C3N4 Graphene Composite

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Energy, Environmental, and Catalysis Applications

1D-2D C3N4/Graphene Composite as a Preferred
Anode Material for Lithium-Ion Batteries – Importance
of Heterostructure Design via DFT Computation
David Adekoya, Shanqing Zhang, and Marlies Hankel
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c04900 • Publication Date (Web): 18 May 2020
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Page 1 of 28 ACS Applied Materials & Interfaces
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1D-2D C3N4/Graphene Composite as a Preferred
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Anode Material for Lithium-Ion Batteries –
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Importance of Heterostructure Design via DFT
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Computation
12 David Adekoyaa, Shanqing Zhanga, Marlies Hankelb*
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16 aCentre for Clean Environment and Energy, Environment Futures Research Institute Griffith School of
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18 Environment, Griffith University Gold Coast, QLD 4222, Australia
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20 bAustralian Institute of Bioengineering & Nanotechnology, The University of Queensland, Brisbane,
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Queensland 4072, Australia
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28 ABSTRACT: Graphene is commonly used to improve the electrochemical performance of electrode
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30 materials in rechargeable batteries by forming graphene-based heterostructures. Two-dimensional
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32 graphitic carbon nitride (C3N4) is an analogue of graphene and it is often used to form a 1D/2D and
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34 2D/2D C3N4/graphene heterostructure. However, a theoretical understanding of the heterointerface in
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36 these heterostructures and how this affects their electrochemical performance is lacking. In this work
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38 we study the heterointerface of a 1D/2D and 2D/2D C3N4/graphene heterostructure and how the
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40 different dimensions influence the lithium ion battery performance of the heterostructure. Our Density
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42 Functional Theory (DFT) study showed that the common problem of C-N bond breakage experienced
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in 2D/2D C3N4/graphene heterostructure does not occur in the 1D/2D heterostructure. Furthermore, the
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47 1D-2D heterostructure showed superior conductivity in comparison to that of the 2D-2D heterostructure
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49 of C3N4/graphene. The 1D/2D C3N4/graphene heterostructure also recorded a high theoretical capacity
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51 and rapid charge transfer. These results suggest that the properties of a heterostructure are influenced
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53 by the dimension of materials at the interface. These discoveries on the relationship between material
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55 dimension in heterostructure electrodes and their electrochemical performance will motivate the design
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57 of advanced electrode materials for rechargeable batteries.
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60 KEYWORDS: 1D-2D, 2D-2D, C3N4/graphene, heterostructure, lithium-ion batteries
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3 INTRODUCTION
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6 The continuous growth of the world’s population and fast-paced development of the technological age
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8 has resulted in an increase in demand for energy and technological devices 1. Similarly, the demand for
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10 portable electronic devices has been on the rise, especially with the discoveries made in the research for
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12 electric vehicles (EV). These developments have intensified the research into rechargeable lithium ion
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batteries (LIBs) with higher specific capacity, long cycle life, high stability and superior rate capability
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16 2-3.
17 Of all the alternative portable electronic devices available in the market, LIBs have continued to
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19 dominate over the last decade, making them applicable for large scale applications such as off-grid
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21 energy storage devices, for electric vehicles (EV) and hybrid vehicles (HEV) 4-5. Current LIBs employ
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23 graphite as the anode material but while it has continued to deliver its theoretical limit of 372 mAh/g,
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25 it falls short in reaching the required minimum for long range EVs 6-7. Graphene, a derivative of
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27 graphite, was discovered decades ago and has proven to be a better form of graphite owing to its superior
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29 conductivity and large surface area. However, its performance as an anode material is still limited.
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31 Therefore, there is a need to explore other materials which can function as suitable anode materials or
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can combine with graphene to improve its performance 8.
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37 Graphene possess a two-dimensional (2D) sheet-like structure which enables it to easily hybridize with
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39 numerous materials to form graphene based heterostructures which can demonstrate outstanding
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41 properties. This hybridization of 2D graphene with other materials can occur as either 0D–2D, 1D–2D,
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43 2D–2D, and 3D heterostructure or composites, depending on the structure of the foreign material 9.
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45 Formation of this type of heterostructures provides a material with improved electronic conductivity,
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47 larger surface area, increased Li reaction sites and well buffered volume expansion 10. For example,
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49 several researchers have reported the design of 2D-2D heterostructures obtained by growing other 2D
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51 materials on 2D graphene 9, 11. Graphene analogues, which have 2D structures (e.g. C3N4 and MoS2 etc.)
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are widely used to form 2D-2D structures with graphene and one of the most reported is C3N4 12.
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Formation of a C3N4/graphene composite is highly beneficial. Due to stronger electronegativity of
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58 nitrogen compared to that of carbon, the electronic and chemical properties of graphene can be easily
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60 tuned and its reversible capacity can be improved by doping it with pyridinic nitrogen 10. Also, because

