress in Materials Science, 2015, 74: 51-124.
23	YAO W , ZHOU H , LU Y . Synthesis and property of novel MnO₂@polypyrrole coaxial nanotubes as electrode material for supercapacitors[J]. Journal of Power Sources, 2013, 241: 359-366.
24	DONG Z H , WEI Y L , SHI W , et al . Characterisation of doped polypyrrole/manganese oxide nanocomposite for supercapacitor electrodes[J]. Materials Chemistry and Physics, 2011, 131: 529-534.
25	TOUPIN M , BROUSSE T , BELANGER D . Charge storage mechanism of MnO₂ electrode used in aqueous electrochemical capacitor[J]. Chemistry of Materials, 2004, 16: 3184-3190.
26	BAHLOUL A , NESSARK B , BRIOR E , et al . Polypyrrole-covered MnO₂ as electrode material for supercapacitor[J]. Journal of Power Sources, 2013, 240: 267-272.
27	WU Q F , HE K X , MI H Y , et al . Electrochemical capacitance of polypyrrole nanowire prepared by using cetyltrimethylammonium bromide (CTAB) as soft template[J]. Materials Chemistry and Physics, 2007, 101(2/3): 367-371.
28	PAN C , GU H T , DONG L . Synthesis and electrochemical performance of polyaniline@MnO₂/graphene ternary composites for electrochemical supercapacitors[J]. Journal of Power Sources, 2016, 303: 175-181.
29	WANG J G , YANG Y , HUANG Z H , et al . MnO₂/polypyrrole nanotubular composites: reactive templatesynthesis, characterization and application as superior electrodematerials for high-performance supercapacitors[J]. Electrochimica Acta, 2014, 130: 642-649.
30	LI J , CUI L , ZHANG X G . Preparation and electrochemistry of one-dimensional nanostructured MnO₂/PPy composite for electrochemical capacitor[J]. Applied Surface Science, 2010, 256(13): 4339-4343.

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