Facile and scalable preparation of ultra-large boron nitride nanosheets and their use for highly thermally conductive polymer composites

Abstract

Due to their excellent physical and chemical properties, boron nitride nanosheets (BNNSs) have shown great application potential in many fields. However, the difficulty in scalable preparation of large-size BNNSs is still the current factor that limits this. Herein, a simple yet efficient microwave-assisted chemical exfoliation strategy is proposed to realize scalable preparation of BNNSs by using perchloric acid as the edge modifier and intercalation agent of h-BN. The as-obtained BNNSs behave a thin-layered structure (average thickness of 3.9 nm) with a high yield of ~16%. Noteworthy, the size of BNNSs is maintained to the greatest extent so as to realize the preparation of BNNSs with ultra-large size (up to 7.1 μm), which is the largest so far obtained for the top-down exfoliated BNNSs. Benefiting from the large size, it can significantly improve the thermal diffusion coefficient and the thermal conductivity of polyvinyl alcohol by 51 and 62 times respectively, both showing a higher value than the one previously reported. This demonstrates that the prepared BNNSs have great promise in enhancing the thermal conductivity of polymer materials.

Graphical abstract

Keywords

boron nitride nanosheet / thermal conductivity / chemical exfoliation / large size

References

[1] Moore A L, Shi L. Emerging challenges and materials for thermal management of electronics. Materials Today, 2014, 17(4): 163–174

[2] Lancaster A, Keswani M. Integrated circuit packaging review with an emphasis on 3D packaging. Integration, 2018, 60: 204–212

[3] Tan C, Dong Z, Li Y, . A high performance wearable strain sensor with advanced thermal management for motion monitoring. Nature Communications, 2020, 11(1): 3530

[4] Feng C P, Chen L B, Tian G L, . Multifunctional thermal management materials with excellent heat dissipation and generation capability for future electronics. ACS Applied Materials & Interfaces, 2019, 11(20): 18739–18745

[5] Feng C P, Chen L B, Tian G L, . Robust polymer-based paper-like thermal interface materials with a through-plane thermal conductivity over 9 W·m⁻¹·K⁻¹. Chemical Engineering Journal, 2020, 392: 123784

[6] Yu C, Gong W, Tian W, . Hot-pressing induced alignment of boron nitride in polyurethane for composite films with thermal conductivity over 50 W·m⁻¹·K⁻¹. Composites Science and Technology, 2018, 160: 199–207

[7] Zhang Z, Qu J, Feng Y, . Assembly of graphene-aligned polymer composites for thermal conductive applications. Composites Communications, 2018, 9: 33–41

[8] Singh S, Shervin S, Sun H, . Using mosaicity to tune thermal transport in polycrystalline aluminum nitride thin films. ACS Applied Materials & Interfaces, 2018, 10(23): 20085–20094

[9] Morishita T, Matsushita M, Katagiri Y, . A novel morphological model for carbon nanotube/polymer composites having high thermal conductivity and electrical insulation. Journal of Materials Chemistry, 2011, 21(15): 5610–5614

[10] Yu C, Zhang J, Li Z, . Enhanced through-plane thermal conductivity of boron nitride/epoxy composites. Composites Part A: Applied Science and Manufacturing, 2017, 98: 25–31

[11] Zhang J, Wang X, Yu C, . A facile method to prepare flexible boron nitride/poly (vinyl alcohol) composites with enhanced thermal conductivity. Composites Science and Technology, 2017, 149: 41–47

[12] Song W L, Wang P, Cao L, . Polymer/boron nitride nanocomposite materials for superior thermal transport performance. Angewandte Chemie, 2012, 124(26): 6604–6607

[13] Zhang K, Feng Y, Wang F, . Two dimensional hexagonal boron nitride (2D-hBN): synthesis, properties and applications. Journal of Materials Chemistry C: Materials for Optical and Electronic Devices, 2017, 5(46): 11992–12022

[14] Chen J, Huang X, Zhu Y, . Cellulose nanofiber supported 3D interconnected BN nanosheets for epoxy nanocomposites with ultrahigh thermal management capability. Advanced Functional Materials, 2017, 27(5): 1604754