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3 of its heterocyclic ring composed of C-N and C=N bonds, C3N4 possess a large number of π bonds, just
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5 like graphene, hence, it can bind effectively to it through a π-π interaction 10, 13. Lastly, the nitrogen
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atom in C3N4 possess p-electrons and a lone pair of electrons which means it can exhibit electron-rich
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10 Lewis base properties, which will provide a heterostructure with rapid electron mobility and superior
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12 conductivity 9-10. C3N4 is mostly synthesized as a 2D sheet structure throughout literature however, it
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14 can be obtained as a 1D fibre/rod structure as previously reported 14-15.
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17 As an anode material for LIBs, although it could deliver a high theoretical capacity (524 mAh/g), C3N4
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19 suffers from low conductivity and an irreversible intercalation mechanism which results in poor battery
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21 performance 16. Veith et al. proved that this irreversible intercalation and resulting poor conductivity
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23 and electrochemical performance of C3N4 anode can be traced to the breakage of a C-N bond in the
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25 structure of C3N4 as Li was added to it.17 Therefore, several researchers have reported C3N4/graphene
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heterostructure for LIBs because it is expected that the higher conductivity and surface area of graphene
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30 will provide a composite with increased performance 10, 18. Although progress have been made, there
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32 are still many unsolved challenges which require further studies to be uncovered e.g. the lithium
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34 intercalation/deintercalation mechanism of this heterostructure in LIBs. Furthermore, we can
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36 categorically say that all previously reported works on C3N4/graphene composite/heterostructure focus
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38 on a 2D-2D C3N4/graphene heterostructure with the assumption that it will perform better than a 1D-
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40 2D C3N4/graphene. However, none of these works provided any electrochemical test or DFT
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42 calculations to prove this claim. There are no reports on the application of 1D-2D C3N4/graphene
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Herein, we report, for the first time, a DFT simulated study and an electrochemical test on the
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application of such a 1D/2D carbon nitride/reduced graphene oxide (1D/2D C3N4/graphene)
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52 heterostructure for LIB application. We also compare the effectiveness of such a 1D/2D heterostructure
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54 to that of a 2D/2D heterostructure by studying the lithium storage mechanism, flexibility of the
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56 membrane, partial density of states and charge density distribution. Our work shows the importance of
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58 material dimension on the electrochemical property of the heterostructure and concludes that the 1D/2D
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60 heterostructure is a preferred anode material for lithium ion batteries.

