Fabricating sustainable lignin-derived porous carbon as electrode for high-performance supercapacitors

Abstract

Lignocellulosic biomass such as plants and agricultural waste are ideal to tackle the current energy crisis and energy-related environmental issues. Carbon-rich lignin is abundant in lignocellulosic biomass, whose high-value transformation and utilization has been the most urgent problem to be solved. Herein, we propose a method for the preparation of porous carbon from lignin employing an H₃PO₄-assisted hydrothermal method. We characterize the as-prepared lignin-derived porous carbon and investigate its potential for energy storage. After assisted hydrothermal treatment followed by carbonization at 800 °C, the lignin-derived porous carbon displays a high specific capacitance (223.6 F·g^–1 at 0.1 A·g^–1) and excellent cycling ability with good capacitance retention. In this present study, the resultant lignin-derived porous carbon was used as the electrode of a supercapacitor, illustrating yet another potential high-value use for lignin, namely as a candidate for the sustainable fabrication of main supercapacitor components.

Key words： lignin; porous carbon; electrode; supercapacitor

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

The authors wish to express their gratitude for the financial support from the National Science Foundation for Post-doctoral Scientists of China (Grant No. 2019M651050), and Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, College of Light Industry and Food Engineering, Guangxi University (Grant No. 2019KF32).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2313-0 and is accessible for authorized users.

References

1 Paraschiv S, Paraschiv L S. Trends of carbon dioxide (CO₂) emissions from fossil fuels combustion (coal, gas and oil) in the EU member states from 1960 to 2018. Energy Reports, 2020, 6: 237–242

2 Ragauskas A J, Beckham G T, Biddy M J, Chandra R, Chen F, Davis M F, Davison B H, Dixon R A, Gilna P, Keller M, Langan P, Naskar A K, Saddler J N, Tschaplinski T J, Tuskan G A, Wyman C E. Lignin valorization: improving lignin processing in the biorefinery. Science, 2014, 344(6185): 1246843

3 Liu F, Wang Z, Zhang H, Zhang H, Jin L, Chu X, Gu B, Huang H, Yang W. Nitrogen, oxygen and sulfur codoped hierarchical porous carbons toward high-performance supercapacitors by direct pyrolysis of kraft lignin. Carbon, 2019, 149: 105–116

4 Ding Z, Li F, Wen J, Wang X, Sun R. Gram-scale synthesis of single-crystalline graphene quantum dots derived from lignin biomass. Green Chemistry, 2018, 20(6): 1383–1390

5 Xiong C, Zheng C, Li B, Ni Y. Wood-based micro-spring composite elastic material with excellent electrochemical performace, high elasticity and elastic recovery rate applied in supercapacitors and sensors. Industrial Crops and Products, 2022, 178: 114565

6 Xiong C, Wang T, Zhang Y, Li B, Han Q, Li D, Ni Y. Li–Na metal compounds inserted into porous natural wood as a bifunctional hybrid applied in supercapacitors and electrocatalysis. International Journal of Hydrogen Energy, 2022, 47(4): 2389–2398

7 Torres-Canas F, Bentaleb A, Fӧllmer M, Roman J, Neri W, Ly I, Derré A, Poulin P. Improved structure and highly conductive lignin-carbon fibers through graphene oxide liquid crystal. Carbon, 2020, 163: 120–127

8 Xu X, Zhou J, Nagaraju D H, Jiang L, Marinov V R, Lubineau G, Alshareef H N, Oh M. Flexible, highly graphitized carbon aerogels based on bacterial cellulose/lignin: catalyst-free synthesis and its application in energy storage devices. Advanced Functional Materials, 2015, 25(21): 3193–3202

9 Liu Y, Shi M, Han M, Yang J, Yu J, Narayanasamy M, Dai K, Angaiah S, Yan C. Spontaneous exfoliation and tailoring derived oxygen-riched porous carbon nanosheets for superior Li⁺ storage performance. Chemical Engineering Journal, 2020, 387: 124104