[15] Zhu Z, Li C, Songfeng E, . Enhanced thermal conductivity of polyurethane composites via engineering small/large sizes interconnected boron nitride nanosheets. Composites Science and Technology, 2019, 170: 93–100

[16] Lin Z, Mcnamara A, Liu Y, . Exfoliated hexagonal boron nitride-based polymer nanocomposite with enhanced thermal conductivity for electronic encapsulation. Composites Science and Technology, 2014, 90: 123–128

[17] Yuan F, Jiao W, Yang F, . Scalable exfoliation for large-size boron nitride nanosheets by low temperature thermal expansion-assisted ultrasonic exfoliation. Journal of Materials Chemistry C: Materials for Optical and Electronic Devices, 2017, 5(25): 6359–6368

[18] Joy J, George E, Haritha P, . An overview of boron nitride based polymer nanocomposites. Journal of Polymer Science, 2020, 58(22): 3115–3141

[19] Khan M H, Liu H K, Sun X, . Few-atomic-layered hexagonal boron nitride: CVD growth, characterization, and applications. Materials Today, 2017, 20(10): 611–628

[20] Zhi C, Bando Y, Tang C, . Large-scale fabrication of boron nitride nanosheets and their utilization in polymeric composites with improved thermal and mechanical properties. Advanced Materials, 2009, 21(28): 2889–2893

[21] Wang X, Yang Y, Jiang G, . A facile synthesis of boron nitride nanosheets and their potential application in dye adsorption. Diamond and Related Materials, 2018, 81: 89–95

[22] Jung J H, Park C H, Ihm J. A rigorous method of calculating exfoliation energies from first principles. Nano Letters, 2018, 18(5): 2759–2765

[23] Lin Y, Williams T V, Xu T B, . Aqueous dispersions of few-layered and monolayered hexagonal boron nitride nanosheets from sonication-assisted hydrolysis: critical role of water. The Journal of Physical Chemistry C, 2011, 115(6): 2679–2685

[24] Deshmukh A R, Jeong J W, Lee S J, . Ultrasound-assisted facile green synthesis of hexagonal boron nitride nanosheets and their applications. ACS Sustainable Chemistry & Engineering, 2019, 7(20): 17114–17125

[25] Chen S, Xu R, Liu J, . Simultaneous production and functionalization of boron nitride nanosheets by sugar-assisted mechanochemical exfoliation. Advanced Materials, 2019, 31(10): 1804810

[26] Lei W, Mochalin V N, Liu D, . Boron nitride colloidal solutions, ultralight aerogels and freestanding membranes through one-step exfoliation and functionalization. Nature Communications, 2015, 6: 8849

[27] Bhimanapati G R, Kozuch D, Robinson J A. Large-scale synthesis and functionalization of hexagonal boron nitride nanosheets. Nanoscale, 2014, 6(20): 11671–11675

[28] Zhao H R, Ding J H, Shao Z Z, . High-quality boron nitride nanosheets and their bioinspired thermally conductive papers. ACS Applied Materials & Interfaces, 2019, 11(40): 37247–37255

[29] Du M, Wu Y, Hao X. A facile chemical exfoliation method to obtain large size boron nitride nanosheets. CrystEngComm, 2013, 15(9): 1782–1786

[30] Lee D, Lee B, Park K H, . Scalable exfoliation process for highly soluble boron nitride nanoplatelets by hydroxide-assisted ball milling. Nano Letters, 2015, 15(2): 1238–1244

[31] Hou J, Li G, Yang N, . Preparation and characterization of surface modified boron nitride epoxy composites with enhanced thermal conductivity. RSC Advances, 2014, 4(83): 44282–44290

[32] Cui Z, Oyer A J, Glover A J, . Large scale thermal exfoliation and functionalization of boron nitride. Small, 2014, 10(12): 2352–2355

[33] Geick R, Perry C H, Rupprecht G. Normal modes in hexagonal boron nitride. Physical Review, 1966, 146(2): 543–547

