A sustainable strategy to prepare porous carbons with tailored pores from shrimp shell for use as the supercapacitor electrode materials
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摘要: 以虾壳作为集碳源、氮源、硬模板、活化剂四功能为一体的唯一原料,采用简单碳化的方法制备了孔结构可调控的氮掺杂多孔炭。采用醋酸溶液浸泡虾壳的方法使碳酸钙的含量在0-100%间变化,碳酸钙在低温时作为硬模板,而在高温时分解产生的氧化钙作为活化剂,进而实现多孔炭的比表面积在117.7-1137.0 m2 g-1,孔体积在0.14-0.64 cm3 g-1,微孔比例在0-73.4%间调控。将制备的多孔炭作为超级电容器电极材料,在KOH体系中,其最大比容量可达328 F g-1,能量密度和功率密度分别达到26.0 Wh kg-1,1470.9 W kg-1。本研究为低成本、绿色化制备生物质基氮掺杂多孔炭提供了可以借鉴的思路。Abstract: Highly efficient synthesis of nitrogen-doped carbons with different porous structures is reported using shrimp shell as the carbon and nitrogen source, and its CaCO3 component as the hard template and the activator. The content of CaCO3 in shrimp shell can be tuned easily in the range of 0-100% by leaching with an acetic acid solution for different times. CaO derived from decomposition of CaCO3 acts as the activator and template to tailor the pore sizes of the carbons. CO2 derived from decomposition of CaCO3 also plays an activating role. Their specific surface areas, pore volumes, ratios of micropore volumes to total pore volumes can be adjusted in the range of 117.6-1137 m2 g-1, 0.14-0.64 cm3 g-1, and 0-73.4%, respectively. When used as the electrodes of supercapacitor, the porous carbon obtained with a leaching time of 92 min exhibits the highest capacitances of 328 F g-1 at 0.05 A g-1 in a 6 M KOH electrolyte and 619.2 F g-1 at 0.05 A g-1 in a 1 M H2SO4 electrolyte. Its corresponding energy density at a power density of 1470.9 W kg-1 is 26.0 Wh kg-1. This work provides a low cost method for fabricating porous carbons to fulfill the high-value-added use of biomass.
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Figure 6. Electrochemical characterizations of C-X% CaCO3(X=0, 25, 50, 100) samples measured in a three-electrolyte: (a) Cyclic voltammetry curves at a scan rate of 10 mV s-1, (b) Galvanostatic charge-discharge curves of these samples at a current density of 100 mA g-1, (c) Specific capacitances of carbon samples at different current densities, (d) Nyquist plots and (e) cycle performance of C-25% CaCO3 electrode measured at a current density of 1 A g-1, and the inset is the last 10 cycles of galvanostatic charge-discharge. All the above tests are conducted in a 6 M KOH solution.
Figure 7. Electrochemical characterizations of C-X% CaCO3 (X=0, 25, 50, 100) samples measured in a three-electrolyte: (a) CV curves at a scan rate of 10 mV s-1, (b) Specific capacitances at different current densities, (c) Galvanostatic charge-discharge curves of these samples at a current density of 100 mA g-1, (d) Nyquist plots and (e) cycle performance of C-25% CaCO3 electrode measured at a current density of 1 A g-1, and the inset is the last 10 cycles of galvanostatic charge-discharge. All the above tests are conducted in 1 M H2SO4 solution.
Figure 8. Electrochemical performance of C-100% CaCO3 and C-25% CaCO3 samples as supercapacitor electrodes in a two-electrode symmetric cell configuration in 6 M KOH: (a) CV curves at 10 mV s-1, (b) Galvanostatic charge-discharge curves at 50 mA g-1, (c) Nyquist plots, (d) Specific capacitances at different current density and (e) power density vs. energy density.
Table 1. Porous properties of the resultant carbons derived from shrimp shell
Sample SBET/m2 g-1 SMic/m2 g-1 SMec/m2 g-1 SMic/SBET/% VTotal/cm3 g-1 VMic/cm3 g-1 VMic/VTotal/% Pore size/nm C-0% CaCO3 117.6 0 117.6 0 0.14 0 0 3.0-5.1 C-25% CaCO3 1371.8 1114 257.8 81.5 0.64 0.47 73.4 0.5-2.5 C-50% CaCO3 678.2 154.1 524.1 22.7 0.51 0.16 33.4 0.95-5.5 C-100%CaCO3 390.2 50.3 339.9 12.9 0.36 0.018 5.3 1.5-5.0 Note: (a) SBET is the specific surface area obtained from BET method, (b) Smic is the microporous surface area calculated from t-plot method, (c) Smes is the mesoporous surface area from t-method external surface area (Smes=SBET-Smic) and (d) Vtotal is the total volume calculated at a relative pressure of 0.99. Table 2. The contents of N, C and O in the resultant carbons from XPS analysis.