10 Xue C, Feng L, Hao Y, Yang F, Zhang Q, Ma X, Hao X. Acid-free synthesis of oxygen-enriched electroactive carbon with unique square pores from salted seaweed for robust supercapacitor with attractive energy density. Green Chemistry, 2018, 20(21): 4983–4994

11 Sun M, Wang X, Ni S, Jiao L, Bian H, Dai H. Structural modification of alkali lignin into higher performance energy storage materials: demethylation and cleavage of aryl ether bonds. Industrial Crops and Products, 2022, 187: 115441

12 Zhang B, Yang D, Qiu X, Qian Y, Yan M, Li Q. Influences of aggregation behavior of lignin on the microstructure and adsorptive properties of lignin-derived porous carbons by potassium compound activation. Journal of Industrial and Engineering Chemistry, 2020, 82: 220–227

13 Cotoruelo L M, Marqués M D, Díaz F J, Rodríguez-Mirasol J, Rodríguez J J, Cordero T. Lignin-based activated carbons as adsorbents for crystal violet removal from aqueous solutions. Environmental Progress & Sustainable Energy, 2012, 31(3): 386–396

14 Xi Y, Huang S, Yang D, Qiu X, Su H, Yi C, Li Q. Hierarchical porous carbon derived from the gas-exfoliation activation of lignin for high-energy lithium-ion batteries. Green Chemistry, 2020, 22(13): 4321–4330

15 Lu T, Ma C, Demir M, Yu Q, Aghamohammadi P, Wang L, Hu X. One-pot synthesis of potassium benzoate-derived porous carbon for CO₂ capture and supercapacitor application. Separation and Purification Technology, 2022, 301: 122053

16 Ma C, Bai J, Demir M, Hu X, Liu S, Wang L. Water chestnut shell-derived N/S-doped porous carbons and their applications in CO₂ adsorption and supercapacitor. Fuel, 2022, 326: 125119

17 Wen F, Zhang W, Jian W, He X, Yin J, Shi J, Lin H, Lu K, Qin Y, Qiu X. Sustainable production of lignin-derived porous carbons for high-voltage electrochemical capacitors. Chemical Engineering Science, 2022, 255: 117672

18 Wu Y, Cao J P, Zhao X Y, Zhuang Q Q, Zhou Z, Huang Y, Wei X Y. High-performance electrode material for electric double-layer capacitor based on hydrothermal pre-treatment of lignin by ZnCl₂. Applied Surface Science, 2020, 508: 144536

19 Zhao X, Chen H, Kong F, Zhang Y, Wang S, Liu S, Lucia L A, Fatehi P, Pang H. Fabrication, characteristics and applications of carbon materials with different morphologies and porous structures produced from wood liquefaction: a review. Chemical Engineering Journal, 2019, 364: 226–243

20 Zhang T, Jiang D, Li Y, Zhang H, Zhang Z, Jing Y, Lu C, Zhang Y, Xia C, Zhang Q. Lignin removal, reducing sugar yield and photo-fermentative biohydrogen production capability of corn stover: effects of different pretreatments. Bioresource Technology, 2022, 346: 126437

21 Kaparaju P, Felby C. Characterization of lignin during oxidative and hydrothermal pre-treatment processes of wheat straw and corn stover. Bioresource Technology, 2010, 101(9): 3175–3181

22 Chen S, Zhao L, Ma J, Wang Y, Dai L, Zhang J. Edge-doping modulation of N, P-codoped porous carbon spheres for high-performance rechargeable Zn-air batteries. Nano Energy, 2019, 60: 536–544

23 Sánchez-Leija R J, López-Salas N, Fierro J L G, Gutiérrez M C, Ferrer M L, Mota-Morales J D, Luna-Bárcenas G, Monte F. Deep eutectic solvents as active media for the preparation of highly conducting 3D free-standing PANI xerogels and their derived N-doped and N-, P-codoped porous carbons. Carbon, 2019, 146: 813–826

24 Zhou C, Wang D, Li A, Pan E, Liu H, Chen X, Jia M, Song H. Three-dimensional porous carbon doped with N, O and P heteroatoms as high-performance anode materials for sodium ion batteries. Chemical Engineering Journal, 2020, 380: 122457

