najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2023-14-4-489-497najo-183Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХThe role and effect of CO2 flow rate on the structure formation of ultrahigh porous activated carbon from H3PO4-impregnated waste cotton used as supercapacitor electrode materialРоль и влияние расхода СО2 на структурообразование сверхвысокопористого активированного угля из хлопковых отходов, пропитанных H3PO4, используемого в качестве электродного материала суперконденсатораhttps://orcid.org/0000-0003-3749-3198ТхачН. К.ThachN. K.

Nguyen K. Thach 

Leninskiy prospect 4, Moscow, 119049

nguyenkienthach@gmail.comhttps://orcid.org/0000-0002-3879-8017КречетовИ. С.KrechetovI. S.

Ilya S. Krechetov

Leninskiy prospect 4, Moscow, 119049

https://orcid.org/0000-0002-5158-1963БерестовВ. В.BerestovV. V.

Valentin V. Berestov

Leninskiy prospect 4, Moscow, 119049

https://orcid.org/0009-0000-6057-6632КанО. И.KanO. I.

O. I. Kan

Leninskiy prospect 4, Moscow, 119049

https://orcid.org/0009-0000-2481-2976МаслоченкоИ. В.MaslochenkoI. A.

Ivan A. Maslochenko

Leninskiy prospect 4, Moscow, 119049

https://orcid.org/0000-0002-0648-411XЛепковаТ. Л.LepkovaT. L.

Tatyana L. Lepkova

Leninskiy prospect 4, Moscow, 119049

https://orcid.org/0000-0002-3397-9556СтахановаС. В.StakhanovaS. V.

Svetlana V. Stakhanova

Leninskiy prospect 4, Moscow, 119049; Miusskaya square 9, Moscow, 125047

National University of Science and Technology “MISIS”; College of electromechanical and civil engineering, Vietnam National University of ForestryRussian FederationNational University of Science and Technology “MISIS”Russian FederationNational University of Science and Technology “MISIS”; Mendeleev University of Chemical Technology of RussiaRussian Federation202303062025144489497Copyright © Thach N.K., Krechetov I.S., Berestov V.V., Kan O.I., Maslochenko I.A., Lepkova T.L., Stakhanova S.V., 20252025Тхач Н.К., Кречетов И.С., Берестов В.В., Кан О.И., Маслоченко И.В., Лепкова Т.Л., Стаханова С.В.Thach N.K., Krechetov I.S., Berestov V.V., Kan O.I., Maslochenko I.A., Lepkova T.L., Stakhanova S.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/183

Ultrahigh porosity activated carbon (AC) was made from H3PO4-impregnated waste cotton precursor by carbonization in Ar and physical activation in variable CO2 flow rate with ultrahigh heating rate. The presence of CO2 in the activation plays an important role in the formation of the porous structure of AC. The obtained AC had outstanding physical and electrochemical properties. The specific surface area and micropore volume of AC reached 4800.7 m2 /g and 2.499 cm3 /g, respectively. The pore size distribution was mainly in the microporous region. The electrochemical double-layer capacitors (EDLCs) with AC-based active electrode and an electrolyte solution of 1 M 1,1-dimethylpyrrolidinium tetrafluoroborate in acetonitrile were fabricated. The specific capacitance of electrode material degraded less than 10 % with the highest value of 105.7 F/g at 0.05 A/g as the specific current varied from 0.05 A/g – 15 A/g. After 8000 charge-discharge cycles at 1 A/g, the specific capacitance of the AC-base electrode material fabricated at CO2 flow rate greater than 200 ml/min degraded less than 15 % with the highest value of 101.2 F/g. The optimal CO2 flow rate for fabricating waste cotton-based AC is 200 ml/min. 

