Effect of two-dimensional graphene oxide on the phase change stability of carbon nanotubes and their application for thermal energy storage

  • Chenzhong Mu
  • Jia Yin SzeEmail author
  • Xuelong Chen
  • Alessandro Romagnoli
Research Paper


Acid-treated carbon nanotubes have a significant improvement on the phase change behavior of nanofluids through the elimination of supercooling degrees and improvement on thermal conductivity. However, it has been found that these carbon nanotubes aggregated after a single phase change cycle. In this study, this problem has been successfully solved by the incorporation of graphene oxide with acid-treated multi-walled carbon nanotubes (of diameters from 10 to 15 nm) to form an interpenetrated structure of nanofillers with good stability of at least 90 cycles. The efficacy of the carbon nanotubes and graphene oxide nanofillers with different ratios has been demonstrated to shorten the phase change duration of the nanofluids with insignificant reduction to their latent heat. The synergy of two different dimensional nanofillers prevented the aggregation of acid-treated carbon nanotubes without the use of surfactants and achieved high-energy storage capacity and reliability.


Carbon nanotubes Graphene oxide Thermal energy storage Cyclic stability Phase change materials 


Funding information

The authors are grateful to the support given by the National Research Foundation, Prime Minister’s Office, Singapore, under its Energy NIC grant (NRF Award No.: NRF-ENIC-SERTD-SMES-NTUJTCI3C-2016), to conduct this study.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Ali AHH, Noeres P, Pollerberg C (2008) Performance assessment of an integrated free cooling and solar powered single-effect lithium bromide-water absorption chiller. Sol Energy 82:1021–1030. CrossRefGoogle Scholar
  2. Aydin D, Casey SP, Riffat S (2015) The latest advancements on thermochemical heat storage systems. Renew Sust Energ Rev 41:356–367. CrossRefGoogle Scholar
  3. Barreneche C, Fernández AI, Mondragon R, Enrique Julia J, Ventura-Espinosa D, Mata J, Cabeza LF (2018) Influence of nanoparticle morphology and its dispersion ability regarding thermal properties of water used as phase change material. Appl Therm Eng 128:121–126. CrossRefGoogle Scholar
  4. Bi S, Liu M, Shen J, Hu XM, Zhang L (2017) Ultrahigh self-sensing performance of geopolymer nanocomposites via unique Interface engineering. ACS Appl Mater Interfaces 9:12851–12858. CrossRefGoogle Scholar
  5. Bryning MB, Milkie DE, Islam MF, Hough LA, Kikkawa JM, Yodh AG (2007) Carbon nanotube aerogels. Adv Mater 19:661–664. CrossRefGoogle Scholar
  6. Delgado AV, González-Caballero F, Hunter RJ, Koopal LK, Lyklema J (2007) Measurement and interpretation of electrokinetic phenomena. J Colloid Interface Sci 309:194–224. CrossRefGoogle Scholar
  7. Fan L-W, Yao X-L, Wang X, Wu Y-Y, Liu X-L, Xu X, Yu Z-T (2015) Non-isothermal crystallization of aqueous nanofluids with high aspect-ratio carbon nano-additives for cold thermal energy storage. Appl Energy 138:193–201. CrossRefGoogle Scholar
  8. Feng L, Zheng J, Yang H, Guo Y, Li W, Li X (2011) Preparation and characterization of polyethylene glycol/active carbon composites as shape-stabilized phase change materials. Sol Energy Mater Sol Cells 95:644–650. CrossRefGoogle Scholar
  9. Hou J, Du W, Meng F, Zhao C, Du X (2018) Effective dispersion of multi-walled carbon nanotubes in aqueous solution using an ionic-gemini dispersant. J Colloid Interface Sci 512:750–757. CrossRefGoogle Scholar
  10. Khodadadi JM, Fan L, Babaei H (2013) Thermal conductivity enhancement of nanostructure-based colloidal suspensions utilized as phase change materials for thermal energy storage: a review. Renew Sust Energ Rev 24:418–444. CrossRefGoogle Scholar
  11. Kim S, Drzal LT (2009) High latent heat storage and high thermal conductive phase change materials using exfoliated graphite nanoplatelets. Sol Energy Mater Sol Cells 93:136–142. CrossRefGoogle Scholar
  12. Kim KH, Vural M, Islam MF (2011) Single-walled carbon nanotube aerogel-based elastic conductors. Adv Mater 23:2865–2869. CrossRefGoogle Scholar
  13. Kumano H, Asaoka T, Saito A, Okawa S (2009) Formulation of the latent heat of fusion of ice in aqueous solution. Int J Refrig 32:175–182. CrossRefGoogle Scholar
  14. Lasfargues M, Bell A, Ding Y (2016) In situ production of titanium dioxide nanoparticles in molten salt phase for thermal energy storage and heat-transfer fluid applications. J Nanopart Res 18:150. CrossRefGoogle Scholar
  15. Li M (2013) A nano-graphite/paraffin phase change material with high thermal conductivity. Appl Energy 106:25–30. CrossRefGoogle Scholar