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3 METHODS
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6 Computational Details: All calculations have been carried out with the Vienna ab initio Simulation
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8 Package (VASP) 19. 3D periodic boundary conditions were applied to simulate the infinitely large
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10 systems. A 20 Å vacuum space between sheets was set to prevent the interaction between two membrane
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12 layers. The cell parameters for a unit cell of the 1D-2D C3N4/graphene heterostructure were found to be
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a = 19.73 Å and b = 7.34 Å. The Brillouin zone of the heterostructure was sampled by a 3 × 3 × 1 k-
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17 points mesh. The electronic structure of the system was treated using the generalized gradient
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19 approximation (GGA) with the PBE functional 20. The van der Waals interactions were added to the
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21 standard DFT description by Grimme's D2 scheme 21. All calculations include spin polarization. In all
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23 calculations the convergence parameters were 10-6 eV for the energy, 0.01 eV/Å for the forces and an
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25 energy cut off of 500 eV was employed. A Gaussian smearing of 0.05 eV was applied. Charge analysis
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27 was performed via Bader analysis 22-23, which included the core charges, and charge density difference
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29 analysis within VASP. For Li atom mobility on the heterostructure, the climbing image nudged elastic
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31 band (CI-NEB) method was employed. Similar parameters to those for geometry optimization were
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used while final structures of geometry optimization calculations for single Li atom were selected.
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37 The strength of the Li-F interaction, where F is the 1D-2D C3N4/graphene or 2D-2D C3N4/graphene, is
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39 usually given by the average adsorption energy, Eads,
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Eads = (nE(Li) + E(F) - E(Lin@F))/n (1)
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44 where n is the total number of adsorbed Li atoms and E(Li), E(F) and E(Lin@F) are the total energies
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46 of a single Li atom, the pristine material and the interacting Lin@F system with n Li atoms, respectively.
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By this definition, a positive Eads indicates that the interacting system is stable, and that the adsorption
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of the Li atom is favourable.
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53 However, due to our recursive process of Li loading we report the recursive adsorption energy per
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lithium, Erec,
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58 Erec = (E(Li) + E(Li(n-1)@F) - E(Lin@F)) (2)
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3 A positive Erec indicates that the adsorption of the most recent Li atom is favourable. Eads represents the
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5 adsorption energy per Li for a certain fixed loading while Erec represents the adsorption energy for the
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most recent adsorbed single Li.
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10 RESULTS AND DISCUSSION
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13 To begin our study, we calculate the diffusion and adsorption properties of Li on the 1D/2D and
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15 2D/2D heterostructures by performing density functional theory (DFT) calculation using the Vienna ab
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17 initio Simulation Package (VASP). For our DFT calculations we built two heterostructures for this
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19 study; (1) a 1D-2D C3N4/graphene heterostructure and (2) a 2D-2D C3N4/graphene heterostructure. For
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the 1D-2D heterostructure a graphene sheet was used to model the 2D graphene structure while a single
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24 unit of the 1D C3N4 fibre was placed on it to create the 1D-2D heterostructure (see Figure 1a). In the
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26 case of our 2D/2D heterostructure, a 6 x 6 graphene sheet and a 2 x 2 C3N4 membrane were combined
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28 to form the 2D/2D heterostructure (see Figure 1b). Geometry and k-point optimization were carried out
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30 for both heterostructure membranes to obtain the stable and preferred structures.
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56 Figure 1. (a) Atomic structure of 1D/2D C3N4/graphene supercell. The numbers represent the possible
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58 adsorption position of Li atom. (b) Atomic structure of 2D/2D C3N4/graphene supercell. Brown balls
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60 represent carbon, blue nitrogen, and pink hydrogen.

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3 In order to identify the preferred lithium adsorption site on the heterostructures, we placed a Li atom
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5 at different positions in each structure, performed geometry optimization and considered the adsorption
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energy and stability of the membrane. To this end, the preferred position (with the strongest recursive
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10 adsorption energy of 3.24 eV) for Li adsorption on the 1D-2D C3N4/graphene heterostructure was inside
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12 a six membered carbon ring of the 2D graphene sheet. All other positions which were tested had very
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14 similar adsorption energies with only slight differences in energies suggesting that the 1D/2D
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16 heterostructure might have a uniform rate of Li mobility across it. From the side view of Figure 2a it is
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18 obvious that the 1D-2D C3N4/graphene structure did not experience any distortion upon Li atom
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20 adsorption which suggests that it is flexible and stable. In the case of the 2D/2D heterostructure, based
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22 on the adsorption energies, rate of membrane distortion and position of the Li atom upon adsorption,
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24 the preferred position for Li in the heterostructure was in the central ring structure of the 2D graphene
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sheet with adsorption energy of -4.45 eV (see Figure 2b). However, compared to the 1D/2D
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29 heterostructure, there was a slight distortion of the C3N4 structure upon Li adsorption and this was due
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31 to the Li getting trapped inside the C3N4 membrane. This early distortion of the membranes at a single
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33 Li adsorption calls for caution as it suggests that the membrane might encounter breakage if distortion
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35 is too high. Based on the results obtained thus far they suggest that the Li atoms will have a mobility
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37 comparable to that of graphene and that the 1D-2D C3N4/graphene heterostructure will experience
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39 excellent Li transport when applied as an anode material for LIBs.
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56 Figure 2. (a) The preferred structure of 1D/2D C3N4/graphene with 1 Li atom adsorbed. (b) The
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58 preferred structure of 2D/2D C3N4/graphene with 1 Li atom adsorbed. Brown balls represent carbon,
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60 blue nitrogen, pink hydrogen, and green lithium.

