Skip to main content
SpringerLink
Log in

Ultrathin nitrogen-doping graphene films for flexible and stretchable EMI shielding materials

  • Energy materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Ultrathin, flexible and highly conductive materials that possess excellent electromagnetic interference (EMI) shielding performance are greatly needed, especially for the fabrication of stretchable shielding materials in practical applications such as wearable and foldable electronics. Graphene oxide (GO) sheets are modified with ethylenediamine to prepare cross-linked graphene films using a pressure-assisted self-assembly technique. FTIR and XPS results demonstrate that amine monomers are chemically bonded to GO sheets, with simultaneous reduction of GO sheets. After thermal annealing and followed with compression, the 6.6-μm-thick nitrogen-doping graphene film (rGO-EDA-2) is obtained with ultrahigh electrical conductivity of 8796 S cm−1. The excellent electrical conductivity is mainly attributed to nitrogen-doping effect, defects repair during chemical functionalization and removal of oxygenated groups. Ultrahigh electrical conductivity, multilayer structure and modified electronic structure with nitrogen doping lead to outstanding shielding performance for the rGO-EDA-2 film, with excellent shielding effectiveness (SE) of 58.5 dB and the specific SE/thickness of 43902 dB cm2 g−1, respectively. By fixing the rGO-EDA-2 film on the pre-stretched wavy substrate, the stretchable shielding composite is obtained, with constant EMI SE of 56.3 dB after repeated stretching. The pre-stretched wavy substrate allows the multilayer graphene film to achieve wavy structure after strain release, which is capable of bearing tensile strain up to 32.6%. This study could be significant in the applications of stretchable and wearable electronic devices.

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

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9

Similar content being viewed by others

References

  1. Chen Z, Xu C, Ma C, Ren W, Cheng HM (2013) Lightweight and flexible graphene foam composites for high-performance electromagnetic interference shielding. Adv Mater 25(9):1296–1300

    Article  CAS  Google Scholar 

  2. Yousefi N, Sun X, Lin X, Shen X, Jia J, Zhang B et al (2014) Highly aligned graphene/polymer nanocomposites with excellent dielectric properties for high-performance electromagnetic interference shielding. Adv Mater 26(31):5480–5487

    Article  CAS  Google Scholar 

  3. Gupta TK, Singh BP, Singh VN, Teotia S, Singh AP, Elizabeth I et al (2014) MnO2 decorated graphene nanoribbons with superior permittivity and excellent microwave shielding properties. J Mater Chem A 2(12):4256

    Article  CAS  Google Scholar 

  4. Shahzad F, Alhabeb M, Hatter CB, Anasori Babak, Hong SM, Koo CM et al (2016) Electromagnetic interference shielding with 2D transition metal carbides (MXenes). Science 353(6304):1137–1140

    Article  CAS  Google Scholar 

  5. Chuang DDL (2001) Electromagnetic interference shielding effectiveness of carbon materials. Carbon 39:279–285

    Article  Google Scholar 

  6. Umrao S, Gupta TK, Kumar S, Singh VK, Sultania MK, Jung JH et al (2015) Microwave-assisted synthesis of boron and nitrogen co-doped reduced graphene oxide for the protection of electromagnetic radiation in Ku-band. ACS Appl Mater Interfaces 7(35):19831–19842

    Article  CAS  Google Scholar 

  7. Kuester S, Merlini C, Barra GMO, Ferreira JC, Lucas A, de Souza AC et al (2016) Processing and characterization of conductive composites based on poly(styrene-b-ethylene-ran-butylene-b-styrene) (SEBS) and carbon additives: a comparative study of expanded graphite and carbon black. Compos Part B-Eng 84:236–247

    Article  CAS  Google Scholar 

  8. Ameli A, Jung PU, Park CB (2013) Electrical properties and electromagnetic interference shielding effectiveness of polypropylene/carbon fiber composite foams. Carbon 60:379–391

    Article  CAS  Google Scholar 

  9. Chaudhary A, Kumari S, Kumar R, Teotia S, Singh BP, Singh AP et al (2016) Lightweight and easily foldable MCMB-MWCNTs composite paper with exceptional electromagnetic interference shielding. ACS Appl Mater Interfaces 8(16):10600–10608

    Article  CAS  Google Scholar 

  10. Zhang L, Alvarez NT, Zhang M, Haase M, Malik R, Mast D et al (2015) Preparation and characterization of graphene paper for electromagnetic interference shielding. Carbon 82:353–359

    Article  CAS  Google Scholar 

  11. Song WL, Guan XT, Fan LZ, Cao WQ, Wang CY, Cao MS (2015) Tuning three-dimensional textures with graphene aerogels for ultra-light flexible graphene/texture composites of effective electromagnetic shielding. Carbon 93:151–160

