Artículos
Publicado 2018-05-05
Palabras clave
- Lignina,
- Xerogeles de Carbono Activados,
- Propiedades Electroquímicas,
- Ácido Fosfórico.
Cómo citar
Diossa, G., Castro, C. D., Zapata-Benabithe, Z., & Quintana, G. (2018). Evaluación de la capacidad de almacenamiento de energía en xerogeles de carbono activados obtenidos a partir lignina. Revista ION, 30(2), 17–30. https://doi.org/10.18273/revion.v30n2-2017002
Resumen
En este trabajo se prepararon dos tipos de xerogeles orgánicos a partir de soluciones sol-gel usando resorcinol (R), formaldehido (F), lignina (L) y NaOH (C) como catalizador. La relación másica L/(R+L) se fijó en 0,27 y el contenido de catalizador se varió en dos relaciones másicas de (R+L)/C, 90,3 (serie G) y 72,1 (serie D). Los xerogeles orgánicos se activaron químicamente con ácido fosfórico a una relación másica de ácido a xerogel de 0,85/1, 1h de impregnación y 2h de activación y una temperatura de activación de 450°C. Los xerogeles de carbono activados se evaluaron electroquímicamente como electrodos para supercondensadores mediante diferentes técnicas como voltamperometría cíclica (VC), cronopotenciometría (CP) y espectroscopía de impedancia electroquímica (EIS) en una configuración de dos y tres electrodos. El valor de la capacidad gravimétrica a partir de las curvas de voltamperometría cíclica a 0,5mV/s (0 – 0,75V) para las muestras activadas GA27 y DA27 fueron 222 y 226F/g, respectivamente. La muestra DA27 mostró una mayor retención de la energía, que es atribuible a un aumento de la presencia de mesoporos en la muestra comparada con la GA27. Los mesoporos s forman debido a la degradación de la lignina en la activación con ácido fosfórico; la muestra DA27 tiene una reticulación superior en comparación con la muestra GA27, ya que el interior del xerogel orgánico es menos accesible. La muestra con mayor contenido de catalizador mostró mejor comportamiento electroquímico para su aplicación como electrodos para supercondensadores.
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Referencias
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[2] Inagaki M, Konno H, Tanaike O. Carbon materials for electrochemical capacitors. J. Power Sources. 2010;195(24):7880– 903.
[3] Sharma P, Bhatti TS. A review on electrochemical double-layer capacitors. Energ. Convers. Manag. 2010;51(12):2901–12.
[4] Pandolfo A, Hollenkamp A. Carbon properties and their role in supercapacitors. J. Power Sources. 2006;157(1):11–27.
[5] Adhyapak PV, Maddanimath T, Pethkar S, Chandwadkar AJ. Application of electrochemically prepared carbon nanofibers in supercapacitors. J. Power Sources. 2002;109(1):105–10.
[6] Miller JR, Simon P. Fundamentals of electrochemical capacitor design and operation. Electrochem. Soc. Interface. 2008;17(1):31–2.
[7] Wang H, Hao Q, Yang X, Lu L, Wang X. Graphene oxide doped polyaniline for supercapacitors. Electrochem. commun. 2009;11(6):1158–61.
[8] Zhao Q, Wangz X, Liu J, Wang H, Zhang Y, Gao J, et al. Surface modification and performance enhancement of carbon derived from chromium carbide for supercapacitor applications. J. Electrochem. Soc. 2015;162(6):845–51.
[9] Kötz R, Carlen M. Principles and applications of electrochemical capacitors. Electrochim. 2010;45(15-16):2483–98.
[10] Zhang Y,Feng H, Wu X, Wang L, Zhang A,Xia T, et al. Progress of electrochemical capacitor electrode materials: A review. Int. J. Hydrog. Energy. 2009;34(11):4889–99.
[11] Halama A, Szubzda B, Pasciak G. Carbon aerogels as electrode material for electrical double layer supercapacitors— Synthesis and properties. Electrochim. 2010;55(25):7501–5.
[12] Largeot C, Portet C, Chmiola J, Taberna PL, Gogotsi Y, Simon P. Relation between the ion size and pore size for an electric double-layer capacitor. J. Am. Chem. Soc. 2008;130(9):2730–1.
[13] Shi H. Activated carbons and double layer capacitance. Electrochim. 1996;41(10):1633–9.
[14] Frackowiak E, Béguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon N. Y.2001;39(6):937–50.
[15] Pekala R. Organic aerogels from the polycondensation of resorcinol with formaldehyde. J. Mater. Sci.1989;24(9):3221–7.
[16] Czakkel O, Marthi K, Geissler E, László K. Influence of drying on the morphology of resorcinol–formaldehyde-based carbon gels. Micropor. Mesopor. Mater.2005;86(1-3):124–33.
[17] Long D, Zhang J, Yang J, Hu Z, Cheng G, Liu X, et al. Chemical state of nitrogen in carbon aerogels issued from phenol– melamine–formaldehyde gels. Carbon N. Y. 2008;46(9):1259–62.