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3 We continue our study by gradually increasing the Li loading on both heterostructures whilst
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5 considering the cohesive energy of Li (1.63 eV) and noting the position of Li in the heterostructures.
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Based on our calculations we find that the 1D/2D heterostructure could accommodate more Li atoms
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10 (14) compared to the 2D/2D heterostructure suggesting that it could provide a higher reversible capacity
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12 when tested electrochemically for LIBs. At a loading of 14 Li for the 1D/2D heterostructure the last Li
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14 had an adsorption energy of 1.85 eV. There was only a slight distortion to both the C3N4 and graphene
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16 membranes and most of the Li atoms were absorbed on the graphene (see Figure 3a). Conversely, the
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18 maximum loading for the 2D/2D heterostructure was only 9 Li atoms. When we consider the fully
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20 loaded membranes of both heterostructures we notice that the C3N4 is greatly strained or bent in Figure
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22 3b compared to that of Figure 3a. Furthermore, the 9 lithium on the 2D-2D heterostructure tend to stay
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24 close to the C3N4 instead of interacting with the graphene membrane. This migration of the Li atoms
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towards the pyridinic nitrogen of the 2D C3N4 sheet is due to the formation of a strong ionic bond
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29 between the Li and pyridinic nitrogen. This interaction between a host anode material and an alkali
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31 metal ion can favour attraction and storage of alkali metal ions which results in high capacity
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33 performance. This observation of lithium strongly interacting with the pyridinic nitrogen of 2D C3N4
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35 membrane is similar to the report of Hankel et al.16. A similar report was given by Veith et al. who
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37 explained that this strong binding is what causes the loss of crystallinity in 2D C3N4 and leads to
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39 breakage of the C-N bond in its structure 17. This breakage of the C-N bond can be clearly seen in Figure
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41 3b (the red dotted line shows the point where a C-N bond is broken). This bond breakage can lead to
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43 the destruction of the host anode material (C3N4) because as more Li atoms are loaded into the structure,
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they tend to move towards the pyridinic nitrogen. This is like the case of electrode destruction after
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several cycles of electrochemical battery testing. The significance of this bond breakage dilemma is that
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50 while combining 2D C3N4 with 2D graphene to form a 2D/2D heterostructure to increase the
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52 conductivity, another problem is created. The lithium still interact too strongly with the 2D C3N4 instead
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54 of with the graphene which in-turn puts too much strain on the C3N4 and this will subsequently lead to
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56 bond breakage or total destruction as more lithium are loaded 16-17, 24. We believe this phenomenon of
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58 bond breakage and possibly electrode destruction could be the reason why most publications on C3N4
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60 and 2D/2D C3N4/graphene heterostructures report gradual increase in capacity (activation of electrode)

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3 after several cycles. Our DFT result show that the 1D/2D C3N4/graphene heterostructure would be more
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C3N4/graphene heterostructure.
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54 Figure 3. (a) Structure of 1D/2D C3N4/graphene with maximum lithium loading (14 Li atoms) adsorbed
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56 (no bond breakage and lithium adsorbed on graphene. (b) Structure of 2D/2D C3N4/graphene with
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58 maximum lithium loading (9 Li atoms) adsorbed showing bond breakage and the lithium trapped by
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60 C3N4. Brown balls represent carbon, blue nitrogen, pink hydrogen, and green lithium.

