Skip to main content
SpringerLink
Log in

Capillary shrinkage of graphene oxide hydrogels

氧化石墨烯水凝胶的毛细收缩机制

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Conventional carbon materials cannot combine high density and high porosity, which are required in many applications, typically for energy storage under a limited space. A novel highly dense yet porous carbon has previously been produced from a three-dimensional (3D) reduced graphene oxide (r-GO) hydrogel by evaporation-induced drying. Here the mechanism of such a network shrinkage in r-GO hydrogel is specifically illustrated by the use of water and 1,4-dioxane, which have a sole difference in surface tension. As a result, the surface tension of the evaporating solvent determines the capillary forces in the nanochannels, which causes shrinkage of the r-GO network. More promisingly, the selection of a solvent with a known surface tension can precisely tune the microstructure associated with the density and porosity of the resulting porous carbon, rendering the porous carbon materials great potential in practical devices with high volumetric performance.

摘要

以两亲性氧化石墨烯为结构单元, 可控组装构建三维网络石 墨烯水凝胶, 动网络致密化, 获得高密多孔碳, 解决 了传统多孔碳电极体积容量低的应用瓶颈. 本文旨在探究氧化石 墨烯水凝胶致密化机理, 阐明了毛细作用力是使溶剂脱出并引发 石墨烯网络收缩的驱动力. 溶剂表面张力决定毛细作用力, 因此通 过调节溶剂表面张力或采用不同表面张力的溶剂, 可以实现“孔”与 “密”的“收放自如”调控, 从而得到不同密度和孔隙率的高密多孔碳, 实现高密和多孔连续精确调控. 氧化石墨烯水凝胶的毛细收缩也 为纳米材料致密化提供了方法论支持.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Geim AK, Novoselov KS. The rise of graphene. Nat Mater, 2007, 6: 183–191

    CAS  Google Scholar 

  2. Allen MJ, Tung VC, Kaner RB. Honeycomb carbon: a review of graphene. Chem Rev, 2009, 110: 132–145

    Google Scholar 

  3. Ye C, Zhou X, Pu D, et al. Rapid cycling of reactive nitrogen in the marine boundary layer. Nature, 2016, 532: 489–491

    CAS  Google Scholar 

  4. Ju Z, Li P, Ma G, et al. Few layer nitrogen-doped graphene with highly reversible potassium storage. Energy Storage Mater, 2018, 11: 38–46

    Google Scholar 

  5. Liu L, Lin Z, Chane-Ching JY, et al. 3D rGO aerogel with superior electrochemical performance for K-Ion battery. Energy Storage Mater, 2019, 19: 306–313

    Google Scholar 

  6. Raymundo-Piñero E, Leroux F, Béguin F. A high-performance carbon for supercapacitors obtained by carbonization of a seaweed biopolymer. Adv Mater, 2006, 18: 1877–1882

    Google Scholar 

  7. Zhang C, Lv W, Tao Y, et al. Towards superior volumetric performance: design and preparation of novel carbon materials for energy storage. Energy Environ Sci, 2015, 8: 1390–1403

    CAS  Google Scholar 

  8. Wang Q, Yan J, Fan Z. Carbon materials for high volumetric performance supercapacitors: design, progress, challenges and opportunities. Energy Environ Sci, 2016, 9: 729–762

    CAS  Google Scholar 

  9. Liu C, Yan X, Hu F, et al. Toward superior capacitive energy storage: recent advances in pore engineering for dense electrodes. Adv Mater, 2018, 30: 1705713

    Google Scholar 

  10. Zhou Y, Ghaffari M, Lin M, et al. High volumetric electrochemical performance of ultra-high density aligned carbon nanotube supercapacitors with controlled nanomorphology. Electrochim Acta, 2013, 111: 608–613

    CAS  Google Scholar 

  11. Murali S, Quarles N, Zhang LL, et al. Volumetric capacitance of compressed activated microwave-expanded graphite oxide (a-MEGO) electrodes. Nano Energy, 2013, 2: 764–768

    CAS  Google Scholar 

  12. Tao Y, Xie X, Lv W, et al. Towards ultrahigh volumetric capacitance: graphene derived highly dense but porous carbons for supercapacitors. Sci Rep, 2013, 3: 2975–2982

    Google Scholar 

  13. Li H, Tao Y, Zheng X, et al. Compressed porous graphene particles for use as supercapacitor electrodes with excellent volumetric performance. Nanoscale, 2015, 7: 18459–18463

    CAS  Google Scholar 

  14. Zhang C, Liu DH, Lv W, et al. A high-density graphene-sulfur assembly: a promising cathode for compact Li-S batteries. Nanoscale, 2015, 7: 5592–5597

