Nitrogen Deficient Graphitic Carbon Nitride as Anodes for Lithium-ion Batteries

Abstract

In order to overcome the problem that the low conductivity and high content of graphitic N will lead to serious irreversible capacity loss, magnesiothermic denitriding method was employed to fabricate nitrogen deficient g-C₃N₄ (ND-g-C₃N₄). By controlling the reaction conditions, ND-g-C₃N₄-675 with optimal electrochemical properties was obtained. The ND-g-C₃N₄-675 has thinner two-dimensional porous structure, with high specific surface area and good conductivity. The ND-g-C₃N₄-675 showed superior cyclic stability and rate capability (After 500 cycles under 1 000 mA·g⁻¹, 2 264.9 mAh·g⁻¹ was obtained). Moreover, it presented high initial coulombic efficiency (42.2%).

Keywords

graphitic carbon nitride / magnesiothermic denitriding / graphene backbone / lithium ion batteries

References

[1] Fu Y, Zhu J, Hu C, et al. Covalently Coupled Hybrid of Graphitic Carbon Nitride with Reduced Graphene Oxide as a Superior Performance Lithium-ion Battery Anode[J]. Nanoscale, 2014, 6(21): 12 555-12 564.

[2] He J, Long F, Peng D, et al. Ribbon-like Cu Doped V₆O₁₃ as Cathode Material for High-performance Lithium Ion Batteries[J]. J. Wuhan Univ. Technol. -Mater. Sci. Ed., 2017, 32(6): 1 397-1 401.

[3] Wang Y, Zhao S, et al. Synthesis and Properties of Li₂MnSiO₄/C Cathode Materials for Li-ion Batteries[J]. J. Wuhan Univ. Technol. -Mater. Sci. Ed., 2016, 1: 945-949.

[4] Chen H, Ma T, Zeng Y, et al. Mechanism of Capacity Fading Caused by Mn (II) Deposition on Anodes for Spinel Lithium Manganese Oxide Cell[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2017, 32(1): 1-10.

[5] Tarascon JM, Armand M. Issues and Challenges Facing Rechargeable Lithium Batteries[J]. Nature, 2001, 414(6861): 359-367.

[6] Jiang Z, Jiang ZJ, Tian X, et al. Nitrogen-doped Graphene Hollow Microspheres as an Efficient Electrode Material for Lithium Ion Batteries[J]. Electrochim. Acta, 2014, 1: 455-463.

[7] Liu C, Liu X, Tan J, et al. Nitrogen-doped Graphene by All-solid-state Ball-milling Graphite with Urea as a High-power Lithium Ion Battery Anode[J]. J. Power Sources, 2017, 1: 157-164.

[8] Hankel M, Searles DJ. Lithium Storage on Carbon Nitride, Graphenylene and Inorganic Graphenylene[J]. Phys. Chem. Chem. Phys., 2016, 18(21): 14 205-14 215.

[9] Teter DM, Hemley RJ. Low-Compressibility Carbon Nitrides[J]. Science, 1996, 1: 53-55.

[10] Yang M, Jin X. Synthesis of BiVO₄-g-C₃N₄ Composite Photocatalyst with Improved Visible Light-induced Photocatalytic Activity[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2015, 30(2): 217-222.

[11] Gong Y, Li M, Wang Y. Carbon Nitride in Energy Conversion and Storage: Recent Advances and Future Prospects[J]. Chem. Sus. Chem., 2015, 8(6): 931-946.

[12] Yang X, Wang H, Lu X, et al. Solid-state Synthesis of Graphite-like C₃N₄ and Its Reversible Li⁺ Intercalation[J]. Acta Chim. Sinica, 2009, 67(11): 1 166-1 170.

[13] Jorge AB, Corà F, Sella A, et al. Electrochemical Properties of Graphitic Carbon Nitrides[J]. Int. J. Nanotechnol, 2014, 11(9/10/11): 737-746.

[14] Hankel M, Ye D, Wang L, et al. Lithium and Sodium Storage on Graphitic Carbon Nitride[J]. J. Phys. Chem. C, 2015, 1: 21 921-21 927.

[15] Hou Y, Li J, Wen Z, et al. N-doped Graphene/porous g-C₃N₄ Nanosheets Supported Layered-MoS₂ Hybrid as Robust Anode Materials for Lithium-ion Batteries[J]. Nano Energy, 2014, 1: 157-164.

[16] Vo V, Nguyen Thi XD, Jin Y S, et al. SnO₂ Nanosheets/g-C₃N₄ Composite with Improved Lithium Storage Capabilities[J]. Chem. Phys. Lett., 2017, 1: 42-47.

[17] Wang G, Wen Z, Yang YE, et al. Ultra-long Life Si@rGO/g-C₃N₄ with a Multiply Synergetic Effect as an Anode Material for Lithium Ion Batteries[J]. J. Mater. Chem. A, 2018, 6(17): 7 557-7 565.