  16. Li M, Huang CP (2010) Stability of oxidized single-walled carbon nanotubes in the presence of simple electrolytes and humic acid. Carbon 48:4527–4534. CrossRefGoogle Scholar
  17. Li Y, Yang J, Zhao Q, Li Y (2013) Dispersing carbon-based nanomaterials in aqueous phase by graphene oxides. Langmuir 29:13527–13534. CrossRefGoogle Scholar
  18. Liu Y, Jiangqing W, Chuangjian S, Shichao G, Yongkun G, Quangui P (2017) Nucleation rate and supercooling degree of water-based graphene oxide nanofluids. Appl Therm Eng 115:1226–1236. CrossRefGoogle Scholar
  19. Ma G, Wang Z, Xie S, Sun J, Jia Y, Jing Y, Du G (2018) Preparation and properties of stearic acid–acetanilide eutectic mixture/expanded graphite composite phase-change material for thermal energy storage. Energy Technol 6:153–160. CrossRefGoogle Scholar
  20. Mantilla Gilart P, Yedra Martínez Á, González Barriuso M, Manteca Martínez C (2012) Development of PCM/carbon-based composite materials. Sol Energy Mater Sol Cells 107:205–211. CrossRefGoogle Scholar
  21. Mateus T, Oliveira AC (2009) Energy and economic analysis of an integrated solar absorption cooling and heating system in different building types and climates. Appl Energy 86:949–957. CrossRefGoogle Scholar
  22. Meng P, Zhang Q, Wu Y, Tan Z, Cheng G, Wu X, Zheng R (2017) Room-temperature dielectric switchable nanocomposites advanced functional materials:1701136-n/a doi:
  23. Mu C, Zhang L, Song Y, Chen X, Liu M, Wang F, Hu X (2016) Modification of carbon nanotubes by a novel biomimetic approach towards the enhancement of the mechanical properties of polyurethane. Polymer 92:231–238. CrossRefGoogle Scholar
  24. Raam Dheep G, Sreekumar A (2014) Influence of nanomaterials on properties of latent heat solar thermal energy storage materials – a review. Energy Convers Manag 83:133–148. CrossRefGoogle Scholar
  25. Shaikh S, Lafdi K, Hallinan K (2008) Carbon nanoadditives to enhance latent energy storage of phase change materials. J Appl Phys 103:094302. CrossRefGoogle Scholar
  26. Vitorino N, Abrantes JCC, Frade JR (2013) Gelled graphite/gelatin composites for latent heat cold storage. Appl Energy 104:890–897. CrossRefGoogle Scholar
  27. Wang Y, Liu Z, Zhang T, Zhang Z (2017) Preparation and characterization of graphene oxide-grafted hexadecanol composite phase-change material for thermal energy storage. Energy Technol 5:2005–2014. CrossRefGoogle Scholar
  28. Wu S, Zhu D, Zhang X, Huang J (2010) Preparation and melting/freezing characteristics of cu/paraffin nanofluid as phase-change material (PCM). Energy Fuel 24:1894–1898. CrossRefGoogle Scholar
  29. Xia L, Zhang P, Wang RZ (2010) Preparation and thermal characterization of expanded graphite/paraffin composite phase change material. Carbon 48:2538–2548. CrossRefGoogle Scholar
  30. Xie H, Wan J, Chen L (2008) Effects on the phase transformation temperature of nanofluids by the nanoparticles. J Mater Sci Technol 24:742Google Scholar
  31. Xu B, Li Z (2014) Paraffin/diatomite/multi-wall carbon nanotubes composite phase change material tailor-made for thermal energy storage cement-based composites. Energy 72:371–380. CrossRefGoogle Scholar
  32. Xu H, Romagnoli A, Sze JY, Py X (2017) Application of material assessment methodology in latent heat thermal energy storage for waste heat recovery. Appl Energy 187:281–290. CrossRefGoogle Scholar
  33. Yang Y, Oztekin A, Neti S, Mohapatra S (2012) Particle agglomeration and properties of nanofluids. J Nanopart Res 14:1–10. CrossRefGoogle Scholar
  34. Zeng JL, Liu YY, Cao ZX, Zhang J, Zhang ZH, Sun LX, Xu F (2008) Thermal conductivity enhancement of MWNTs on the PANI/tetradecanol form-stable PCM. J Therm Anal Calorim 91:443–446. CrossRefGoogle Scholar
  35. Zhang L, Shi H, Li W, Han X, Zhang X (2013) Structure and thermal performance of poly(ethylene glycol) alkyl ether (Brij)/porous silica (MCM-41) composites as shape-stabilized phase change materials. Thermochim Acta 570:1–7. CrossRefGoogle Scholar
  36. Zhang L, Pu J, Wang L, Xue Q (2015) Synergistic effect of hybrid carbon nanotube–graphene oxide as nanoadditive enhancing the frictional properties of ionic liquids in high vacuum. ACS Appl Mater Interfaces 7:8592–8600. CrossRefGoogle Scholar
  37. Zhang S, Wu W, Wang S (2017) Preparation, thermal properties and thermal reliability of a novel mid-temperature composite phase change material for energy conservation. Energy 130:228–235. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Energy Research InstituteNanyang Technological UniversitySingaporeSingapore
  2. 2.School of Materials Science and EngineeringNanyang Technological UniversitySingaporeSingapore
  3. 3.School of Mechanical and Aerospace EngineeringNanyang Technological UniversitySingaporeSingapore

Personalised recommendations