Активированный уголь сверхвысокой пористости (АУ) был изготовлен из пропитанной H3PO4 отходов хлопка путем карбонизации в атмосфере аргона и физической активации в атмосфере CO2 с регулируемой скоростью потока и чрезвычайно высокой скоростью нагрева для обоих процессов до 585℃/мин и 751℃/мин соответственно. Наличие СО2 в процессе активации играет важную роль в формировании пористой структуры АУ. Полученный АУ представлял собой аморфный углерод и обладал выдающимися физическими и электрохимическими свойствами. Удельная поверхность и объем микропор АУ для образца СТ4 достигали 4800,7 м2/г и 2,499 см3/г соответственно. Распределение пор в АУ по размерам было в основном в микропористой области. Изготовлены электрические двойнослойные конденсаторы (ЭДСК) с активным электродом на основе переменного тока и раствором электролита 1 М тетрафторбората 1,1-диметилпирролидиния (DMP×BF4) в ацетонитриле (ACN). Электродный материал обладал высокой стабильностью и хорошими электрохимическими обратимыми свойствами. Удельная емкость материала электрода ухудшилась менее чем на 10 % с максимальным значением 105,7 Ф/г при 0,05 А/г при изменении удельного тока от 0,05 А/г до 15 А/г. После 8000 циклов заряда-разряда при плотности тока 1 А/г удельная емкость электродного материала на основе переменного тока, изготовленного при расходе СО2 более 200 мл/мин, ухудшилась менее чем на 15 % с максимальным значением 101,2 Ф/мин. грамм. Оптимальный расход СО2 для изготовления АУ на основе хлопка из отходов составляет 200 мл/мин. Полученный АУ может быть использован в качестве электродного материала для высокоэффективных суперконденсаторов.