Sample XPS(wt.%) N-6[% (eV)] N-5[% (eV)] N-Q[% (eV)] N-X[% (eV)] O-I[% (eV)] O-II[% (eV)] C N O 398.0 399.7 400.8 402.0 531.0 532.2 C-0% CaCO3 83.8 4.2 12.0 21.1 20.6 20.6 37.7 92.0 8.0 C-25% CaCO3 88.0 3.6 8.4 17.8 18.3 35.0 29.0 25.8 74.2 C-50% CaCO3 87.2 4.1 8.7 16.3 21.3 32.6 29.8 9.5 90.5 C-100% CaCO3 86.9 4.0 9.1 15.1 20.0 34.6 30.3 19.2 80.8 Table 3. Kinetic parameters of the C-X% CaCO3 electrodes.
Sample Rs (Ω) Rct (Ω) C-0% CaCO3 0.72 6.27 C-25% CaCO3 0.05 1.55 C-50% CaCO3 1.03 0.95 C-100% CaCO3 0.62 3.01 Table 4. Supercapacitor performance comparison of carbon materials.
Raw Material Synthesis method Energy densities
(Wh kg-1)Reference Shrimp shells self-template and self-activator 26.0 This work Rice husk NaOH activation 5.1 Reference[40] Cauliflower KOH activation 20.5 Reference[43] Corncob KOH activation 20.1 Reference[41] White clover ZnCl2 activation 13.1-25.0 Reference[42] Shrimp shells H3PO4 activation 5.2 Reference[23] Loofah sponge KOH activation 16.1 Reference[44] Wool fiber LiCl/KCl/KNO3 20.1 Reference[45] -
[1] Sun J, Li P, Qu J, et al. Electricity generation from a Ni-Al layered double hydroxide-based flexible generator driven by natural water evaporation[J]. Nano Energy,2019,57:269-278. doi: 10.1016/j.nanoen.2018.12.042 [2] Wang Q, Yan J, Fan Z. Carbon materials for high volumetric performance supercapacitors: Design, progress, challenges and opportunities[J]. Energy Environ Sci,2016,9(3):729-762. doi: 10.1039/C5EE03109E [3] Wang Y, Song Y, Xia Y. Electrochemical capacitors: mechanism, materials, systems, characterization and applications[J]. Chem Soc Rev,2016,45(21):5925-5950. doi: 10.1039/C5CS00580A [4] Shao Y, El-Kady M F, Sun J, et al. Design and mechanisms of asymmetric supercapacitors[J]. Chem Rev,2018,118(18):9233-9280. doi: 10.1021/acs.chemrev.8b00252 [5] Zhao Y, Yu Y, Lv C X, et al. A high energy density fiber-shaped supercapacitor based on zinc-cobalt bimetallic oxide nanowire forests on carbon nanotube fibers[J]. New Carbon Mater,2019,34(6):559-568. doi: 10.1016/S1872-5805(19)60031-4 [6] Xu G, Han J, Bing D, et al. Biomass-derived porous carbon materials with sulfur and nitrogen dual-doping for energy storage[J]. Green Chem,2015,17(3):1668-1674. doi: 10.1039/C4GC02185A [7] He X, Zhang N, Shao X, 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. doi: 10.1016/j.cej.2016.03.153 [8] Wei J, Luo C, Li H, et al. Direct assembly of micron-size porous graphene spheres with a high density as supercapacitor materials[J]. Carbon,2019,149:492-498. doi: 10.1016/j.carbon.2019.04.071 [9] Kai W, Chao G, Li S E, et al. Electrochemical performance of high surface area activated carbons derived from coal tar pitch.[J]. New Carbon Mater,2018,33(6):562-570. [10] Gao F, Geng C, Xiao N, et al. Hierarchical porous carbon sheets derived from biomass containing an activation agent and in-built template for lithium ion batteries[J]. Carbon,2018,139:1085-1092. doi: 10.1016/j.carbon.2018.08.010 [11] Liu M, Niu J, Zhang Z, et al. Potassium compound-assistant synthesis of multi-heteroatom doped ultrathin porous carbon nanosheets for high performance supercapacitors[J]. Nano Energy,2018,51:366-372. doi: 10.1016/j.nanoen.2018.06.037 [12] Peng X, Gao F, Zhao J, et al. Self-assembly of a graphene oxide/MnFe2O4 motor by coupling shear force with capillarity for removal of toxic heavy metals[J]. J Mater Chem A,2018,6(42):20861-20868. doi: 10.1039/C8TA06663A [13] He X, Ling P, Qiu J, et al. Efficient preparation of biomass-based