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3 Although we tried to add more Li atoms to the 1D-2D heterostructure we observed that the adsorption
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5 energy with 15 Li was either too close to that of bulk Li (1.63 eV) or the Li atoms began to intercalate
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between the two 2D sheets. This will eventually result in the destruction of the heterostructure and
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10 finally the C3N4 membrane and give an unrealistic result or irreversible capacity which cannot be
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12 replicated in experiments. It is also important to note that the Li-Li distance in the 1D-2D C3N4/graphene
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14 heterostructure loaded with 14 Li was 2.96 Å which is above that of Li2 (2.6 Å). This configuration in
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16 Figure 3a is therefore acceptable but adding more Li atoms will bring the Li even closer together leading
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18 to shorter Li –Li distances, which is not acceptable. After several trials we discovered the most stable
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20 and feasible configuration is the one presented in Figure 3a. The 14 Li loaded on 1D-2D C3N4/graphene
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22 heterostructure resulted in a capacity of 719 mAh/g which is larger than that of both C3N4 and graphene.
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24 Therefore, the concept of 1D-2D heterostructure can be a promising approach to improving the capacity
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of electrode materials for LIB.
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Figure 4. (a) SEM, (b) TEM and (c) HRTEM images of the as-prepared 1D-2D C3N4/graphene
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54 heterostructure. (d) Cyclic voltammogram curves of the 1D/2D C3N4/graphene heterostructure in the
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56 first three cycles (e) Typical charge and discharge curves of the 1D/2D C3N4/graphene heterostructure
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58 (f) Charge and discharge capacities of 1D/2D C3N4/graphene heterostructure at the 0.1C in the first 90
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3 The results and conclusions of our DFT simulation were further justified by synthesizing and testing
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5 the electrochemical performance of our 1D/2D C3N4/graphene heterostructure as an anode material for
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LIBs. Details of the synthesis method for the 1D-2D C3N4/graphene heterostructure is provided in the
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10 supporting information and it is depicted by the schematic in Figure S1. Surface characterization of the
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12 as prepared 1D-2D C3N4/graphene heterostructure were carried out to observe its morphology. From
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14 Figure 4a (Scanning electron microscope micrograph of 1D-2D C3N4/graphene) it is obvious that C3N4
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16 is a 1D fibre/rod-like structure aligned on and surrounded by different sheets of 2D graphene. Figure
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18 4b displays the Transmission electron micrograph (TEM) of the 1D-2D C3N4/graphene heterostructure
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20 and the graphene layers. Folds and wrinkles can be seen as well as the 1D C3N4 fibre structure. The
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22 high-resolution TEM (HRTEM) result shown in Figure 4c shows that the 1D-C3N4 was well-aligned on
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24 top of the 2D graphene sheet. These surface analysis results confirm that 1D-2D C3N4/graphene was
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successfully obtained. For the battery test we prepared the slurry of the heterostructure and coated it on
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29 a copper foil, dried it in an oven and assembled the cut electrodes into a coin cell using Li metal as the
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31 counter electrode while 1 m LiPF6 in 1:1 v/v ethylene carbonate (EC)/diethyl carbonate (DEC) was
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33 used as the electrolyte. The cyclic voltammetry (CV) and charge-discharge curves of the heterostructure
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35 were tested between 0.001 – 3.000 V at 0.1 mV/s. From Figure 4d the CV curves of 1D/2D
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37 C3N4/graphene heterostructure show a cathodic peak at ~0.75 and 1.6 V with anodic peaks at 0.36 and
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39 1.20 V. These peaks can be attributed to the intercalation process of Li into the electrode, development
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41 of the solid electrolyte interphase film and the occurrence of other possible side reactions 13, 18. The
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43 charge/discharge curves for the 1st, 2nd, 20th, 40th, 50th and 90th cycles of the heterostructure cycled at
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0.1C are shown in Figure 4e. The charge/discharge curves do not show a prominent voltage plateau
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which suggests that the 1D/2D C3N4/graphene is quite stable as an anode material 25. The initial
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50 discharge capacity of the 1D/2D C3N4/graphene anode was 1427 mAh/g (56% columbic efficiency) but
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52 this capacity dropped to 862.2 mAh/g at the 2nd cycle and stabilised within this capacity range for the
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54 20th cycle - 849.7 mAh/g (90.4% columbic efficiency), slightly increased for the 40th cycle (918.7
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56 mAh/g) and dropped to 718.3 mAh/g for the 90th cycle. This trend is clearly seen in Figure 4f. The drop
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58 in capacity after the first cycle can be traced to the formation of a passivated Solid Electrolyte Interphase
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60 layer over the surface of the 1D/2D C3N4/graphene anode. However, we must highlight that the