    CAS  Google Scholar 

  15. Xu Y, Tao Y, Zheng X, et al. A metal-free supercapacitor electrode material with a record high volumetric capacitance over 800 F cm−3. Adv Mater, 2015, 27: 8082–8087

    CAS  Google Scholar 

  16. Zhang C, Yang QH. Packing sulfur into carbon framework for high volumetric performance lithium-sulfur batteries. Sci China Mater, 2015, 58: 349–354

    CAS  Google Scholar 

  17. Qin L, Zhai D, Lv W, et al. Dense graphene monolith oxygen cathodes for ultrahigh volumetric energy densities. Energy Storage Mater, 2017, 9: 134–139

    Google Scholar 

  18. Zhang J, Lv W, Tao Y, et al. Ultrafast high-volumetric sodium storage of folded-graphene electrodes through surface-induced redox reactions. Energy Storage Mater, 2015, 1: 112–118

    Google Scholar 

  19. Dreyer DR, Park S, Bielawski CW, et al. The chemistry of graphene oxide. Chem Soc Rev, 2010, 39: 228–240

    CAS  Google Scholar 

  20. Kim J, Cote LJ, Kim F, et al. Graphene oxide sheets at interfaces. J Am Chem Soc, 2010, 132: 8180–8186

    CAS  Google Scholar 

  21. Dikin DA, Stankovich S, Zimney EJ, et al. Preparation and characterization of graphene oxide paper. Nature, 2007, 448: 457–460

    CAS  Google Scholar 

  22. Zhao Y, Hu C, Hu Y, et al. A versatile, ultralight, nitrogen-doped graphene framework. Angew Chem Int Ed, 2012, 51: 11371–11375

    CAS  Google Scholar 

  23. Ge J, Shi LA, Wang YC, et al. Joule-heated graphene-wrapped sponge enables fast clean-up of viscous crude-oil spill. Nat Nanotech, 2017, 12: 434–440

    CAS  Google Scholar 

  24. Shao JJ, Lv W, Yang QH. Self-assembly of graphene oxide at interfaces.. Adv Mater, 2014, 26: 5586–5612

    CAS  Google Scholar 

  25. Cong HP, Chen JF, Yu SH. Graphene-based macroscopic assemblies and architectures: an emerging material system. Chem Soc Rev, 2014, 43: 7295–7325

    CAS  Google Scholar 

  26. Chen W, Yan L. In situ self-assembly of mild chemical reduction graphene for three-dimensional architectures. Nanoscale, 2011, 3: 3132

    CAS  Google Scholar 

  27. Xu Y, Sheng K, Li C, et al. Self-assembled graphene hydrogel via a one-step hydrothermal process. ACS Nano, 2010, 4: 4324–4330

    CAS  Google Scholar 

  28. Xu Y, Lin Z, Zhong X, et al. Solvated graphene frameworks as high-performance anodes for lithium-ion batteries. Angew Chem Int Ed, 2015, 54: 5345–5350

    CAS  Google Scholar 

  29. Padmajan Sasikala S, Poulin P, Aymonier C. Prospects of supercritical fluids in realizing graphene-based functional materials. Adv Mater, 2016, 28: 2663–2691

    CAS  Google Scholar 

  30. Qiu L, Liu JZ, Chang SLY, et al. Biomimetic superelastic graphene-based cellular monoliths. Nat Commun, 2012, 3: 1241–1246

    Google Scholar 

  31. Sun H, Xu Z, Gao C. Multifunctional, ultra-flyweight, synergistically assembled carbon aerogels. Adv Mater, 2013, 25: 2554–2560

    CAS  Google Scholar 

  32. Job N, Théry A, Pirard R, et al. Carbon aerogels, cryogels and xerogels: Influence of the drying method on the textural properties of porous carbon materials. Carbon, 2005, 43: 2481–2494

    CAS  Google Scholar 

  33. Yang X, Cheng C, Wang Y, et al. Liquid-mediated dense integration of graphene materials for compact capacitive energy storage. Science, 2013, 341: 534–537

    CAS  Google Scholar 

  34. Tao Y, Kong D, Zhang C, et al. Monolithic carbons with spheroidal and hierarchical pores produced by the linkage of functionalized graphene sheets. Carbon, 2014, 69: 169–177

    CAS  Google Scholar 

  35. Jia X, Zhang C, Liu J, et al. Evolution of the effect of sulfur confinement in graphene-based porous carbons for use in Li-S batteries. Nanoscale, 2016, 8: 4447–4451

    CAS  Google Scholar 

  36. Sierra U, Álvarez P, Santamaría R, et al. A multi-step exfoliation approach to maintain the lateral size of graphene oxide sheets. Carbon, 2014, 80: 830–832