mesoporous carbons for supercapacitors with both high energy density and high power density[J]. J Power Sources,2013,240:109-113. doi: 10.1016/j.jpowsour.2013.03.174 [14] Zhang Q H, Z S-l, Wei X Y, et al. H3PO4 activated carbons as the electrode materials of supercapacitors using an ionic liquid electrolyte[J]. New Carbon Mater,2018,33(1):61-70. [15] Cao D, Zhang Q, Hafez A M, et al. Lignin-derived holey, layered, and thermally conductive 3D scaffold for lithium dendrite suppression[J]. Small Methods,2019,3(5):1800539-1800549. doi: 10.1002/smtd.201800539 [16] Hu Y S, Adelhelm P, Smarsly B M, et al. Synthesis of hierarchically porous carbon monoliths with highly ordered microstructure and their application in rechargeable lithium batteries with high-rate capability[J]. Adv Funct Mater,2010,17(12):1873-1878. [17] Xu G, Ding B, Shen L, et al. Sulfur embedded in metal organic framework-derived hierarchically porous carbon nanoplates for high performance lithium-sulfur battery[J]. J Mater Chem A,2013,1(14):4490-4496. doi: 10.1039/c3ta00004d [18] He X, Li X, Ma H, et al. ZnO template strategy for the synthesis of 3D interconnected graphene nanocapsules from coal tar pitch as supercapacitor electrode materials[J]. J Power Sources,2017,340:183-191. doi: 10.1016/j.jpowsour.2016.11.073 [19] Feng W, Han-fang Z, Xiao-jun H, et al. Synthesis of porous carbons from coal tar pitch for high-performance supercapacitors[J]. New Carbon Mater,2019,34(2):132-139. doi: 10.1016/S1872-5805(19)60006-5 [20] Qiu D, Cao T, Zhang J, et al. Precise carbon structure control by salt template for high performance sodium-ion storage[J]. J Energy Chem,2019,31:101-106. doi: 10.1016/j.jechem.2018.05.014 [21] Guo H, Bing D, Jie W, et al. Template-induced self-activation route for nitrogen-doped hierarchically porous carbon spheres for electric double layer capacitors[J]. Carbon,2018,136:204-210. doi: 10.1016/j.carbon.2018.04.079 [22] White R J, Antonietti MTitirici M M. Naturally inspired nitrogen doped porous carbon[J]. J Mater Chem,2009,19(45):8645-8650. doi: 10.1039/b911528e [23] Qu J, Geng C, Lv S, et al. Nitrogen, oxygen and phosphorus decorated porous carbons derived from shrimp shells for supercapacitors[J]. Electrochim Acta,2015,176:982-988. doi: 10.1016/j.electacta.2015.07.094 [24] Gao F, Qu J Y, Geng C, et al. Self-templating synthesis of nitrogen-decorated hierarchical porous carbon from shrimp shell for supercapacitors[J]. J Mater Chem A,2016,4(19):7445-7452. doi: 10.1039/C6TA01314G [25] Gao F, Qu J, Zhao Z, et al. Nitrogen-doped activated carbon derived from prawn shells for high-performance supercapacitors[J]. Electrochim Acta,2016,190:1134-1141. doi: 10.1016/j.electacta.2016.01.005 [26] Xiao C, Zhang W, Lin H, et al. Modification of a rice husk-based activated carbon by thermal treatment and its effect on its electrochemical performance as a supercapacitor electrode[J]. New Carbon Mater,2019,34(4):341-348. doi: 10.1016/S1872-5805(19)30021-6 [27] Tajima T, Tsutsui A, Fujii T, et al. Fabrication of novel core-shell microspheres consisting of single-walled carbon nanotubes and CaCO3 through biomimetic mineralization[J]. Polym J,2012,44(6):620-624. doi: 10.1038/pj.2012.36 [28] Liu H, Cao C, Wei F, et al. Fabrication of Macroporous/Mesoporous Carbon Nanofiber Using CaCO3 Nanoparticles as Dual Purpose Template and Its Application as Catalyst Support[J]. The Journal of Physical Chemistry C,2013,117(41):21426-21432. doi: 10.1021/jp4078807 [29] Huanlei