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3 activation in our 1D/2D C3N4/graphene anode is highly insignificant compared to previous reports on
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5 C3N4 based anode materials 18. Despite this, the performance of this 1D/2D C3N4/graphene anode
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exceeds that of previously reported C3N416, 18, C3N4 fibre15, nitrogen doped graphene26 and C3N4/reduced
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10 graphene oxide composite 13 (see Table S1). It is obvious that the result of our electrochemical LIB
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12 battery testing closely matches our DFT simulation because the reversible capacity of 719 mAh/g
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14 obtained from DFT calculation is very close to the capacity of 718.3 mAh/g recorded from battery
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16 testing. This shows further confirms that our study of this heterostructure is well detailed and shows the
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53 Figure 5. (a) Charge density difference of 1D/2D C3N4/graphene with 1 Li atom adsorbed. (b) Charge
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density difference of 2D/2D C3N4/graphene with 1 Li atom adsorbed. Brown balls represent carbon,
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58 blue nitrogen, pink hydrogen, and green lithium. Red clouds represent electron depletion while blue
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60 represent electron gain. The isosurface level is drawn at 0.005 e/bohr3

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3 To obtain an in-depth understanding of the interaction between adsorbed Li atoms and the
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5 heterostructure membranes, we carry out a charge density distribution study as well as Bader charge
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analysis. In the case of the 1D/2D heterostructure, the charge density distribution when 1 Li atom was
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10 loaded (see Figure 5a) shows a significant charge depletion around the Li atom in the membrane which
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12 suggests that most of the charge was transferred from the Li atom into the 1D-2D membrane. Figure 5a
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14 shows that both, the graphene and C3N4 participate in the charge transfer process and that there is
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16 significant interaction between the Li atom and both membranes. The Bader charge analysis determined
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18 that with 1 Li loaded a total of 0.88 |e| was transferred to the 1D-2D C3N4/graphene heterostructure
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20 from the Li atom. A similar phenomenon can be observed in the membrane of the 2D-2D heterostructure
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22 (see Figure 5b). In the case of 1 Li adsorbed on the 2D/2D heterostructure the majority of the charge
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24 accumulation region was on the C3N4 structure and only a small amount can be seen on the graphene
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membrane suggesting that charges from the Li atom were transferred to the C3N4 membrane. Bader
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29 analysis calculated showed that 0.91 |e| was transferred by 1 Li atom in the case of the 2D/2D
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31 heterostructure. This seems to suggest much less interaction of the Li atom with the graphene. We then
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33 consider the 1D/2D heterostructure with 14 Li loaded. Bader analysis records that each Li transferred
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35 0.77 |e| to the heterostructure. The charge density distribution study (Figure 6a) shows that most of the
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37 light blue region (electron rich regions) is across the surface of the 1D-C3N4 which could be due to the
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39 lone pair electron rich nitrogens on C3N4. For the 2D/2D heterostructure (see Figure 6b), the charge
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41 density distribution was like the case of 1 Li loaded and in the case of the Bader charge each Li
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43 transferred 0.87 |e| . This shows that the 1D/2D heterostructure interaction of 1D-C3N4 and graphene
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can greatly improve electrostatic interactions of Li and the electron transfer within the heterostructure.
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Figure 6. (a) Charge density difference of 1D/2D C3N4/graphene with 14 Li atoms adsorbed. (b) Charge
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56 density difference of 2D/2D C3N4/graphene with 9 Li atoms adsorbed. Brown balls represent carbon,
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58 blue nitrogen, pink hydrogen, and green lithium. Blue clouds represent electron gain and red clouds
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60 electron loss. The isosurface level is drawn at 0.005 e/bohr3

