Mg(OH)_2模板策略合成高性能超级电容器用煤沥青基多孔炭（英文）
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摘要
采用Mg(OH)_2模板策略结合原位KOH活化法合成出超级电容器用煤沥青基多孔炭(PCs)。运用透射电子显微镜、拉曼光谱仪、X射线光电子能谱仪和N_2吸脱附技术对PCs进行表征。利用恒流充放电、电化学阻抗谱和循环伏安法对PCs的电化学性能进行研究。结果表明,PC具有大的比表面积(3 145 m~2 g~(-1))和大量的短孔。当作为超级电容器的电极材料时,在6 mol L~(-1) KOH电解液中,在0.05 A g~(-1)电流密度下,显示出272 F g~(-1)的高比电容;在20 A g~(-1)电流密度下,比电容为217 F g~(-1),呈现好的倍率性能;经10 000次充放电循环后,其比电容保持率为96.69%,展现出优异的循环稳定性。本工作为高性能超级电容器用沥青基多孔炭的制备提供了一种简单的方法。
Porous carbons(PCs) for supercapacitors were synthesized by a combined Mg(OH)_2 templating and in-situ KOH activation method using coal tar pitch as the carbon precursor, and were characterized by TEM, Raman spectroscopy, XPS and N_2 adsorption. Their electrochemical properties were investigated by galvanostatic charge-discharge, electrochemical impedance spectroscopy and cyclic voltammetry. Results show that the specific surface area of the PCs increases with the KOH dosage and exhibits a maximum with an activation temperature at 800 ℃. The optimum PC has a high surface area up to 3145 m~2 g~(-1) with abundant micropores, and exhibits a high specific capacitance of 272 F g~(-1) at 0.05 A g~(-1), a rate capability of 217 F g~(-1) at 20 A g~(-1) and a good cycle stability with a 96.69% capacitance retention after 10000 cycles in a 6 M KOH electrolyte. This work provides a simple method for the large-scale production of PCs from pitch-based carbon sources for high-performance supercapacitors.
Porous carbons(PCs) for supercapacitors were synthesized by a combined Mg(OH)_2 templating and in-situ KOH activation method using coal tar pitch as the carbon precursor, and were characterized by TEM, Raman spectroscopy, XPS and N_2 adsorption. Their electrochemical properties were investigated by galvanostatic charge-discharge, electrochemical impedance spectroscopy and cyclic voltammetry. Results show that the specific surface area of the PCs increases with the KOH dosage and exhibits a maximum with an activation temperature at 800 ℃. The optimum PC has a high surface area up to 3145 m~2 g~(-1) with abundant micropores, and exhibits a high specific capacitance of 272 F g~(-1) at 0.05 A g~(-1), a rate capability of 217 F g~(-1) at 20 A g~(-1) and a good cycle stability with a 96.69% capacitance retention after 10000 cycles in a 6 M KOH electrolyte. This work provides a simple method for the large-scale production of PCs from pitch-based carbon sources for high-performance supercapacitors.
引文
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[38] Zhang W L,Xu C,Ma C Q,et al.Nitrogen-superdoped 3D graphene networks for high-performance supercapacitors [J].Adv Mater,2017,29:1701677.
[39] Wang L Q,Wang J Z,Jia F,et al.Nanoporous carbon synthesized with coal tar pitch and its capacitive performance [J].J Mater Chem A,2013,1:9498-9507.
[40] Zhang C,Kong R,Wang X,et al.Porous carbons derived from hypercrosslinked porous polymers for gas adsorption and energy storage [J].Carbon,2017,114:608-618.
[41] Zhang Z Y,Lee C S,Zhang W J.Vertically aligned graphene nanosheet arrays:synthesis,properties,and applications in electrochemical energy conversion and storage [J].Adv Energy Mater,2017,29:1700678.
[42] Xu B,Wang H R,Zhu Q Z,et al.Reduced graphene oxide as a multi-functional conductive binder for supercapacitor electrodes [J].Energy Storage Mater,2018,12:128-136.
[43] Bu Y F,Sun T,Cai Y J,et al.Compressing carbon nanocages by capillarity for optimizing porous structures toward ultrahigh-volumetric-performance supercapacitors [J].Adv Mater,2017,29:1700470.
[2] Li W Q,Liu S M,Pan N,et al.Post-treatment-free synthesis of highly mesoporous carbon for high performance supercapacitor in aqueous electrolytes [J].J Power Sources,2017,357:138-143.
