Environmental Science and Pollution Research

, Volume 26, Issue 14, pp 14693–14702 | Cite as

Ball-milled biochar for alternative carbon electrode

  • Honghong Lyu
  • Zebin YuEmail author
  • Bin Gao
  • Feng He
  • Jun Huang
  • Jingchun TangEmail author
  • Boxiong Shen
Short Research and Discussion Article


Ball-milled biochars (BM-biochars) were produced through ball milling of pristine biochars derived from different biomass at three pyrolysis temperatures (300, 450, and 600 °C). The results of scanning electron microscopic (SEM), surface area, hydrodynamic diameter test, and Fourier transform infrared spectroscopy (FTIR) revealed that BM-biochars had smaller particle size (140–250 nm compared to 0.5–1 mm for unmilled biochar), greater stability, and more oxygen-containing functional groups (2.2–4.4 mmol/g compared to 0.8–2.9 for unmilled biochar) than the pristine biochars. With these changes, all the BM-biochar-modified glassy carbon electrodes (BM-biochar/GCEs) exhibited prominent electrochemical properties (e.g., ΔEp of 119–254 mV compared to 850 mV for bare GCE). Cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) show that ball-milled 600 °C biochar/GCE (BMBB600/GCE and BMBG600/GCE) had the smallest peak-to-peak separation (ΔEp = 119 and 132 mV, respectively), series resistance (RS = 88.7 and 89.5 Ω, respectively), and charge transfer resistance (RCT = 1224 and 1382 Ω, respectively), implying its best electrocatalytic activity for the reduction of Fe(CN)63−. It is supposed that the special structure (i.e., internal surface area, pore volume, oxygen-containing functional groups, and graphitic structure) facilitates the electron transfer and reduces interface resistance. Economic cost of BM-biochar/GCE was 1.97 × 10−7 USD/cm2, much lower than that of a “low-cost platinum electrode” (0.03 USD/cm2). The results indicate potential application of the novel BM-biochar for low cost and high efficient electrodes.

Graphical abstract


Ball-milled biochar Electrode Surface area Oxygen-containing functional groups Mechanisms 


Funding information

This work was partially supported by the Key Laboratory of Original Agro-Environmental Pollution Prevention and Control, Ministry of Agriculture/Tianjin Key Laboratory of Agro-environment and Safe-product [18nybcdhj-5 and 18nybcdhj-1], the National Natural Science Foundation of China (41807363), Guangxi Natural Science Foundation (Nos.AD17195058), the Key Research and Development Project of the Ministry of Science and Technology (2018YFB0605101), and the Key Project Natural Science Foundation of Tianjin (18JCZDJC39800).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11356_2019_4899_MOESM1_ESM.docx (5.8 mb)
ESM 1 (DOCX 5916 kb)