[18] Wang S, Shi Y, Fan C, et al. Layered g-C₃N₄@Reduced Graphene Oxide Composites as Anodes with Improved Rate Performance for Lithium-Ion Batteries[J]. ACS Appl. Mater. Interfaces, 2018, 1: 30 330-30 336.

[19] Chen J, Mao Z, Zhang L, et al. Nitrogen Deficient Graphitic Carbon Nitride with Enhanced Performance for Lithium Ion Battery Anodes[J]. ACS Nano, 2017, 11(12): 12 650-12 657.

[20] Dong F, Wang Z, Sun Y, et al. Engineering the Nanoarchitecture and Texture of Polymeric Carbon Nitride Semiconductor for Enhanced Visible Light Photocatalytic Activity[J]. J. Colloid Interf. Sci., 2013, 401(8): 70-79.

[21] Waleed MA, Rouby E. Crumpled Graphene: Preparation and Applications[J]. RSC Adv., 2015, 5(82): 66 767-66 796.

[22] Qin J, He C, Zhao N, et al. Graphene Networks Anchored with Sn@Graphene as Lithium Ion Battery Anode[J]. ACS Nano, 2014, 8(2): 1 728-1 738.

[23] Zhang SW, Zhao LP, Zeng MY, et al. Hierarchical Nanocomposites of Polyaniline Nanorods Arrays on Graphitic Carbon Nitride Sheets with Synergistic Effect for Photocatalysis[J]. Catal. Today, 2014, 224(4): 114-121.

[24] Niu P, Liu G, Cheng HM. Nitrogen Vacancy-Promoted Photocatalytic Activity of Graphitic Carbon Nitride[J]. J. Phys. Chem. C, 2012, 116(20): 1 1013-1 1018.

[25] Senthil C, Kishore SC, Sasidharan M. Ultrathin MoS₂ Sheets Supported on N-rich Carbon Nitride Nanospheres with Enhanced Lithium Storage Properties[J]. Appl. Surf. Sci., 2017, 1: 215-224.

[26] Wang H, Lu J, Wang F, et al. Preparation, Characterization and Photocatalytic Performance of g-C₃N₄/Bi₂WO₆ Composites for Methyl Orange Degradation[J]. Ceram. Int., 2014, 40(7): 9 077-9 086.

[27] Ma Y, Sun L, Huang W, et al. Three-Dimensional Nitrogen-Doped Carbon Nanotubes/Graphene Structure Used as a Metal-Free Electrocatalyst for the Oxygen Reduction Reaction[J]. J. Phys. Chem. C, 2011, 115(50): 24 592-24 597.

[28] Li X, Geng D, Zhang Y, et al. Superior Cycle Stability of Nitrogen-doped Graphene Nanosheets as Anodes for Lithium Ion Batteries[J]. Electrochem. Commun., 2011, 13(8): 822-825.

[29] Ferrari A C, Basko D M. Raman Spectroscopy as a Versatile Tool for Studying the Properties of Graphene[J]. Nat. Nanotechnol., 2013, 1: 235-246.

[30] Ma C, Shao X, Cao D. Nitrogen-doped Graphene Nanosheets as Anode Materials for Lithium Ion Batteries: A First-principles Study[J]. J. Mater. Chem., 2012, 22(18): 8 911-8 915.

[31] Zheng F, Yang Y, Chen Q. High Lithium Anodic Performance of Highly Nitrogen-doped Porous Carbon Prepared from a Metal-organic Framework[J]. Nat. Commun., 2014, 5(5): 5 261

[32] Subramaniyam CM, Deshmukh KA, Tai Z, et al. 2D Layered Graphitic Carbon Nitride Sandwiched with Reduced Graphene Oxide as Nanoarchitectured Anode for Highly Stable Lithium-ion Battery[J]. Electrochim. Acta, 2017, 1: 69-77.

[33] Tang J, Chen G, Yang J, et al. Silica-assistant Synthesis of Three-dimensional Graphene Architecture and Its Application as Anode Material for Lithium Ion Batteries[J]. Nano Energy, 2014, 1: 62-70.

[34] Qie L, Chen WM, Wang ZH, et al. Nitrogen-Doped Porous Carbon Nanofiber Webs as Anodes for Lithium Ion Batteries with a Superhigh Capacity and Rate Capability[J]. Adv. Mater., 2012, 24(15): 2047-2050.

[35] Ye D, Wang B, Chen Y, et al. Understanding the Stepwise Capacity Increase of High Energy Low-Co Li-rich Cathode Materials for Lithium Ion Batteries[J]. J. Mater. Chem. A, 2014, 1: 18 767-18 774.

[36] Shi Y, Zhang LL, Schon TB, et al. Porous Carbon with Willow-Leaf-Shaped Pores for High-Performance Supercapacitors[J]. ACS Appl. Mater. Interfaces, 2017, 1: 42 699-42 707.