[3] Meng X Y,Cao Q,Jin L,et al.Carbon electrode materials for supercapacitors obtained by co-carbonization of coal-tar pitch and sawdust [J].J Mater Sci,2017,52:760-769.
[4] Zhang H W,Lu J M,Yang L,et al.N,S co-doped porous carbon nanospheres with a high cycling stability for sodium ion batteries [J].New Carbon Mater,2017,32:517-526.
[5] Boota M,Anosori B,Voigt C,et al.Pseudocapacitive electrodes produced by oxidant-free polymerization of pyrrole between the layers of 2D titanium carbide (mxene) [J].Adv Mater,2016,28:1517-1522.
[6] Ding L,Zou B,Liu H,et al.A new route for conversion of corncob to porous carbon by hydrolysis and activation [J].Chem Eng J,2013,225:300-305.
[7] Wang H,Sun X,Liu Z,et al.Creation of nanopores on graphene planes with MgO template for preparing high-performance supercapacitor electrodes [J].Nanoscale,2014,6:6577-6584.
[8] Liang C,Bao J P,Li C G,et al.One-dimensional hierarchically porous carbon from biomass with high capacitance as supercapacitor materials [J].Micropor Mesopor Mater,2017,215:77-82.
[9] Rajagopal R,Lee Y S,Ryu K S.Synthesis and electrochemical analysis of Nb2O5-TiO2/H-rGO sandwich type layered architecture electrode for supercapacitor application [J].Chem Eng J,2017,325:611-623.
[10] Jin Z,Yan X D,Yu Y H,et al.Sustainable activated carbon fibers from liquefied wood with controllable porosity for high-performance supercapacitors [J].J Mater Chem A,2014,2:11706-11715.
[11] Qin T F,Peng S L,Hao J X,et al Flexible and wearable all-solid-state supercapacitor with ultrahigh energy density based on a carbon fiber fabric electrode [J].Adv Energy Mater,2017,1700409.
[12] Wang Z Q,Wu Z Q,Benedetto G D,et al.Microwave synthesis of highly oxidized and defective carbon nanotubes for enhancing the performance of supercapacitors [J].Carbon,2015,91:103-113.
[13] He X J,Ma H,Wang J X,et al.Porous carbon nanosheets from coal tar for high-performance supercapacitors [J].J Power Source,2017,357:41-46.
[14] Huan Y,Sen X,Ya X Y,et al.Advanced porous carbon materials for high efficient lithium metal anodes [J].Adv Energy Mater,2017,7:1700530.
[15] Su Y Z,Yao Z Q,Zhang F,et al.Sulfur-enriched conjugated polymer nanosheet derived sulfur and nitrogen co-doped porous carbon nanosheets as electrocatalysts for oxygen reduction reaction and zinc-air battery [J].Adv Funct Mater,2016,26:5893-5902.
[16] He X J,Li X J,Wang J X,et al.From diverse polycyclic aromatic molecules to interconnected graphene nanocapsules for supercapacitors [J].Micropor Mesopor Mater,2017,245:73-81.
[17] He X J,Li X J,Wang J X,et al.ZnO template strategy for the synthesis of 3D interconnected graphene nanocapsules from coal tar pitch as supercapacitors electrode materials [J].J Power Source,2017,340:183-191.
[18] Wang H Q,Zhao Z B,Chen M,et al.Nitrogen-doped mesoporous carbon nanosheets from coal tar as high performance anode materials for lithium ion batteries [J].New Carbon Mater,2014,29:280-286.
[19] Blackburn J L,Ferguson A J,Cho C,et al.Carbon-nanotube-based thermoelectric materials and devices [J].Adv Mater,2018,1704386.
[20] Choudhary N,Li C,Moore J L,et al.Asymmetric supercapacitor electrodes and devices [J].Adv Mater,2017,29:1605336.
[21] Dong X M,Jin H L,Wang R Y,et al.High volumetric capacitance,ultralong life supercapacitors enabled by waxberry-derived hierarchical porous carbon materials [J].Adv Energy Mater,2018,1702695.
[22] Xia J S,Zhang N,Chong S K,et al.Three-dimensional porous graphene-like sheets synthesized from biocarbon via low-temperature graphitization for a supercapacitor [J].Green Chem,2018,20:694-700.
[23] Cai Y J,Ying L Y,Dong H D,et al.Hierarchically porous carbon nanosheets derived from Moringa oleifera stems as electrode material for high-performance electric double-layer capacitors [J].J Power Sources,2017,353:260-269.
