细乳液法制备MnO_2/PPy复合材料及其电化学性能
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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MnO_2/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MnO_2/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MnO_2/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MnO_2/PPy复合材料比表面积为177.1m~2/g,比容量在0.5A/g时达到231.9F/g。同时,也表明MnO_2与PPy的协同作用有效提高了MnO_2/PPy的比容量和循环稳定性。
The MnO_2/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 ptoluenesulfonic acid, concentration of potassium permanganate and reaction time on the specificcapacitance of MnO_2/PPy composite materials were studied. And the electrochemical performances wereinvestigated also. The results showed that the optimum conditions of synthesis MnO_2/PPy compositematerials 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 suitableoperating conditions, the specific surface area of MnO_2/PPy composite materials was 177.1m~2/g and the specific capacitance was 231.9F/g at 0.5A/g. The specific capacitance and cycle stability of MnO_2/PPy electrode were enhanced due to synergistic effect between MnO_2 and PPy.
The MnO_2/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 ptoluenesulfonic acid, concentration of potassium permanganate and reaction time on the specificcapacitance of MnO_2/PPy composite materials were studied. And the electrochemical performances wereinvestigated also. The results showed that the optimum conditions of synthesis MnO_2/PPy compositematerials 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 suitableoperating conditions, the specific surface area of MnO_2/PPy composite materials was 177.1m~2/g and the specific capacitance was 231.9F/g at 0.5A/g. The specific capacitance and cycle stability of MnO_2/PPy electrode were enhanced due to synergistic effect between MnO_2 and PPy.
引文
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[11] GONG T, YANG D, HU J G. Preparation of monodispersed hybridnanospheres with high magnetite content from uniform Fe3O4clusters[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 byin situ emulsion polymerization for high-performance supercapacitorelectrodes[J]. Journal of Solid State Electrochemistry, 2014, 18:2139-2147.
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[14] FAN H L, ZHOU S F, GAO J,et al.Continuous preparation of Fe3O4nanoparticles through impinging stream-rotating packed bed reactorand 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 Fe3O4nanoparticles using impinging stream-rotating packed bed reactor andmagnetic 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 ofnanoscale zero-valent iron and degradation of nitrobenzene inwastewater 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 packedbed 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-dispersednanometer 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 electrodematerial 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 ofpolypyrrole doped by p-tolyl sulfonic acid and its anticorrosionproperty for magnesium[J]. Acta Chemica Sinica, 2008, 66(5):571-575.
[22] WANG J G, KANG F Y, WEI B Q. Engineering of MnO2-basednanocomposites for high-performance supercapacitors[J]. Progress inMaterials Science, 2015, 74:51-124.
[23] YAO W, ZHOU H, LU Y. Synthesis and property of novelMnO2@polypyrrole coaxial nanotubes as electrode material forsupercapacitors[J]. Journal of Power Sources, 2013, 241:359-366.
[24] DONG Z H, WEI Y L, SHI W, et al. Characterisation of dopedpolypyrrole/manganese oxide nanocomposite for supercapacitorelectrodes[J]. Materials Chemistry and Physics, 2011, 131:529-534.
[25] TOUPIN M, BROUSSE T, BELANGER D. Charge storage mechanismof MnO2electrode used in aqueous electrochemical capacitor[J].Chemistry of Materials, 2004, 16:3184-3190.
[26] BAHLOUL A, NESSARK B, BRIOR E, et al. Polypyrrole-coveredMnO2as electrode material for supercapacitor[J]. Journal of PowerSources, 2013, 240:267-272.
[27] WU Q F, HE K X, MI H Y, et al. Electrochemical capacitance ofpolypyrrole nanowire prepared by using cetyltrimethylammoniumbromide(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 performanceof polyaniline@MnO2/graphene ternary composites for electrochemicalsupercapacitors[J]. Journal of Power Sources, 2016, 303:175-181.
[29] WANG J G, YANG Y, HUANG Z H, et al. MnO2/polypyrrolenanotubular composites:reactive templatesynthesis, characterizationand application as superior electrodematerials for high-performancesupercapacitors[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 electrochemicalcapacitor[J]. Applied Surface Science, 2010, 256(13):4339-4343.