активированный угольпористый активированный угольцеллюлозамакулатурасуперконденсаторацетонитрилтетрафторборат 11-диметилпирролидинияactivated carbonporous activated carboncellulosewaste cottonsupercapacitorThe authors would like to thank Dr. Alexey Igoreevich Salimon, Dean of the Department of Physical Chemistry, the College of New Materials and Nanotechnologies, the University of Science and Technology “MISiS”, Moscow, Russia, for valuable recommendations on the content of the article. The authors would also like to thank The Hierarchically Structured Materials Lab, Center for Digital Engineering, Skoltech, Moscow, Russia, for helping us to conduct the BET and SEM measurements.ReferencesS¸ ahin M., Blaabjerg F., and Sangwongwanich A. A Comprehensive Review on Supercapacitor Applications and Developments. Energies (Basel), 2022, 15(3), P. 674–699.S¸ ahin M., Blaabjerg F., and Sangwongwanich A. A Comprehensive Review on Supercapacitor Applications and Developments. Energies (Basel), 2022, 15(3), P. 674–699.Kumar G.V.B., Kaliannan P., Padmanaban S., Holm-Nielsen J.B., and Blaabjerg F. Effective Management System for Solar PV Using Real-Time Data with Hybrid Energy Storage System. Applied Sciences, 2020, 10(3), P. 1108–1122.Kumar G.V.B., Kaliannan P., Padmanaban S., Holm-Nielsen J.B., and Blaabjerg F. Effective Management System for Solar PV Using Real-Time Data with Hybrid Energy Storage System. Applied Sciences, 2020, 10(3), P. 1108–1122.Yang Y., Han Y., Jiang W., Zhang Y., Xu Y., and Ahmed A.M. Application of the Supercapacitor for Energy Storage in China: Role and Strategy. Applied Sciences, 2021, 12(1), P. 354–372.Yang Y., Han Y., Jiang W., Zhang Y., Xu Y., and Ahmed A.M. Application of the Supercapacitor for Energy Storage in China: Role and Strategy. Applied Sciences, 2021, 12(1), P. 354–372.Winter M., Brodd R.J. What Are Batteries, Fuel Cells, and Supercapacitors? Chem Rev, 2004, 104(10), P. 4245–4270.Winter M., Brodd R.J. What Are Batteries, Fuel Cells, and Supercapacitors? Chem Rev, 2004, 104(10), P. 4245–4270.Kotz R. and Carlen M. Principles and applications of electrochemical capacitors. ¨ Electrochim Acta, 2000, 45(15–16), P. 2483–2498.Kotz R. and Carlen M. Principles and applications of electrochemical capacitors. ¨ Electrochim Acta, 2000, 45(15–16), P. 2483–2498.Burke A. Ultracapacitors: why, how, and where is the technology. J. Power Sources, 2000, 91(1), P. 37–50.Burke A. Ultracapacitors: why, how, and where is the technology. J. Power Sources, 2000, 91(1), P. 37–50.Miller J.R. and Burke A. Electrochemical Capacitors: Challenges and Opportunities for Real-World Applications. Electrochem Soc Interface, 2008, 17(1), P. 53–57.Miller J.R. and Burke A. Electrochemical Capacitors: Challenges and Opportunities for Real-World Applications. Electrochem Soc Interface, 2008, 17(1), P. 53–57.Luo Y., Li D., Chen Y., Sun X., Cao Q., and Liu X. The performance of phosphoric acid in the preparation of activated carbon-containing phosphorus species from rice husk residue. J. Mater. Sci., 2019, 54(6), P. 5008–5021.Luo Y., Li D., Chen Y., Sun X., Cao Q., and Liu X. The performance of phosphoric acid in the preparation of activated carbon-containing phosphorus species from rice husk residue. J. Mater. Sci., 2019, 54(6), P. 5008–5021.Sych N.V., et al. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob. Appl. Surf. Sci., 2012, 261, P. 75–82.Sych N.V., et al. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob. Appl. Surf. Sci., 2012, 261, P. 75–82.Yakout S.M. and Sharaf El-Deen G. Characterization of activated carbon prepared by phosphoric acid activation of olive stones. Arabian Journal of Chemistry, 2016, 9, P. S1155–S1162.Yakout S.M. and Sharaf El-Deen G. Characterization of activated carbon prepared by phosphoric acid activation of olive stones. Arabian Journal of Chemistry, 2016, 9, P. S1155–S1162.Adib M.R.M., et al. Effect of Phosphoric Acid Concentration on the Characteristics of Sugarcane Bagasse Activated Carbon. IOP Conf. Ser. Mater. Sci. Eng., 2016, 136, P. 012061–012069.Adib M.R.M., et al. Effect of Phosphoric Acid Concentration on the Characteristics of Sugarcane Bagasse Activated Carbon. IOP Conf. Ser. Mater. Sci. Eng., 2016, 136, P. 012061–012069.Nahil M.A. and Williams P.T. Characterisation of Activated Carbons with High Surface Area and Variable Porosity Produced from Agricultural Cotton Waste by Chemical Activation and Co-activation. Waste Biomass Valorization, 2012, 3(2), P. 117–130.Nahil M.A. and Williams P.T. Characterisation of Activated Carbons with High Surface Area and Variable Porosity Produced from Agricultural Cotton Waste by Chemical Activation and Co-activation. Waste Biomass Valorization, 2012, 3(2), P. 117–130.Sartova K., Omurzak E., Kambarova G., Dzhumaev I., Borkoev B., and