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3 We also determined the partial density of states (PDOS) for both, 1D/2D and 2D/2D heterostructures,
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5 and compared the PDOS to that of pristine 1D and 2D-C3N4. We also considered the membranes when
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they were fully loaded with Li atoms. We begin by studying the effect of making a graphene based
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10 heterostructure by comparing the PDOS for the 1D/2D and 2D/2D heterostructure with that of their
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12 individual pristine C3N4 structures. From Figure 7a we can see that the pristine 1D C3N4 shows a band
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14 gap showing that the pristine material is a semiconductor. The PDOS of the 1D-2D heterostructure is
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16 shown in Figure 7b. Here we can see that the minimum of the conduction band has shifted very close
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18 to the fermi level for both the N and the C atoms of the 1D-C3N4, while the maximum of the valence
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20 bands shifts away from the fermi level. It is the C atoms of the graphene that provide the system with
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22 improved conductivity resulting in a very small gap. When we test the PDOS of 2D-C3N4 and 2D/2D
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24 heterostructure (Figure 7c) we notice a similar phenomenon. Here the shift of the C and N bands from
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the C3N4 towards or away from the Fermi level is a bit less than was see for the 1D-2D hetero structure
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29 but also in the 2D-2D case, the graphene significantly improves the conductivity of the material. These
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31 results show that the addition of graphene to either dimensionality of C3N4 will be beneficial to the
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33 electronic property of the obtained hybrid structure.
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36 Figure 7. Comparison of the partial density of states (PDOS) for 1D-C3N4, 1D/2D, 2D-C3N4, and 2D/2D
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38 C3N4/graphene (a) 1D-C3N4, (b) 1D/2D C3N4/graphene (c) 2D-C3N4, (d) 2D/2D C3N4/graphene.
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41 Figure 8a presents the PDOS when 1 Li atom is loaded onto the 1D-2D heterostructure. We can see
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43 that the minimum of the conduction band of all membrane atoms have shifted across the fermi level
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making the material a conductor. This is due to the Li atom transferring its electron to the material.
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Figure 8b confirms this. Here we show the PDOS of the single Li atoms and representative C and N
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50 atoms close by. We can see no overlap between the Li(s) orbitals and those of the material. Again, we
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52 can see that the C(p) and N(p) orbitals have shifted across the Fermi level. A similar picture is observed
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54 for the 2D-2D material with 1 Li atom. As for the 1D-2D material the C and N conduction bands shift
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56 across the Fermi level, see Figure 8c. Figure 8d confirms that there is no overlap between the Li atom
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58 orbitals and those of the material. As for the 1D-2D material this shows that the interaction of the Li
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60 atom and the two different materials is ionic. From Figure 8e, when 1D/2D was fully loaded with 14 Li

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3 atoms, there was a significant shift of the conduction bands towards the Fermi level now showing
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5 significant amplitudes across the Fermi level indicating that the material is now conductive. Noticeably,
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the electrons in the conductive band are mainly stored in the p orbital of carbon from graphene although
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10 those of C3N4 also contribute. Conversely, when we consider the PDOS of fully loaded 2D/2D with 9
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12 Li (see Figure 8f), the evident shift of the conduction band can be equally attributed to the p orbitals of
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14 the material. These observed features of the PDOS of the fully loaded systems are due to the electron
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16 transfer from the Li atoms to the material which is in line with our understanding that the interaction is
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18 ionic. In summary, the PDOS results showed that both can will possess a small gap when no Li atom is
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20 loaded. When a single Li atom is loaded both structures experience migration of the conduction band
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22 and as more Li atoms are loaded a sizeable shift of the conduction band will occur. This shift of the
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24 conduction band to more negative energies can be traced to the significant charge transfer of Li atoms
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to the membranes. The PDOS results prove that designing a graphene based heterostructure is beneficial
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29 to the conductivity and stability of an electrode material which improves its overall LIBs performance.
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49 Figure 8. Partial density of states for 1D/2D and 2D/2D C3N4/graphene (a) PDOS of 1D/2D
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51 C3N4/graphene with 1 Li loaded, (b) PDOS of 1D/2D C3N4/graphene - the Li and single C and N close
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53 by, (c) PDOS of 2D/2D C3N4/graphene with 1 Li loaded, (d) PDOS of 2D/2D C3N4/graphene - the Li
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55 and single C and N close by, (e) fully loaded (14 Li loaded) 1D/2D C3N4/graphene membrane, (f) fully
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57 loaded (9 Li loaded) 2D/2D C3N4/graphene membrane.
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60