[18] Pekala R, Alviso C, Lu X, Gross J, Fricke J. New organic aerogels based upon a phenolic-furfural reaction. J. Non-Cryst Solids.1995;188(34-40):34–40.
[19] Long D, Zhang J, Yang J, Hu Z, Cheng G, Zhang R, et al. Preparation and microstructure control of carbon aerogels produced using m-cresol mediated sol-gel polymerization of phenol and furfural. New Carbon Mater. 2008;23(2):165–70.
[20] Wu D, Fu R. Synthesis of organic and carbon aerogels from phenol–furfural by twostep polymerization. Micropor. Mesopor. Mater.2006;96(1–3):115–20.
[21] Scherdel C, Reichenauer G. Carbon xerogels synthesized via phenol–formaldehyde gels. Micropor. Mesopor. Mater. 2009;126(1–2):133–42.
[22] Fairén D, Carrasco F, Moreno C. Inter- and IntraPrimary-Particle Structure of Monolithic Carbon Aerogels Obtained with Varying Solvents. Langmuir. 2008;24(6):2820-5.
[23] Lin C, Ritter JA. Carbonization and activation of sol-gel derived carbon xerogels. Carbon. 2000;38(6):849–61.
[24] Hulicova D, et al. Effect of surface phosphorus functionalities of activated carbons containing oxygen and nitrogen on electrochemical capacitance. Carbon. 2009;47(6):1576–84.
[25] Park SJ, Jung WY. Effect of KOH activation on the formation of oxygen structure in activated carbons synthesized from polymeric precursor. J. Colloid Interface Sci. 2002;250(1):93–8.
[26] Carvalho A, Cardoso B, Pires J, De Carvalho MB. Preparation of activated carbons from cork waste by chemical activation with KOH. Carbon. 2003;41(14):2873–6.
[27] Basta A, Fierro V, El-Saied H, Celzard A. 2-Steps KOH activation of rice straw: An efficient method for preparing high-performance activated carbons. Bioresour. Technol. 2009;100(17):3941–7.
[28] Lillo M, Cazorla D, Linares A. Understanding chemical reactions between carbons and NaOH and KOH an insight into the chemical activation mechanism. Carbon. 2003;41(2):267–75.
[29] Kierzek K, Frackowiak E, Lota G, Gryglewicz G, Machnikowski J. Electrochemical capacitors based on highly porous carbons prepared by KOH activation. Electrochim. 2004;49(4):515–23.
[30] Kıiliç M, Apaydın-Varol E, and Pütün AE. Preparation and surface characterization of activated carbons from Euphorbia rigida by chemical activation with ZnCl2, K2CO3, NaOH and H3PO4. Appl. Surf. Sci. 2012;261:247–54.
[31] Deng H, Li G, Yang H, Tang J, Tang J. Preparation of activated carbons from cotton stalk by microwave assisted KOH and K2CO3 activation. Chem. Eng. J. 2010;163(3):373–81.
[32] Kim J, Lee D, Bae T, Lee Y. The electrochemical enzymatic glucose biosensor based on mesoporous carbon fibers activated by potassium carbonate. J. Ind. Eng. Chem. 2015;25:192–8.
[33] Mestre AS, Bexiga AS, Proença M, Andrade M, Pinto ML, Matos I, et al. Activated carbons from sisal waste by chemical activation with K2CO3: Kinetics of paracetamol and ibuprofen removal from aqueous solution. Bioresour. Technol. 2011;102(17):8253–60.
[34] Liu Y, Wang Y, Zhang G, Liu W, Wang D, Dong Y. Preparation of activated carbon from willow leaves and evaluation in electric double-layer capacitors. Mater. Lett. 2016;176:60–63.
[35] Zhang ZJ, Dong C, Ding XY, Xia YK. A generalized ZnCl2 activation method to produce nitrogen-containing nanoporous carbon materials for supercapacitor applications. J. Alloys Compd. 2015;636:275–81.
[36] Attia AA, Girgis BS, Fathy NA. Removal of methylene blue by carbons derived from peach stones by H3PO4 activation: Batch and column studies. Dye. Pigment. 2008;76(1):282–9.
[37] Gonzalez E, Cordero T, Rodriguez J, Cotoruelo L, Rodriguez JJ. Removal of water pollutants with activated carbons prepared from H3PO4 activation of lignin from kraft black liquors. Water Res. 2004;38(13):3043–50.
[38] Kumar KS, Al Shoaibi A, Srinivasakannan C. A comparison of microstructure and adsorption characteristics of activated carbons by CO2 and H3PO4 activation from date palm pits. New Carbon Mater. 2012;27(5):344–51.
[39] Pang L, Zou B, Han X, Cao L, Wang W, Guo Y. One-step synthesis of highperformance porous carbon from corn starch for supercapacitor. Mater. Lett. 2016;184:88–91.
[40] Pang L, Zou B, Zou Y,Han X, Cao L, Wang W, Guo Y et al. A new route for the fabrication of corn starch-based porous carbon as electrochemical supercapacitor electrode material. Colloids Surfaces A: Physicochem. Eng. Asp. 2016;504:26–33.