Abdullaeva Z. Activated carbon obtained from the cotton processing wastes. Diam. Relat. Mater., 2019, 91, P. 90–97.Sartova K., Omurzak E., Kambarova G., Dzhumaev I., Borkoev B., and Abdullaeva Z. Activated carbon obtained from the cotton processing wastes. Diam. Relat. Mater., 2019, 91, P. 90–97.Ma G. et al. Cotton-based porous activated carbon with a large specific surface area as an electrode material for high-performance supercapacitors. RSC Adv., 2015, 5(79), P. 64704–64710.Ma G. et al. Cotton-based porous activated carbon with a large specific surface area as an electrode material for high-performance supercapacitors. RSC Adv., 2015, 5(79), P. 64704–64710.Nahil M.A. and Williams P.T. Pore characteristics of activated carbons from the phosphoric acid chemical activation of cotton stalks. Biomass Bioenergy, 2012, 37, P. 142–149.Nahil M.A. and Williams P.T. Pore characteristics of activated carbons from the phosphoric acid chemical activation of cotton stalks. Biomass Bioenergy, 2012, 37, P. 142–149.Liou T.-H. Development of mesoporous structure and high adsorption capacity of biomass-based activated carbon by phosphoric acid and zinc chloride activation. Chemical Engineering Journal, 2009, 158, 2, P. 129–142.Liou T.-H. Development of mesoporous structure and high adsorption capacity of biomass-based activated carbon by phosphoric acid and zinc chloride activation. Chemical Engineering Journal, 2009, 158, 2, P. 129–142.Xia M., Shao X., Sun Z., and Xu Z. Conversion of cotton textile wastes into porous carbons by chemical activation with ZnCl2, H3PO4, and FeCl3. Environmental Science and Pollution Research, 2020, 27(20), P. 25186–25196.Xia M., Shao X., Sun Z., and Xu Z. Conversion of cotton textile wastes into porous carbons by chemical activation with ZnCl2, H3PO4, and FeCl3. Environmental Science and Pollution Research, 2020, 27(20), P. 25186–25196.Budinova T. et al. Characterization and application of activated carbon produced by H3PO4 and water vapor activation. Fuel Processing Technology, 2006, 87(10), P. 899–905.Budinova T. et al. Characterization and application of activated carbon produced by H3PO4 and water vapor activation. Fuel Processing Technology, 2006, 87(10), P. 899–905.Ma G. et al. Cotton-based porous activated carbon with a large specific surface area as an electrode material for high-performance supercapacitors. RSC Adv, 2015, 5(79), P. 64704–64710.Ma G. et al. Cotton-based porous activated carbon with a large specific surface area as an electrode material for high-performance supercapacitors. RSC Adv, 2015, 5(79), P. 64704–64710.Wakelyn P.J. Cotton Fiber Chemistry and Technology. CRC Press, 2006.Wakelyn P.J. Cotton Fiber Chemistry and Technology. CRC Press, 2006.Thach N.K., Krechetov I.S., Berestov V.V., Lepkova T.L., and Stakhanova S.V. Optimizing the carbonization temperature in the fabrication of waste cotton based activated carbon used as electrode material for supercapacitor. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13(5), P. 565–573.Thach N.K., Krechetov I.S., Berestov V.V., Lepkova T.L., and Stakhanova S.V. Optimizing the carbonization temperature in the fabrication of waste cotton based activated carbon used as electrode material for supercapacitor. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13(5), P. 565–573.Raveendran K. Pyrolysis characteristics of biomass and biomass components. Fuel, 1996, 75(8), P. 987–998.Raveendran K. Pyrolysis characteristics of biomass and biomass components. Fuel, 1996, 75(8), P. 987–998.Fu P., Hu S., Xiang J., Sun L., Su S., and An S. Study on the gas evolution and char structural change during pyrolysis of cotton stalk. J Anal Appl Pyrolysis, 2012, 97, P. 130–136.Fu P., Hu S., Xiang J., Sun L., Su S., and An S. Study on the gas evolution and char structural change during pyrolysis of cotton stalk. J Anal Appl Pyrolysis, 2012, 97, P. 130–136.Sing K.S.W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure and Applied Chemistry, 1985, 57(4), P. 603–619.Sing K.S.W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure and Applied Chemistry, 1985, 57(4), P. 603–619.Thommes M. et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 2015, 87(9–10), P. 1051–1069.Thommes M. et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 2015, 87(9–10), P. 1051–1069.Schutter C., Pohlmann S., and Balducci A. Industrial Requirements of Materials for Electrical Double Layer Capacitors: Impact on Current and ¨ Future Applications. Adv Energy Mater, 2019, 9(25), P. 1900334–1900344.Schutter C., Pohlmann S., and Balducci A. Industrial Requirements of Materials for Electrical Double Layer Capacitors: Impact on Current and ¨ Future Applications. Adv Energy Mater, 2019, 9(25), P. 1900334–1900344.

The authors declare that there are no conflicts of interest present.