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3 Considering that the most feasible heterostructure in this study was the 1D/2D heterostructure we
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5 conclude our study by determining the mobility and diffusion path of Li atoms in the 1D-2D
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C3N4/graphene heterostructure using the transition state theory (TST). Figure 9a shows one transition
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10 path along with the atomic structures of the initial, transition and final states (denoted as IS, TS and FS,
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12 respectively). At the IS (Figure 9b) the Li atom sits in a carbon ring of graphene. It then moves to the
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14 TS (Figure 9c), which is over the C-C bond and finally, to the FS (Figure 9d), where it sits above another
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16 graphene carbon ring. From the plot in Figure 9, the diffusion barrier for Li movement is below 0.4 eV
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18 which is like the previously reported barrier for graphene analogues and carbon allotropes (between
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20 0.32 and 0.46 eV).27
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34 Figure 9. (a) The energy minimum diffusion pathway of a Li atom on the 1D/2D C3N4/graphene
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36 heterostructure. (b) the atomic structure of initial state (IS), (c) transition state (TS), and (d) final state
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(FS).
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41 CONCLUSIONS
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44 In conclusion, our DFT calculations provided insight into the importance of the 1D-2D heterointerface
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46 and how it influences Li adsorption and mobility, the role of both the C3N4 and graphene and how their
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48 properties affect the performance of the heterostructure as an anode material. While C3N4 can provide
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50 electron rich centres due to the presence of its nitrogen to increase capacity, graphene provides the
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larger surface area and improves the conductivity of the heterostructure which facilitates more electron
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transport across the entire heterostructure. This 1D-2D heterointerface can produce an anode material
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57 with improved Li transport and storage, fast electron transfers and produce a LIB electrode with superior
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60

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3 performance. This work inspires the design of heterostructures which can serve as advanced anode
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5 materials for high performance lithium ion batteries.
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8 ASSOCIATED CONTENT
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Supporting Information
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13 Details of material synthesis and characterization, schematic illustration of synthesis procedure of 1D-
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15 2D C3N4/graphene heterostructure and table of LIBs performance comparison. This material is
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17 available free of charge via the Internet at http://pubs.acs.org.
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20 AUTHOR INFORMATION
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23 Corresponding Author
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26 *E-mail: m.hankel@uq.edu.au.
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ORCID
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31 David Adekoya: http://orcid.org/0000-0001-6400-827X
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34 Shanqing Zhang: http://orcid.org/0000-0001-5192-1844
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37 Marlies Hankel: 0000-0002-8297-7231
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Notes
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42 The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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47 This work is financially supported by the Australian Research Council (ARC) Discovery Projects
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49 (DP160102627 and DP1701048343). The authors thank the Australian Research Council for support of
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this project through the LIEF program. The authors appreciate the University of Queensland Research
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Computing Centre (RCC), the Queensland Cyber Infrastructure Foundation (QCIF) and the Australian
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56 Institute for Bioengineering and Nanotechnology (AIBN) at the University of Queensland for the
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58 computational resources provided for this project. This research was undertaken with the assistance of
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60 resources provided through the NCI National Facility systems at the Australian National University,

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3 the PAWSEY Supercomputing Centre located in Western Australia through the National Merit
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5 Allocation Scheme.
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3 GRAPHICAL TABLE OF CONTENTS
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19 A DFT simulated study and an electrochemical test on the application of 1D-2D
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22 C3N4/graphene heterostructure for LIBs. The fabricated 1D/2D C3N4/graphene electrode
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24 delivered a reversible capacity of 718.3 mAh/g which aligns closely with the 719 mAh/g predicted
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26 from our DFT calculations. This performance can be ascribed to the structural stability,
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29 conductivity and effective charge transfer exhibited by the 1D-2D heterostructure.
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