[41] Wu M, Li L, Liu J, Li Y, Ai P, Wu W, et al. Template-free preparation of mesoporous carbon from rice husks for use in supercapacitors. New Carbon Mater.2015;30(5):471–5.
[42] Qu J, Geng C, Lv S, Shao G, Ma S, Wu M. Nitrogen, oxygen and phosphorus decorated porous carbons derived from shrimp shells for supercapacitors. Electrochim. 2015;176:982–8.
[43] Molina M, Rodríguez F. Role of chemical activation in the development of carbon porosity. Colloids Surfaces A Physicochem. Eng. Asp. 2004;241(1–3):15–25.
[44] Sun J, Chen G, Wu J, Dong H, Xiong G. Bismuth vanadate hollow spheres: Bubble template synthesis and enhanced photocatalytic properties for photodegradation. Appl. Catal. B. 2013;132:304–14.
[45] Carrott PJM, Ribeiro MML. Lignin – from natural adsorbent to activated carbon: A review. Bioresour. Technol.2007; 98(12): 2301–12.
[46] Saha D, Li Y, Bi Z, Chen J, Keum JK, Hensley DK et al. Studies on Supercapacitor Electrode Material from Activated LigninDerived Mesoporous Carbon. Langmuir. 2014;30(3):900–10.
[47] Grishechko LI, Amaral G, Szczurek A, Fierro V, Kuznetsov BN, Celzard A. Lignin-phenol-formaldehyde aerogels and cryogels. Microporous Mesoporous Mater. 2013;168:19–29.
[48] Castro CD, Quintana GC. Mixture Design Approach on the Physical Properties of Lignin-Resorcinol-Formaldehyde Xerogels. Int. J. Polym. Sci.2015;2015.
[49] Dubinin M. Generalization of the theory of volume filling of micropores to nonhomogeneous microporous structures. Carbon. 1985;23(4):373–80.
[50] Zapata Z, Carrasco F, Moreno C. Preparation, surface characteristics, and electrochemical doublelayer capacitance of KOH-activated carbon aerogels and their O- and N-doped derivatives. J. Power Sources. 2012;219:80–8.
[51] Rodríguez F, Linares A. Microporous structure of activated carbons as revealed adsorption methods. Chemistry and physics of carbon. 1989;21:1.
[52] Hayashi J., Kazehaya A, Muroyama K, Watkinson AP. Preparation of activated carbon from lignin by chemical activation. Carbon. 2000;38(13):1873–8.
[53] Chen F, Li J. Synthesis and Structural Characteristics of Organic Aerogels with Different Content of Lignin. Adv. Mater. Res. 2010;113:1837–40.
[54] Chen F, Xu M, Wang L, Li J. Preparation and characterization of organic aerogels from a lignin - resorcinol - formaldehíde copolymer. Bioresources. 2011;6(2):1262–72.
[55] Grishechkoa LI, Amaral G, Szczurek A, Fierro V, Kuznetsov BN, Pizzi A et al. New tannin–lignin aerogels. Ind. Crops Prod. 2013;41:347– 55.
[56] Alonso MV, Oliet M, García J, Rodríguez F, Echeverría J. Gelation and isoconversional kinetic analysis of ligninphenol-formaldehyde resol resins cure. Chem. Eng. J. 2006;122(3):159–66.
[57] Li W, Wang J. Significant enhancement of the cycling performance and rate capability of the P/C composite via chemical bonding ( P-C ). J. Mater. Chem. A. 2016;4(2):505–11.
[58] Puziy AM, Poddubnaya OI, Ziatdinov AM. On the chemical structure of phosphorus compounds in phosphoric acidactivated carbon. Appl. Surf. Sci. 2006;252(23):8036–8.
[59] Liu Y, Li K, Liu Y, Pu L, Chen Z, Deng S. The high-performance and mechanism of P-doped activated carbon as a catalyst for aircathode microbial fuel cells. J. Mater. Chem. A. 2015;3(42):21149–58.
[60] Qing X, Caoa Y, Wang J, Chen J, Lu Y. P/N/O co-doped carbonaceous materials based supercapacitor with voltage up to 1.9 V in the aqueous electrolyte. RSC Adv. 2014;4(99):55971–9.
[61] Xie H, Zhu Y, Wu Y, Wu Z, Liu E. The effect of hydroquinone as an electrolyte additive on electrochemical performance of the polyaniline supercapacitor. Mater. Res. Bull. 2014;50:303–6.
[62] Mahata N, Pereira M, Suárez F, Martínez A, Tascón J, Figueiredo J. Tuning of texture and surface chemistry of carbon xerogels. J. Colloid Interface Sci. 2008;324(1–2):150–5.
[63] Su F, Poh CK, Chen JS, Xu G, Wang D, Li Q, et al. Nitrogen-containing microporous carbon nanospheres with improved capacitive properties. Energy Environ. Sci. 2011;4(3):717–24.
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