[34] Sainsbury T, Satti A, May P, . Oxygen radical functionalization of boron nitride nanosheets. Journal of the American Chemical Society, 2012, 134(45): 18758–18771

[35] Zhu W, Gao X, Li Q, . Controlled gas exfoliation of boron nitride into few-layered nanosheets. Angewandte Chemie, 2016, 128(36): 10924–10928

[36] Cheng Z L, Ma Z S, Ding H L, . Environmentally friendly, scalable exfoliation for few-layered hexagonal boron nitride nanosheets (BNNSs) by multi-time thermal expansion based on released gases. Journal of Materials Chemistry C: Materials for Optical and Electronic Devices, 2019, 7(46): 14701–14708

[37] Chao Y, Liu M, Pang J, . Gas-assisted exfoliation of boron nitride nanosheets enhancing adsorption performance. Ceramics International, 2019, 45(15): 18838–18843

[38] Li L H, Cervenka J, Watanabe K, . Strong oxidation resistance of atomically thin boron nitride nanosheets. ACS Nano, 2014, 8(2): 1457–1462

[39] Gorbachev R V, Riaz I, Nair R R, . Hunting for monolayer boron nitride: optical and Raman signatures. Small, 2011, 7(4): 465–468

[40] Li X, Hao X, Zhao M, . Exfoliation of hexagonal boron nitride by molten hydroxides. Advanced Materials, 2013, 25(15): 2200–2204

[41] Cao C, Xue Y, Liu Z, . Scalable exfoliation and gradable separation of boric-acid-functionalized boron nitride nanosheets. 2D Materials, 2019, 6(3): 035014 doi:10.1088/2053-1583/ab0eb4

[42] Zhu M, Li G, Zhang X, . High yield and concentration exfoliation of defect-free 2D nanosheets via gentle water freezing-thawing approach and stabilization with PVP. Materials Research Express, 2019, 6(11): 1150c9 doi:10.1088/2053-1591/ab2de3

[43] Zhang C, Tan J, Pan Y, . Mass production of 2D materials by intermediate-assisted grinding exfoliation. National Science Review, 2020, 7(2): 324–332

[44] Xie B H, Huang X, Zhang G J. High thermal conductive polyvinyl alcohol composites with hexagonal boron nitride microplatelets as fillers. Composites Science and Technology, 2013, 85: 98–103

[45] E S, Zhu Z, Xie L, . An integrated strategy towards the high-yield fabrication of soluble boron nitride nanosheets. Chemical Engineering Journal, 2019, 360: 1407–1415

[46] Liu Z, Li J, Liu X. Novel functionalized BN nanosheets/epoxy composites with advanced thermal conductivity and mechanical properties. ACS Applied Materials & Interfaces, 2020, 12(5): 6503–6515

[47] Fu K, Yang J, Cao C, . Highly multifunctional and thermoconductive performances of densely filled boron nitride nanosheets/epoxy resin bulk composites. ACS Applied Materials & Interfaces, 2021, 13(2): 2853–2867

[48] Zeng X, Ye L, Yu S, . Artificial nacre-like papers based on noncovalent functionalized boron nitride nanosheets with excellent mechanical and thermally conductive properties. Nanoscale, 2015, 7(15): 6774–6781

[49] Wang M, Jiao Z, Chen Y, . Enhanced thermal conductivity of poly(vinylidene fluoride)/boron nitride nanosheet composites at low filler content. Composites Part A: Applied Science and Manufacturing, 2018, 109: 321–329

[50] Yin C G, Liu Z J, Mo R, . Copper nanowires embedded in boron nitride nanosheet-polymer composites with enhanced thermal conductivities for thermal management. Polymer, 2020, 195: 122455

Disclosure of potential conflicts of interest

The authors declare that they have no conflict of interest.

Acknowledgements

Projects 52172052 and 51872253 supported by the National Natural Science Foundation of China and Project E2019203480 supported by the Hebei Natural Science Foundation of China.

RIGHTS & PERMISSIONS

2022 Higher Education Press