    Article  CAS  Google Scholar 

  12. Zeng Z, Jin H, Chen M, Li W, Zhou L, Zhang Z (2016) Lightweight and anisotropic porous MWCNT/WPU composites for ultrahigh performance electromagnetic interference shielding. Adv Funct Mater 26(2):303–310

    Article  CAS  Google Scholar 

  13. Liang J, Wang Y, Huang Y, Ma Y, Liu Z, Cai J et al (2009) Electromagnetic interference shielding of graphene/epoxy composites. Carbon 47(3):922–925

    Article  CAS  Google Scholar 

  14. Yan DX, Pang H, Li B, Vajtai R, Xu L, Ren PG et al (2015) Structured reduced graphene oxide/polymer composites for ultra-efficient electromagnetic interference shielding. Adv Funct Mater 25(4):559–566

    Article  CAS  Google Scholar 

  15. Cao MS, Wang XX, Cao WQ, Yuan J (2015) Ultrathin graphene: electrical properties and highly efficient electromagnetic interference shielding. J Mater Chem C 3(26):6589–6599

    Article  CAS  Google Scholar 

  16. Shen B, Zhai W, Zheng W (2014) Ultrathin flexible graphene film: an excellent thermal conducting material with efficient EMI shielding. Adv Funct Mater 24(28):4542–4548

    Article  CAS  Google Scholar 

  17. Ye S, Chen B, Feng J (2015) Fracture mechanism and toughness optimization of macroscopic thick graphene oxide film. Sci Rep 5:13102

    Article  CAS  Google Scholar 

  18. Chen J, Li Y, Huang L, Jia N, Li C, Shi G (2015) Size fractionation of graphene oxide sheets via filtration through track-etched membranes. Adv Mater 27(24):3654–3660

    Article  CAS  Google Scholar 

  19. Compton OC, Dikin DA, Putz KW, Brinson LC, Nguyen ST (2010) Electrically conductive “alkylated” graphene paper via chemical reduction of amine-functionalized graphene oxide paper. Adv Mater 22(8):892–896

    Article  CAS  Google Scholar 

  20. Li WJ, Tang XZ, Zhang HB, Jiang ZG, Yu ZZ, Du XS et al (2011) Simultaneous surface functionalization and reduction of graphene oxide with octadecylamine for electrically conductive polystyrene composites. Carbon 49(14):4724–4730

    Article  CAS  Google Scholar 

  21. Ma HL, Zhang HB, Hu QH, Li WJ, Jiang ZG, Yu ZZ et al (2012) Functionalization and reduction of graphene oxide with p-phenylene diamine for electrically conductive and thermally stable polystyrene composites. ACS Appl Mater Interfaces 4(4):1948–1953

    Article  CAS  Google Scholar 

  22. Chua CK, Pumera M (2014) Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. Chem Soc Rev 43(1):291–312

    Article  CAS  Google Scholar 

  23. Luo D, Zhang G, Liu J, Sun X (2011) Evaluation criteria for reduced graphene oxide. J Phys Chem C 115(23):11327–11335

    Article  CAS  Google Scholar 

  24. Hung WS, Tsou CH, De Guzman M, An QF, Liu YL, Zhang YM et al (2014) Cross-linking with diamine monomers to prepare composite graphene oxide-framework membranes with varying d-spacing. Chem Mater 26(9):2983–2990

    Article  CAS  Google Scholar 

  25. Kim NH, Kuila T, Lee JH (2013) Simultaneous reduction, functionalization and stitching of graphene oxide with ethylenediamine for composites application. J Mater Chem A 1(4):1349–1358

    Article  CAS  Google Scholar 

  26. Hu Y, Shen J, Li N, Shi M, Ma H, Yan B et al (2010) Amino-functionalization of graphene sheets and the fabrication of their nanocomposites. Polym Compos 31(12):1987–1994

    Article  CAS  Google Scholar 

  27. Wang Z, Dong Y, Li H, Zhao Z, Wu HB, Hao C et al (2014) Enhancing lithium-sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide. Nat Commun 5:5002

    Article  CAS  Google Scholar 

  28. Lv R, Li Q, Botello-Mendez AR, Hayashi T, Wang B, Berkdemir A et al (2012) Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing. Sci Rep 2:586

    Article  CAS  Google Scholar 

  29. Liu ZF, Fang S, Moura FA, Ding JN, Jiang N, Di J et al (2015) Hierarchically buckled sheath-core fibers for superelastic electronics, sensors, and muscles. Science 349(6246):400–404

