logo

Capillary shrinkage of graphene oxide hydrogels

More info
  • ReceivedNov 30, 2019
  • AcceptedDec 3, 2019
  • PublishedDec 5, 2019

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.


Funded by

the National Natural Science Fund for the Distinguished Young Scholars

China(51525204)

the National Natural Science Foundation of China(51702229,51872195)

the CAS Key Laboratory of Carbon Materials(KLCM,KFJJ1704)

Shenzhen Basic Research Project(ZDSYS201405,09172959981)


Acknowledgment

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).


Interest statement

The authors declare no conflict of interest.


Contributions statement

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.


Author information

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 lithium-sulfur batteries. See http://nanoyang.tju.edu.cn for more details about Nanoyang Group.


Supplement

Supplementary information

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


References

[1] Geim AK, Novoselov KS. The rise of graphene. Nat Mater, 2007, 6: 183-191 CrossRef PubMed Google Scholar

[2] Allen MJ, Tung VC, Kaner RB. Honeycomb carbon: a review of graphene. Chem Rev, 2009, 110: 132-145 CrossRef PubMed 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 CrossRef PubMed 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 CrossRef 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 CrossRef 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 CrossRef 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 CrossRef 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 CrossRef 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 CrossRef PubMed 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 CrossRef 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 CrossRef 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 CrossRef PubMed 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 CrossRef PubMed 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 CrossRef PubMed 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 CrossRef PubMed 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 CrossRef 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 CrossRef 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 CrossRef Google Scholar

[19] Dreyer DR, Park S, Bielawski CW, et al. The chemistry of graphene oxide. Chem Soc Rev, 2010, 39: 228-240 CrossRef PubMed Google Scholar

[20] Kim J, Cote LJ, Kim F, et al. Graphene oxide sheets at interfaces. J Am Chem Soc, 2010, 132: 8180-8186 CrossRef PubMed Google Scholar

[21] Dikin DA, Stankovich S, Zimney EJ, et al. Preparation and characterization of graphene oxide paper. Nature, 2007, 448: 457-460 CrossRef PubMed 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 CrossRef PubMed 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 CrossRef PubMed Google Scholar

[24] Shao JJ, Lv W, Yang QH. Self-assembly of graphene oxide at interfaces.. Adv Mater, 2014, 26: 5586-5612 CrossRef PubMed 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 CrossRef PubMed Google Scholar

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

[30] Qiu L, Liu JZ, Chang SLY, et al. Biomimetic superelastic graphene-based cellular monoliths. Nat Commun, 2012, 3: 1241-1246 CrossRef PubMed Google Scholar

[31] Sun H, Xu Z, Gao C. Multifunctional, ultra-flyweight, synergistically assembled carbon aerogels. Adv Mater, 2013, 25: 2554-2560 CrossRef PubMed 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 CrossRef 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 CrossRef PubMed 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 CrossRef 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 CrossRef PubMed 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 CrossRef 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 CrossRef PubMed Google Scholar

[38] Hovorka F, Schaefer RA, Dreisbach D. The system dioxane and water. J Am Chem Soc, 1936, 58: 2264-2267 CrossRef Google Scholar

[39] Baker NB, Gilbert EC. Surface tension in the system hydrazine—water at 25°. J Am Chem Soc, 1940, 62: 2479-2480 CrossRef 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 CrossRef Google Scholar

[41] Steiner T. The hydrogen bond in the solid state. Angew Chem Int Ed, 2002, 41: 48-76 CrossRef 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 CrossRef PubMed 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 CrossRef Google Scholar

  • Figure 1

    (a) Two typical assembly models for conventional carbon materials, which can be regarded as assemblies with graphene as building blocks; (b) preparation of different porous carbons by removing residual solvents in different ways.

  • Figure 2

    Capillary shrinkage of r-GO hydrogels using two solvents with almost the same boiling point yet different surface tensions. (a) An integral r-GO hydrogel obtained after hydrothermal treatment; (b, c) SEM images and inset photos of the monoliths obtained by immersion of patent hydrogels in water or 1,4-dioxane for solvent-exchange and then dried; (d) XRD patterns of these r-GO monoliths; (e) N2 adsorption-desorption isotherms; (f) BET surface area and (g) PSD of the resulting HPGM and Diox-G.

  • Figure 3

    Capillary shrinkage of the r-GO hydrogel during solvent evaporation. (a) Schematic of the r-GO hydrogel capillary shrinkage process; (b) capillary force exerted on the r-GO sheets during solvent evaporation.

  • Figure 4

    Characterizations of the r-GO monoliths obtained in solvents with different surface tensions. (a) Photos of the r-GO monoliths after solvent evaporation; (b) N2 adsorption/desorption isotherms of the desolvated r-GO monoliths; (c) relationship between the BET surface area and solvent surface tension; (d) bulk density and cumulative pore volume of the desolvated r-GO monoliths as a function of solvent surface tension; (e) the EtOH-G monolith can be further densified to EtOH-HPGM by second drying after immersion in water. It has similar isotherms to HPGM.

Copyright 2020 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有

京ICP备18024590号-1