    CAS  Google Scholar 

  37. Nair RR, Wu HA, Jayaram PN, et al. Unimpeded permeation of water through helium-leak-tight graphene-based membranes. Science, 2012, 335: 442–444

    CAS  Google Scholar 

  38. Hovorka F, Schaefer RA, Dreisbach D. The system dioxane and water. J Am Chem Soc, 1936, 58: 2264–2267

    CAS  Google Scholar 

  39. Baker NB, Gilbert EC. Surface tension in the system hydrazine—water at 25°. J Am Chem Soc, 1940, 62: 2479–2480

    CAS  Google Scholar 

  40. Thommes M, Kaneko K, Neimark AV, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem, 2015, 87: 1051–1069

    CAS  Google Scholar 

  41. Steiner T. The hydrogen bond in the solid state. Angew Chem Int Ed, 2002, 41: 48–76

    CAS  Google Scholar 

  42. Xu X, Zhang Q, Yu Y, et al. Naturally dried graphene aerogels with superelasticity and tunable Poisson’s ratio. Adv Mater, 2016, 28: 9223–9230

    CAS  Google Scholar 

  43. Shang T, Lin Z, Qi C, et al. 3D macroscopic architectures from self-assembled MXene hydrogels. Adv Funct Mater, 2019, 29: 1903960

    Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Fund for the Distinguished Young Scholars, China (51525204), the National Natural Science Foundation of China (51702229 and 51872195), the CAS Key Laboratory of Carbon Materials (KLCM KFJJ1704).

Author information

Author notes

  1. These authors are equal major contributors to this work.

Authors and Affiliations

  1. Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin, 300350, China

    Changsheng Qi  (戚昌盛), Ying Tao  (陶莹), Huan Li  (李欢), Junwei Han  (韩俊伟) & Quan-Hong Yang  (杨全红)

  2. Shenzhen Geim Graphene Center and Engineering Laboratory for Functionalized Carbon Materials, Graduate School at Shenzhen, Tsinghua University, Shenzhen, 518055, China

    Chong Luo  (罗冲), Wei Lv  (吕伟) & Yaqian Deng  (邓亚茜)

  3. School of Marine Science and Technology, Tianjin University, Tianjin, 300350, China

    Chen Zhang  (张辰) & Guowei Ling  (凌国维)

  4. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China

    Changsheng Qi  (戚昌盛), Ying Tao  (陶莹), Huan Li  (李欢), Junwei Han  (韩俊伟) & Quan-Hong Yang  (杨全红)

Authors
  1. Changsheng Qi  (戚昌盛)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chong Luo  (罗冲)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ying Tao  (陶莹)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wei Lv  (吕伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Chen Zhang  (张辰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yaqian Deng  (邓亚茜)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Huan Li  (李欢)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Junwei Han  (韩俊伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Guowei Ling  (凌国维)
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Quan-Hong Yang  (杨全红)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Yang QH conceived and supervised the study. Qi C and Tao Y designed the experiment and Qi C carried out it. Qi C, Luo C, Tao Y and Yang QH discussed the data. Lv W, Zhang C, Deng Y, Li H, Han J, Ling G provided the technical support and commented the results.

Corresponding author

Correspondence to Quan-Hong Yang  (杨全红).

Additional information

Conflict of interest

The authors declare no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Changsheng Qi received his Bachelor’s degree and Master’s degree of applied chemistry from the North University of China in 2005 and 2008, respectively. He is a PhD candidate under the guidance of Prof. Quan-Hong Yang. His research interest focuses on the liquid phase assembly and mechanism of GO, and its applications.

Chong Luo received his Bachelor’s degree of materials science and engineering from the Central South University in 2013 and now is a PhD candidate under the guidance of Prof. Quan-Hong Yang and Prof. Wei Lv. His research interest focuses on the liquid phase assembly of GO and mechanism study on energy storage.

Ying Tao is an associate professor at the School of Chemical Engineering and Technology at Tianjin University. Her main research interests focus on the assembly of low dimensional materials, carbon-based materials and their applications in electrochemical energy storage and environmental remediation.

Quan-Hong Yang joined Tianjin University as a full professor in 2006 and became a Chair Professor in the same university in 2016. His research focuses on novel functional carbon materials with the applications in energy and environmental fields. Specifically, he has made significant advances in high volumetric performance EES devices and the catalysis in lithiumsulfur batteries. See http://nanoyang.tju.edu.cn for more details about Nanoyang Group.

Supporting Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Qi, C., Luo, C., Tao, Y. et al. Capillary shrinkage of graphene oxide hydrogels. Sci. China Mater. 63, 1870–1877 (2020). https://doi.org/10.1007/s40843-019-1227-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-019-1227-7

Keywords

Search

Navigation