W, Zhanwei X, Alireza K, et al. Interconnected carbon nanosheets derived from hemp for ultrafast supercapacitors with high energy[J]. ACS Nano,2013,7(6):5131-5141. doi: 10.1021/nn400731g [30] Mahasweta N, Keisuke O, Arghya D, et al. Unprecedented CO2 uptake over highly porous N-doped activated carbon monoliths prepared by physical activation[J]. Chem Commun,2012,48(83):10283-10285. doi: 10.1039/c2cc35334b [31] Laine J, Calafat A, Labady M. Preparation and characterization of activated carbons from coconut shell impregnated with phosphoric acid[J]. Carbon,1989,27(2):191-195. doi: 10.1016/0008-6223(89)90123-1 [32] Liu H, Song H, Chen X, et al. Effects of nitrogen- and oxygen-containing functional groups of activated carbon nanotubes on the electrochemical performance in supercapacitors[J]. J Power Sources,2015,285:303-309. doi: 10.1016/j.jpowsour.2015.03.115 [33] Lu W, Liu M, Ling M, et al. Nitrogen-containing ultramicroporous carbon nanospheres for high performance supercapacitor electrodes[J]. Electrochim Acta,2016,205:132-141. doi: 10.1016/j.electacta.2016.04.114 [34] Li J, Liu W, Xiao D, et al. Oxygen-rich hierarchical porous carbon made from pomelo peel fiber as electrode material for supercapacitor[J]. Appl Surf Sci,2017,416:918-924. doi: 10.1016/j.apsusc.2017.04.162 [35] Kang W, Lin B, Huang G, et al. Peanut bran derived hierarchical porous carbon for supercapacitor[J]. J Mater Sci - Mater Electron,2018,29(8):6361-6368. doi: 10.1007/s10854-018-8615-1 [36] Cheng L, Yu H, Yong J, et al. Camellia pollen-derived carbon for supercapacitor electrode material[J]. J Power Sources,2018,394:9-16. doi: 10.1016/j.jpowsour.2018.05.032 [37] Yan L, Li D, Yan T, et al. Catalytic transfer hydrogenolysis of lignin-derived aromatic ethers promoted by bimetallic Pd/Ni systems[J]. ACS Sustain Chem Eng,2018,6(7):5265-5272. [38] Zhang Z, Zhou Z, Peng H, et al. Nitrogen- and oxygen-containing hierarchical porous carbon frameworks for high-performance supercapacitors[J]. Electrochim Acta,2014,134(21):471-477. [39] He X, Zhao N, Qiu J, et al. Synthesis of hierarchical porous carbons for supercapacitors from coal tar pitch with nano-Fe2O3 as template and activation agent coupled with KOH activation[J]. J Mater Chem A,2013,1(33):9440-9450. doi: 10.1039/c3ta10501f [40] Teo E, Muniandy L, Ng E, et al. High surface area activated carbon from rice husk as a high performance supercapacitor electrode[J]. Electrochim Acta,2016,192:110-119. doi: 10.1016/j.electacta.2016.01.140 [41] Yang S, Zhang K. Converting corncob to activated porous carbon for supercapacitor application[J]. Nanomaterials,2018,8(4):181-191. doi: 10.3390/nano8040181 [42] Ma G, Zhang Z, Sun K, et al. White clover based nitrogen-doped porous carbon for a high energy density supercapacitor electrode[J]. Rsc Advances,2015,5(130):107707-107715. doi: 10.1039/C5RA20327A [43] Men B, Guo P, Sun Y, et al. High-performance nitrogen-doped hierarchical porous carbon derived from cauliflower for advanced supercapacitors[J]. J Mater Sci,2018,54(3):2446-2457. [44] Su X, Chen J, Zheng G, et al. Three-dimensional porous activated carbon derived from loofah sponge biomass for supercapacitor applications[J]. Appl Surf Sci,2018,436:327-336. doi: 10.1016/j.apsusc.2017.11.249 [45] Zeng D, Dou Y, Li M, et al. Wool fiber-derived nitrogen-doped porous carbon prepared from molten salt carbonization method for supercapacitor application[J]. J Mater Sci,2018,53(11):8372-8384. doi: 10.1007/s10853-018-2035-8 -