    Article  CAS  Google Scholar 

  30. Wang R, Jiang N, Su J, Yin Q, Zhang Y, Liu Z et al (2017) A Bi-sheath fiber sensor for giant tensile and torsional displacements. Adv Funct Mater 27(35):1702134

    Article  CAS  Google Scholar 

  31. Jung J, Lee H, Ha I, Cho H, Kim KK, Kwon J et al (2017) Highly stretchable and transparent electromagnetic interference shielding film based on silver nanowire percolation network for wearable electronics applications. ACS Appl Mater Interfaces 9(51):44609–44616

    Article  CAS  Google Scholar 

  32. Wang H, Liu Z, Ding J, Lepro X, Fang S, Jiang N et al (2016) Downsized sheath-core conducting fibers for weavable superelastic wires, biosensors, supercapacitors, and strain sensors. Adv Mater 28(25):4998–5007

    Article  CAS  Google Scholar 

  33. Qi D, Liu Z, Liu Y, Leow WR, Zhu B, Yang H et al (2015) Suspended wavy graphene microribbons for highly stretchable microsupercapacitors. Adv Mater 27(37):5559–5566

    Article  CAS  Google Scholar 

  34. Hong JY, Kim W, Choi D, Kong J, Park HS (2016) Omnidirectionally stretchable and transparent graphene electrodes. ACS Nano 10(10):9446–9455

    Article  CAS  Google Scholar 

  35. Xi J, Li Y, Zhou E, Liu Y, Gao W, Guo Y et al (2018) Graphene aerogel films with expansion enhancement effect of high-performance electromagnetic interference shielding. Carbon 135:44–51

    Article  CAS  Google Scholar 

  36. Lee JU, Lee W, Yi JW, Yoon SS, Lee SB, Jung BM et al (2013) Preparation of highly stacked graphene papers via site-selective functionalization of graphene oxide. J Mater Chem A 1(41):12893

    Article  CAS  Google Scholar 

  37. Peng L, Xu Z, Liu Z, Guo Y, Li P, Gao C (2017) Ultrahigh thermal conductive yet superflexible graphene films. Adv Mater 29(27):1700589. https://doi.org/10.1002/adma.201700589

    Article  CAS  Google Scholar 

  38. Yang S (2006) Electromagnetic shielding theory and the practice. National Defense Industry Press, Beijing

    Google Scholar 

  39. Huang Y, Li N, Ma Y, Du F, Li F, He X et al (2007) The influence of single-walled carbon nanotube structure on the electromagnetic interference shielding efficiency of its epoxy composites. Carbon 45(8):1614–1621

    Article  CAS  Google Scholar 

  40. Zhang HB, Yan Q, Zheng WG, He Z, Yu ZZ (2011) Tough graphene-polymer microcellular foams for electromagnetic interference shielding. ACS Appl Mater Interfaces 3(3):918–924

    Article  CAS  Google Scholar 

  41. Yan D-X, Ren P-G, Pang H, Fu Q, Yang M-B, Li Z-M (2012) Efficient electromagnetic interference shielding of lightweight graphene/polystyrene composite. J Mater Chem 22:18772–18774

    Article  CAS  Google Scholar 

  42. Ling J, Zhai W, Feng W, Shen B, Zhang J, Zheng W (2013) Facile preparation of lightweight microcellular polyetherimide/graphene composite foams for electromagnetic interference shielding. ACS Appl Mater Interfaces 5(7):2677–2684

    Article  CAS  Google Scholar 

  43. Shen B, Zhai W, Tao M, Ling J, Zheng W (2013) Lightweight, multifunctional polyetherimide/graphene@Fe3O4 composite foams for shielding of electromagnetic pollution. ACS Appl Mater Interfaces 5(21):11383–11391

    Article  CAS  Google Scholar 

  44. Crespo M, González M, Elías AL, Pulickal Rajukumar L, Baselga J, Terrones M et al (2014) Ultra-light carbon nanotube sponge as an efficient electromagnetic shielding material in the GHz range. Phys Status Solidi-R 8(8):698–704

    Article  CAS  Google Scholar 

  45. Ji K, Zhao H, Zhang J, Chen J, Dai Z (2014) Fabrication and electromagnetic interference shielding performance of open-cell foam of a Cu–Ni alloy integrated with CNTs. Appl Surf Sci 311(9):351–356

    Article  CAS  Google Scholar 

  46. Micheli D, Pastore R, Vricella A, Morles RB, Marchetti M, Delfini A et al (2014) Electromagnetic characterization and shielding effectiveness of concrete composite reinforced with carbon nanotubes in the mobile phones frequency band. Mater Sci Eng, B 188:119–129