[2] DING K Q, CHENG F M. Cyclic voltammetrically prepared MnO2-PPycomposite material and its electrocatalysis towards oxygen reductionreaction(ORR)[J]. Synthetic Metals, 2009, 159:2122-2127.
[3] JI J Y, ZHANG X Y, LIU J Y, et al. Assembly of polypyrrolenanotube@MnO2composites with an improved electrochemicalcapacitance[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 morphologyand supercapacitive properties of manganese oxide/polypyrrolenanocomposite[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 ofElectrochemical Science, 2015, 10:9456-9465.
[6] ASUA J M. Miniemulsion polymerization[J]. Progress in PolymerScience, 2002, 27(7):1283-1346.
[7] ASUA J M. Challenges for industrialization of miniemulsionpolymerization[J]. Progress in Polymer Science, 2014, 39(10):1797-1826.
[8] FRICKE M, VOIGT A, VEIT P, et al. Miniemulsion-based process forcontrolling 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 assistedminiemulsion 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-basednanoparticles through high-pressure homogenization andminiemulsion cross-linking:influence of various process parameterson particle size and stability[J]. Carbohydrate Polymers, 2011, 83:1604-1610.
[11] GONG T, YANG D, HU J G. Preparation of monodispersed hybridnanospheres with high magnetite content from uniform Fe3O4clusters[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 byin situ emulsion polymerization for high-performance supercapacitorelectrodes[J]. Journal of Solid State Electrochemistry, 2014, 18:2139-2147.
[13] FUKUI Y, FUJIMOTO K. Bio-inspired nanoreactor based on aminiemulsion system to create organic-inorganic hybrid nanoparticlesand 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 Fe3O4nanoparticles through impinging stream-rotating packed bed reactorand 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 Fe3O4nanoparticles using impinging stream-rotating packed bed reactor andmagnetic 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 ofnanoscale zero-valent iron and degradation of nitrobenzene inwastewater 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 packedbed 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-dispersednanometer 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 electrodematerial 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 ofpolypyrrole doped by p-tolyl sulfonic acid and its anticorrosionproperty for magnesium[J]. Acta Chemica Sinica, 2008, 66(5):571-575.
[22] WANG J G, KANG F Y, WEI B Q. Engineering of MnO2-basednanocomposites for high-performance supercapacitors[J]. Progress inMaterials Science, 2015, 74:51-124.
[23] YAO W, ZHOU H, LU Y. Synthesis and property of novelMnO2@polypyrrole coaxial nanotubes as electrode material forsupercapacitors[J]. Journal of Power Sources, 2013, 241:359-366.
[24] DONG Z H, WEI Y L, SHI W, et al. Characterisation of dopedpolypyrrole/manganese oxide nanocomposite for supercapacitorelectrodes[J]. Materials Chemistry and Physics, 2011, 131:529-534.
[25] TOUPIN M, BROUSSE T, BELANGER D. Charge storage mechanismof MnO2electrode used in aqueous electrochemical capacitor[J].Chemistry of Materials, 2004, 16:3184-3190.
[26] BAHLOUL A, NESSARK B, BRIOR E, et al. Polypyrrole-coveredMnO2as electrode material for supercapacitor[J]. Journal of PowerSources, 2013, 240:267-272.
[27] WU Q F, HE K X, MI H Y, et al. Electrochemical capacitance ofpolypyrrole nanowire prepared by using cetyltrimethylammoniumbromide(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 performanceof polyaniline@MnO2/graphene ternary composites for electrochemicalsupercapacitors[J]. Journal of Power Sources, 2016, 303:175-181.
[29] WANG J G, YANG Y, HUANG Z H, et al. MnO2/polypyrrolenanotubular composites:reactive templatesynthesis, characterizationand application as superior electrodematerials for high-performancesupercapacitors[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 electrochemicalcapacitor[J]. Applied Surface Science, 2010, 256(13):4339-4343.