  1. Bal AltuntaŞ D, AkgÜL G, Yanik J, Anik Ü (2017) A biochar-modified carbon paste electrode. Turk J Chem 41:455–465. CrossRefGoogle Scholar
  2. Chen L, Tang Y, Wang K, Liu C, Luo S (2011) Direct electrodeposition of reduced graphene oxide on glassy carbon electrode and its electrochemical application. Electrochem Commun 13:133–137. CrossRefGoogle Scholar
  3. Chen J, Chen Q, Ma Q, Li Y, Zhu Z (2012) Chemical treatment of CNTs in acidic KMnO 4 solution and promoting effects on the corresponding Pd–Pt/CNTs catalyst. J Mol Catal A:Chem 356:114–120.
  4. Chen Z, Xiao X, Chen B, Zhu L (2015) Quantification of chemical states, dissociation constants and contents of oxygen-containing groups on the surface of biochars produced at different temperatures. Environ Sci Technol 49:309–317. CrossRefGoogle Scholar
  5. Chen J, Li Q, Zhang L, Zheng C (2017) Application and economic benefit analysis of ceramic continuous ball milling system. China Ceram 53:71–73Google Scholar
  6. Cheng BH, Zeng RJ, Jiang H (2017) Recent developments of post-modification of biochar for electrochemical energy storage. Bioresour Technol 246:224–233. CrossRefGoogle Scholar
  7. Choi J, Jin J, Jung IG, Kim JM, Kim HJ, Son SU (2011) SnSe2 nanoplate-graphene composites as anode materials for lithium ion batteries. Chem Commun (Camb) 47:5241–5243. CrossRefGoogle Scholar
  8. Creamer AE, Gao B, Zhang M (2014) Carbon dioxide capture using biochar produced from sugarcane bagasse and hickory wood. Chem Eng J 249:174–179. CrossRefGoogle Scholar
  9. Gabhi RS, Kirk DW, Jia CQ (2017) Preliminary investigation of electrical conductivity of monolithic biochar. Carbon 116:435–442. CrossRefGoogle Scholar
  10. Gao J, Wang W, Rondinone AJ, He F, Liang LY (2015) Degradation of trichloroethene with a novel ball milled Fe-C nanocomposite. J Hazard Mater 300:443–450. CrossRefGoogle Scholar
  11. Gong Y, Tang J, Zhao D (2016) Application of iron sulfide particles for groundwater and soil remediation: a review. Water Res 89:309–320 CrossRefGoogle Scholar
  12. Gu Y, Wang B, He F, Bradley MJ, Tratnyek PG (2017) Mechanochemically sulfidated microscale zero valent iron: pathways, kinetics, mechanism, and efficiency of trichloroethylene dechlorination. Environ Sci Technol 51:12653–12,662CrossRefGoogle Scholar
  13. Guai GH, Leiw MY, Ng CM, Li CM (2012) Sulfur-doped nickel oxide thin film as an alternative to Pt for dye-sensitized solar cell counter electrodes. Adv Energy Mater 2:334–338. CrossRefGoogle Scholar
  14. Huggins T, Wang HM, Kearns J, Jenkins P, Ren ZJ (2014) Biochar as a sustainable electrode material for electricity production in microbial fuel cells. Bioresour Technol 157:114–119. CrossRefGoogle Scholar
  15. Ju MJ, Jeon IY, Lim K, Kim JC, Choi HJ, Choi IT, Eom YK, Kwon YJ, Ko J, Lee JJ, Baek JB, Kim HK (2014) Edge-carboxylated graphene nanoplatelets as oxygen-rich metal-free cathodes for organic dye-sensitized solar cells. Energy Environ Sci 7:1044–1052. CrossRefGoogle Scholar
  16. Kruusenberg I, Matisen L, Jiang H, Huuppola M, Kontturi K, Tammeveski K (2010) Electrochemical reduction of oxygen on double-walled carbon nanotube modified glassy carbon electrodes in acid and alkaline solutions. Electrochem Commun 12:920–923. CrossRefGoogle Scholar
  17. Li Q, Wu J, Tang Q, Lan Z, Li P, Lin J, Fan L (2008) Application of microporous polyaniline counter electrode for dye-sensitized solar cells. Electrochem Commun 10:1299–1302. CrossRefGoogle Scholar
  18. Li GR, Wang F, Jiang QW, Gao XP, Shen PW (2010) Carbon nanotubes with titanium nitride as a low-cost counter-electrode material for dye-sensitized solar cells. Angew Chem Int Ed Eng 49:3653–3656. CrossRefGoogle Scholar
  19. Li G, Chen X, Gao G (2014) Bi2S3 microspheres grown on graphene sheets as low-cost counter-electrode materials for dye-sensitized solar cells. Nanoscale 6:3283–3288. CrossRefGoogle Scholar
  20. Lyu H, Gao B, He F, Ding C, Tang J, Crittenden JC (2017) Ball-milled carbon nanomaterials for energy and environmental applications. ACS Sustain Chem Eng 5:9568–9585. CrossRefGoogle Scholar
  21. Lyu H, Gao B, He F, Zimmerman AR, Ding C, Huang H, Tang J (2018a) Effects of ball milling on the physicochemical and sorptive properties of biochar: experimental observations and governing mechanisms. Environ Pollut 233:54–63. CrossRefGoogle Scholar
  22. Lyu H, Gao B, He F, Zimmerman AR, Ding C, Tang J, Crittenden JC (2018b) Experimental and modeling investigations of ball-milled biochar for the removal of aqueous methylene blue. Chem Eng J 335:110–119. CrossRefGoogle Scholar
  23. Magnacca G, Guerretta F, Vizintin A, Benzi P, Valsania MC, Nisticò R (2018) Preparation, characterization and environmental/electrochemical energy storage testing of low-cost biochar from natural chitin obtained via pyrolysis at mild conditions. Appl Surf Sci 427:883–893. CrossRefGoogle Scholar
