Rapid synthesis of nitrogen-doped graphene for a lithium ion battery anode with excellent rate performance and super-long cyclic stability

Abstract

Chemical doping of nitrogen into graphene can significantly enhance the reversible capacity and cyclic stability of the graphene-based lithium ion battery (LIB) anodes, and first principles calculations based on density functional theory suggested that pyridinic-N shows stronger binding with Li with reduced energy barrier for Li diffusion and thus is more effective for Li storage than pyrrolic and graphitic-N. Here, we report a novel and rapid (~30 seconds) process to fabricate nitrogen-doped graphene (NGr) by simultaneous thermal reduction of graphene oxide with ammonium hydroxide. The porous NGr with dominant pyridinic N atoms displays greatly enhanced reversible capacities, rate performance and exceptional cyclic stability as compared with pristine graphene. The reversible discharge capacity of the NGr electrode cycled between 0.01-3 V can reach 453 mA h g(-1) after 550 cycles at a charge rate of 2 A g(-1) (~5.4 C), and 180 mA h g(-1) after 2000 cycles at a high charge rate of 10 A g(-1) (~27 C) without any capacity fading. When charged within 0.01-1.5 V, the NGr anode still exhibits high reversible capacities of 224 mA h g(-1) and 169 mA h g(-1) after 700 cycles and 800 cycles at a charge rate of 1 A g(-1) and 5 A g(-1), respectively. Ex situ X-ray photoelectron spectroscopy (XPS) analysis of the NGr electrode upon lithiation and delithiation indicated that the pyridinic-N dominates the capacity enhancement at 3 V, while the pyrrolic-N contributes primarily to Li ion storage below 1.5 V.

High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework

“…High-rate discharge and charging processes are important for many practical battery applications [53][54][55][56] , including their use in electric vehicles and portable power tools. The very high capacity, excellent cyclic performance and rate capabilities of the MOFderived N-doped graphene analogous particles (N-C-800) make them a promising candidate as anode materials for highperformance LIBs.…”

Porous nitrogen-doped graphene/carbon nanotubes composite with an enhanced supercapacitor performance

“…As presented in Fig.2b, all samples have two obvious peaks, the one is D band (~1320 cm -1 ) corresponded to the defects and disordered degree in the graphite crystal lattice, the other is G band (~1575 cm -1 ) attributed to the stretching of the C-C bond [42]. According to the literature [43,44], the D band frequency will move to higher location when graphene is doped by nitrogen atoms, and the G band frequency will shift lower frequency when graphene is stacked more layers. Compared with GC, D and G band locations of NGC are higher by 4.5 cm -1 and 3.7 cm -1 , respectively.…”

“…4b, the overlapping C 1s can be divided into four components of carbon bond. One core peak of C 1s is located at 284.8 eV corresponds to C=C bond [44], which suggests that most carbon atoms of PNGC are sp 2 carbon atoms existing in conjugated honeycomb lattice. Another peak of C 1s appearing at 285.9 eV is C-C/C=N bond [39], signifying N atom has introduced into graphene or CNTs, because of no N atom existing in LS.…”

Graphene‐Based Nanocomposites for Supercapacitors

“…Besides increasing the pore distribution and SSA of rGO, doping heteroatoms (nitrogen or boron) can also effectively enhance its electrochemical performance [11,31]. An electrode based on N-doped rGO from a simple plasma treatment exhibited lower resistivity [11].…”