    Article  CAS  Google Scholar 

  47. Teotia S, Singh BP, Elizabeth I, Singh VN, Ravikumar R, Singh AP et al (2014) Multifunctional, robust, light-weight, free-standing MWCNT/phenolic composite paper as anodes for lithium ion batteries and EMI shielding material. RSC Adv 4(63):33168–33174

    Article  CAS  Google Scholar 

  48. Agnihotri N, Chakrabarti K, De A (2015) Highly efficient electromagnetic interference shielding using graphite nanoplatelet/poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) composites with enhanced thermal conductivity. RSC Adv 2015(5):43765–43771

    Article  CAS  Google Scholar 

  49. Li Y, Pei X, Shen B, Zhai W, Zhang L, Zheng W (2015) Polyimide/graphene composite foam sheets with ultrahigh thermostability for electromagnetic interference shielding. RSC Adv 5(31):24342–24351

    Article  CAS  Google Scholar 

  50. Ma J, Wang K, Zhan M (2015) A comparative study of structure and electromagnetic interference shielding performance for silver nanostructure hybrid polyimide foams. RSC Adv 2015(5):65283–65296

    Article  CAS  Google Scholar 

  51. Paliotta L, De Bellis G, Tamburrano A, Marra F, Rinaldi A, Balijepalli SK et al (2015) Highly conductive multilayer-graphene paper as a flexible lightweight electromagnetic shield. Carbon 89:260–271

    Article  CAS  Google Scholar 

  52. Song WL, Guan XT, Fan LZ, Cao WQ, Wang CY, Zhao QL et al (2015) Magnetic and conductive graphene papers toward thin layers of effective electromagnetic shielding. J Mater Chem A 3(5):2097–2107

    Article  CAS  Google Scholar 

  53. Shen B, Li Y, Yi D, Zhai W, Wei X, Zheng W (2016) Microcellular graphene foam for improved broadband electromagnetic interference shielding. Carbon 102:154–160

    Article  CAS  Google Scholar 

  54. Song Q, Ye F, Yin X, Li W, Li H, Liu Y, et al (2013) Carbon nanotube-multilayered graphene edge plane core-shell hybrid foams for ultrahigh-performance electromagnetic-interference shielding. Adv Mater 29(31):1701583. https://doi.org/10.1002/adma.201701583

    Article  CAS  Google Scholar 

  55. Liu Y, Zeng J, Han D, Wu K, Yu B, Chai S et al (2018) Graphene enhanced flexible expanded graphite film with high electric, thermal conductivities and EMI shielding at low content. Carbon 133:435–445

    Article  CAS  Google Scholar 

  56. Lu S, Shao J, Ma K, Chen D, Wang X, Zhang L et al (2018) Flexible, mechanically resilient carbon nanotube composite films for high-efficiency electromagnetic interference shielding. Carbon 136:387–394

    Article  CAS  Google Scholar 

  57. Wu HY, Jia LC, Yan DX, Gao JF, Zhang XP, Ren PG et al (2018) Simultaneously improved electromagnetic interference shielding and mechanical performance of segregated carbon nanotube/polypropylene composite via solid phase molding. Compos Sci Technol 156:87–94

    Article  CAS  Google Scholar 

  58. Zhou E, Xi J, Guo Y, Liu Y, Xu Z, Peng L et al (2018) Synergistic effect of graphene and carbon nanotube for high-performance electromagnetic interference shielding films. Carbon 133:316–322

    Article  CAS  Google Scholar 

  59. Xu JS, Chen J, Zhang M, Hong JD, Shi GQ (2016) Highly conductive stretchable electrodes prepared by in situ reduction of wavy graphene oxide films coated on elastic tapes. Adv Electron Mater 2(6):1600022

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Authors Shaofeng Lin and Su Ju contribute equally to the article. The authors are grateful to the financial support from National Natural Science Foundation of China (Grant No. 51803236) and Natural Science Foundation of Hunan Province, China (Grant No. 2017JJ3354).

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, National University of Defense Technology, Changsha, 410073, Hunan Province, China

    Shaofeng Lin, Su Ju, Gang Shi, Jianwei Zhang, Yonglyu He & Dazhi Jiang

Authors
  1. Shaofeng Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Su Ju
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Gang Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jianwei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yonglyu He
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dazhi Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jianwei Zhang or Dazhi Jiang.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 8625 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lin, S., Ju, S., Shi, G. et al. Ultrathin nitrogen-doping graphene films for flexible and stretchable EMI shielding materials. J Mater Sci 54, 7165–7179 (2019). https://doi.org/10.1007/s10853-019-03372-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-019-03372-4

Search

Navigation