  24. Mukherjee A, Zimmerman AR, Harris W (2011) Surface chemistry variations among a series of laboratory-produced biochars. Geoderma 163:247–255. CrossRefGoogle Scholar
  25. Musameh M, Wang J, Merkoci A, Lin Y (2002) Low-potential stable NADH detection at carbon-nanotube-modified glassy carbon electrodes. Electrochem Commun 4:743–746.
  26. Nagaraju G, Lim JH, Cha SM, Yu JS (2017) Three-dimensional activated porous carbon with meso/macropore structures derived from fallen pine cone flowers: a low-cost counter electrode material in dye-sensitized solar cells. J Alloys Compd 693:1297–1304. CrossRefGoogle Scholar
  27. Pereira R, Marchesi LF, Freitas RG, Matos R, Pereira EC (2013) A low-cost platinum film deposited direct on glass substrate forelectrochemical counter electrodes. J Power Sources 232:254–257CrossRefGoogle Scholar
  28. Pringle JM, Armel V, Macfarlane DR (2010) Electrodeposited PEDOT-on-plastic cathodes for dye-sensitized solar cells. Chem Commun 46:5367–5369CrossRefGoogle Scholar
  29. Shao L-L, Chen M, Yuan Z-Y (2014) Hierarchical porous carbons as a metal-free electrocatalyst of triiodide reduction for dye-sensitized solar cells. J Power Sources 272:1091–1099. CrossRefGoogle Scholar
  30. Vikrant K, Kim K-H, Ok YS, Tsang DCW, Tsang YF, Giri BS, Singh RS (2018) Engineered/designer biochar for the removal of phosphate in water and wastewater. Sci Total Environ 616:1242–1260. CrossRefGoogle Scholar
  31. Wan S, Wu J, Zhou S, Wang R, Gao B, He F (2018) Enhanced lead and cadmium removal using biochar-supported hydrated manganese oxide (HMO) nanoparticles: behavior and mechanism. Sci Total Environ 616-617:1298–1306CrossRefGoogle Scholar
  32. Wang S, Gao B, Li Y, Creamer AE, He F (2017) Adsorptive removal of arsenate from aqueous solutions by biochar supported zero-valent iron nanocomposite: batch and continuous flow tests. J Hazard Mater 322:172–181. CrossRefGoogle Scholar
  33. Wei J, Liang P, Huang X (2011) Recent progress in electrodes for microbial fuel cells. Bioresour Technol 102:9335–9344. CrossRefGoogle Scholar
  34. Wu J, Li Q, Fan L, Zhang L, Li P, Lin J, Hao S (2008) High-performance polypyrrole nanoparticles counter electrode for dye-sensitized solar cells. J Power Sources 181:172–176CrossRefGoogle Scholar
  35. Wu MX, Lin X, Wang TH, Qiu JS, Ma TL (2011) Low-cost dye-sensitized solar cell based on nine kinds of carbon counter electrodes. Energy Environ Sci 4:2308–2315. CrossRefGoogle Scholar
  36. Xu SJ (2016) Photovoltaic properties of 9 natural leaves derived biochars as counter electrodes for dye-sensitized solar cells. J Chem Ind Eng (China) 67:4851–4857. Google Scholar
  37. Yoon K, Cho D-W, Tsang DCW, Bolan N, Rinklebe J, Song H (2017) Fabrication of engineered biochar from paper mill sludge and its application into removal of arsenic and cadmium in acidic water. Bioresour Technol 246:69–75. CrossRefGoogle Scholar
  38. You S, Ok YS, Chen SS, Tsang DCW, Kwon EE, Lee J, Wang CH (2017) A critical review on sustainable biochar system through gasification: energy and environmental applications. Bioresour Technol 246:242–253. CrossRefGoogle Scholar
  39. Yuan Y, Yuan T, Wang D, Tang J, Zhou S (2013) Sewage sludge biochar as an efficient catalyst for oxygen reduction reaction in an microbial fuel cell. Bioresour Technol 144:115–120. CrossRefGoogle Scholar
  40. Zhang X, Yang Y, Guo S, Hu F, Liu L (2015) Mesoporous Ni0.85Se nanospheres grown in situ on graphene with high performance in dye-sensitized solar cells. ACS Appl Mater Interfaces 7:8457–8464. CrossRefGoogle Scholar
  41. Zhao X, Liu W, Cai Z, Han B, Qian T, Zhao D (2016) An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation. Water Res 100:245–266. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Original Agro-Environmental Pollution Prevention and Control, Ministry of Agriculture/Tianjin Key Laboratory of Agro-environment and Safe-product, School of Energy and Environmental EngineeringHebei University of TechnologyTianjinChina
  2. 2.School of Resources, Environment and MaterialsGuangxi UniversityNanningChina
  3. 3.Department of Agricultural and Biological EngineeringUniversity of FloridaGainesvilleUSA
  4. 4.College of EnvironmentZhejiang University of TechnologyHangzhouChina
  5. 5.Hualan Design and Consulting Group Co. Ltd.NanningChina
  6. 6.College of Civil Engineering and ArchitectureGuangxi UniversityNanningChina
  7. 7.Key Laboratory of Pollution Processes and Environmental Criteria (Ministry of Education), Tianjin Engineering Center of Environmental Diagnosis and Contamination Remediation, College of Environmental Science and EngineeringNankai UniversityTianjinChina

Personalised recommendations