[24] Xu X W,Wang Y,Chen B,et al.Phosphorus-doped porous graphene nanosheet as metal-free electrocatalyst for triiodide reduction reaction in dye-sensitized solar cell [J].Appl Surf Sci,2017,405:308-315.
[25] Hedayat N,Du Y H,Ilkhani H.Review on fabrication techniques for porous electrodes of solid oxide fuel cells by sacrificial template methods [J].Renew Sust Energy Rev,2017,77:1221-1239.
[26] Wang G P,Zhang L,Zhang J J.A review of electrode materials for electrochemical supercapacitors [J].Chem Soc Rev,2012,41:797-828.
[27] Deka B K,Hazarika A,Kwon O,et al.Multifunctional enhancement of woven carbon fiber/ZnO nanotube-based structural supercapacitor and polyester resin-domain solid-polymer electrolytes [J].Chem Eng J,2017,325:672-680.
[28] He X J,Zhang N,Shao X L,et al.A layered-template-nanospace-confinement strategy for production of corrugated graphene nanosheets from petroleum pitch for supercapacitors [J].Chem Eng J,2016,297:121-127.
[29] Zhang Z X,Wang H,Zhang Y X,et al.Carbon nanotube/hematite core/shell nanowires on carbon cloth for supercapacitor anode with ultrahigh specific capacitance and superb cycling stability [J].Chem Eng J,2017,325:221-228.
[30] Wang Y L,Chang B B,Guan D X,et al.Preparation of nanospherical porous NiO by a hard template route and its supercapacitor application [J].Mater Lett,2014,135:172-175.
[31] Wang H R,Yu S K,Xu B.Hierarchical porous carbon materials prepared using nano-ZnO as a template and activation agent for ultrahigh power supercapacitors [J].Chem Commun,2016,52:11512-11515.
[32] Yu S K,Wang H R,Hu C,et al.Facile synthesis of nitrogen-doped,hierarchical porous carbon with high surface area:activation effect of nano-ZnO template [J].J Mater Chem A,2016,4:16341-16348.
[33] Shao J Q,Ma F W,Wu G,et al.In-situ MgO (CaCO3) templating coupled with KOH activation strategy for high yield preparation of various porous carbons as supercapacitor electrode materials [J].Chem Eng J,2017,321:301-313.
[34] Zhao J,Jiang Y F,Fao H,et al.Porous 3D few-layer graphene-like carbon for ultrahigh-power supercapacitors with well-defined structure-performance relationship [J].Adv Mater,2017,29:1604569.
[35] Zhao J,Lai H W,Jiang Z Y,et al.Hydrophilic hierarchical nitrogen-doped carbon nanocages for ultrahigh supercapacitive performance [J].Adv Mater,2015,27:3541-3545.
[36] Guo Y,Shi Z,Chen M,et al.Hierarchical porous carbon derived from sulfonated pitch for electrical double layer capacitors [J].J Power Sources,2014,252:235-243.
[37] Xiao P W,Meng Q H,Zhao L,et al.Biomass-derived flexible porous carbon materials and their applications in supercapacitor and gas adsorption [J].Mater Des,2017,129:164-172.
[38] Zhang W L,Xu C,Ma C Q,et al.Nitrogen-superdoped 3D graphene networks for high-performance supercapacitors [J].Adv Mater,2017,29:1701677.
[39] Wang L Q,Wang J Z,Jia F,et al.Nanoporous carbon synthesized with coal tar pitch and its capacitive performance [J].J Mater Chem A,2013,1:9498-9507.
[40] Zhang C,Kong R,Wang X,et al.Porous carbons derived from hypercrosslinked porous polymers for gas adsorption and energy storage [J].Carbon,2017,114:608-618.
[41] Zhang Z Y,Lee C S,Zhang W J.Vertically aligned graphene nanosheet arrays:synthesis,properties,and applications in electrochemical energy conversion and storage [J].Adv Energy Mater,2017,29:1700678.
[42] Xu B,Wang H R,Zhu Q Z,et al.Reduced graphene oxide as a multi-functional conductive binder for supercapacitor electrodes [J].Energy Storage Mater,2018,12:128-136.
[43] Bu Y F,Sun T,Cai Y J,et al.Compressing carbon nanocages by capillarity for optimizing porous structures toward ultrahigh-volumetric-performance supercapacitors [J].Adv Mater,2017,29:1700470.