25 Chen J, Chang B, Liu F, Wei H, Wei W, Lin H, Han S. Modification of porous carbon with nitrogen elements to enhance the capacitance of supercapacitors. Journal of Materials Science, 2019, 54(18): 11959–11971

26 Yang S, Wen J L, Yuan T Q, Sun R C. Characterization and phenolation of biorefinery technical lignins for lignin-phenol-formaldehyde resin adhesive synthesis. RSC Advances, 2014, 4(101): 57996–58004

27 Shu Y, Bai Q, Fu G, Xiong Q, Li C, Ding H, Shen Y, Uyama H. Hierarchical porous carbons from polysaccharides carboxymethyl cellulose, bacterial cellulose, and citric acid for supercapacitor. Carbohydrate Polymers, 2020, 227: 115346

28 Li Y, Wang G, Wei T, Fan Z, Yan P. Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors. Nano Energy, 2016, 19: 165–175

29 Xu Y, Wang S, Hou X, Sun Z, Jiang Y, Dong Z, Tao Q, Man J, Cao Y. Coal-derived nitrogen, phosphorus and sulfur co-doped graphene quantum dots: a promising ion fluorescent probe. Applied Surface Science, 2018, 445: 519–526

30 Yorgun S, Yıldız D. Preparation and characterization of activated carbons from Paulownia wood by chemical activation with H₃PO₄. Journal of the Taiwan Institute of Chemical Engineers, 2015, 53: 122–131

31 Ma X, Su C, Liu B, Wu Q, Zhou K, Zeng Z, Li L. Heteroatom-doped porous carbons exhibit superior CO₂ capture and CO₂/N₂ selectivity: understanding the contribution of functional groups and pore structure. Separation and Purification Technology, 2021, 259: 118065

32 Chen W, Luo M, Yang K, Zhou X. Microwave-assisted KOH activation from lignin into hierarchically porous carbon with super high SSA by utilizing the dual roles of inorganic salts: microwave absorber and porogen. Microporous and Mesoporous Materials, 2020, 300: 110178

33 Zhu L, Shen F, Smith R L Jr, Yan L, Li L, Qi X. Black liquor-derived porous carbons from rice straw for high-performance supercapacitors. Chemical Engineering Journal, 2017, 316: 770–777

34 Mao J, Iocozzia J, Huang J, Meng K, Lai Y, Lin Z. Graphene aerogels for efficient energy storage and conversion. Energy & Environmental Science, 2018, 11(4): 772–799

35 Li H, Zhao Y, Liu S, Li P, Yuan D, He C. Hierarchical porous carbon monolith derived from lignin for high areal apacitance supercapacitors. Microporous and Mesoporous Materials, 2020, 297: 109960

36 Zeng L, Lou X, Zhang J, Wu C, Liu J, Jia C. Carbonaceous mudstone and lignin-derived activated carbon and its application for supercapacitor electrode. Surface and Coatings Technology, 2019, 357: 580–586

37 Li H, Yuan D, Tang C, Wang S, Sun J, Li Z, Tang T, Wang F, Gong H, He C. Lignin-derived interconnected hierarchical porous carbon monolith with large areal/volumetric capacitances for supercapacitor. Carbon, 2016, 100: 151–157

38 Xu J, Zhou X, Chen M, Shi S, Cao Y. Preparing hierarchical porous carbon aerogels based on enzymatic hydrolysis lignin through ambient drying for supercapacitor electrodes. Microporous and Mesoporous Materials, 2018, 265: 258–265

39 Yu B M, Gele A, Wang L P. Iron oxide/lignin-based hollow carbon nanofibers nanocomposite as an application electrode materials for supercapacitors. International Journal of Biological Macromolecules, 2018, 118: 478–484

40 Chen W M, Wang X, Feizbakhshan M, Liu C, Hong S, Yang P, Zhou X. Preparation of lignin-based porous carbon with hierarchical oxygen-enriched structure for high-performance supercapacitors. Journal of Colloid and Interface Science, 2019, 540: 524–534