Pseudocapacitive Na-Ion Storage Boosts High-Rate and Areal Capacity of Self-Branched 2D Layered Metal Chalcogenide Nanoarrays

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1 Supporting information for Pseudocapacitive Na-Ion Storage Boosts High-Rate and Areal Capacity of Self-Branched 2D Layered Metal Chalcogenide Nanoarrays Dongliang Chao, Pei Liang, Zhen Chen, Linyi Bai, He Shen, Xiaoxu Liu, Xinhui Xia, Yanli Zhao, Serguei V. Savilov, Jianyi Lin, and Ze Xiang Shen The file includes: Scheme 1. Formation of the big-flake SnS2, small-sheet SnS2, and self-branched SnS2. Figure S1. FESEM images of GF backboned small-sheet, and big-flake SnS2. Figure S2. Cross section of GF backboned big-flake SnS2 and B-SnS2. Table S1. Mass loading of different SnS2 nanoarray electrodes. Figure S3. EDX spectrum of B-SnS2. Figure S4. N2 adsorption/desorption isotherm of SnS2 without branches. Figure S5. CVs and galvanostatic discharge-charge profiles for B-SnS2. Figure S6. Cycling performance of SnS2 and B-SnS2 and pure GF. Figure S7. CVs of SnS2 without branches. Figure S8. Electrochemical AC impedance spectrum. Figure S9. Na diffusion pathways on the SnS2. Figure S10. Raman spectrum of B-SnS2 nanoarray. Table S2. A survey of electrochemical properties of anodes in top performance sodium ion batteries. More Details on DFT calculations. 1

2 Scheme S1. Schematic illustration of the formation of the big-flake SnS 2, small-sheet SnS 2, and inspiration for Self-branched SnS 2 (B-SnS 2) architectures. 2

3 Figure S1. a,b) FESEM images of GF backboned small-sheet SnS 2 electrode after 40, and 80 min reaction, respectively. Insets: cross section of SnS 2 electrode. Scale bar: 200 nm. c,d) FESEM images of GF backboned big-flake SnS 2 electrode after 40, and 80 min reaction, respectively. Insets: cross section of SnS 2 electrode. Scale bar: 200 nm. The figures show that there is no obvious difference after prolonging the reaction time. e,f) Photo and FESEM image of pure GF substrate. Scale bar: 100 µm. Proposed electrode formation process: The growth mechanism of thin SnS 2 nanosheets is proposed, which involves: (i) the hydrolysis of thioacetamide and the in-situ metathesis reactions; (ii) self-assembly and oriented crystallization processes. 1-5 During the hot bath reaction, the Sn 4+ ions are favorably adsorbed onto the surface of GF with the help of ethanol, where bonding between the particles reduces the overall energy. Meanwhile, the trace water from tin chloride molecules is surrounded by ethanol molecules with hydrogen bonds. 6, 7 CH 3C(S)NH 2 which is homogeneously dispersed in ethanol reacts with trace water as shown in Eq. (1). 6, 7 The H 2S produced in-situ reacts with Sn 4+, forming sulfide nanocrystallites as shown in Eq. (2). SnS 2 tends to form two-dimensional layered hexagonal nanoflakes, which can be explained by the self-repair epitaxial growth mechanism. 2 The unique hexagonal CdI 2-type layered structure nature of the SnS 2 phase provides an oriented crystallization mechanism with limited growth along the [001] direction. 1 The bonding within the (001) layer is dominated by tight ionic bonding between Sn and S ions, whereas the stacking between the layers is maintained by weak van der Waal forces. Due to this weakly bound interlayer characteristic, crystal growth along the [001] direction is strongly oppressed in order to lower the free energy of the materials system. So SnS 2 crystallizes onto edges of the existing nanocrystallites and forms regular hexagonal nanoflakes following the thermodynamic behavior, which looks as if the nanoflakes repaired themselves at the same time as epitaxial growth. 2 3

4 Figure S2. a) Cross section of GF backboned big-flake SnS 2 electrode after 80 min reaction. b) Cross section of GF backboned self-branch SnS 2 electrode. Electrode description: Our GF backboned B-SnS 2 freestanding electrode could deliver an excellent active material mass loading percentage (ca. 83 %, 3.98 mg cm -2 active material and 0.8 mg cm -2 current collector GF), while traditional copper foil pasted electrode can only get a percentage of ca. 31 % with the same active material loading (including 3.98 mg cm -2 active material, 5 % binder, 5 % conductive agent, ca. 10 mg cm -2 copper foil). And even extending the loading to 20 mg cm -2, the copper-foil based electrode reaches an active material mass loading ca. 60 %. 4

5 Reaction time (min) Table S1. Mass loading of different SnS 2 nanoarray electrodes. Small-sheet SnS2 Mass loading (mg cm -2 ) Big-flake SnS2 Self-branched SnS

6 Figure S3. EDX spectrum, which gives Sn:S ratio of nearly 1:2.05 for B-SnS 2 nanoarrays electrode. 6

7 Figure S4. a,b) Pore size distribution (a) and the corresponding N 2 adsorption/desorption isotherm (b) of SnS 2 without branches electrode. c,d) Pore size distribution (c) and the corresponding N 2 adsorption/desorption isotherm (d) of pure graphene foam. 7

8 Figure S5. a) CVs for the first three cycles of the GF supported B-SnS 2 electrode at a scanning rate of 0.2 mv s -1. b) The first three galvanostatic discharge-charge profiles of B-SnS 2 electrode. 8

9 Figure S6. The cycling performance of SnS 2 and B-SnS 2 and pure GF at 200 ma g -1. 9

10 Figure S7. Electrochemical performance of SnS 2 without branches. a) CVs for the first three cycles at a scanning rate of 0.2 mv s -1. b) CVs at different scan rates from mv s

11 Figure S8. Electrochemical AC impedance spectrum. At full-charged state after the first three cycles of SnS 2 and B-SnS 2 electrodes. The resistance is simulated using equivalent circuit of R S(Q(R ctz w)), where R S is the ohmic resistance of solution and electrodes, R ct is the charge transfer resistance, Q is the double layer capacitance, and Z w represents Warburg resistance. The Na ion diffusion coefficient is determined by the slope of linear response of Z and ω -1/2 (Z = R S + R ct + σω -1/2 ) at lowfrequency Warburg part according to equation: D = R 2 T 2 /2A 2 n 4 F 4 C 2 σ 2, where D, R, T, A, n, F, C, σ are diffusion coefficient, gas constant (8.31 J mol -1 K -1 ), absolute temperature (298 K), surface area of the electrode (~ 1 cm 2 ), number of electrons involved in the reaction, Faraday constant, molar concentration of Na ions, slope in the linear relationship between Z and ω - 1/2, respectively. The calculated D values shows that B-SnS 2 is of higher apparent diffusion coefficient ( cm 2 s -1, coincident with the reported results), 8, 9 which may relate with shortened Na + transport pathway for B-SnS 2 electrode. 11

12 Figure S9. a) Diffusion pathways of Na on the SnS 2. b) Energy barriers of Na-ion diffusion on SnS 2 surfaces. IS, TS and FS denote surface binding sites. The arrows indicate optimum diffusion paths. The numbers show Na-diffusion energy barriers (in ev) relative to the most stable binding site. IS, TS, and FS denote initial state, transition state, and final state respectively. For NEB calculations The charging and circuit rate performance of the battery is related with the Na mobility on the electrode material. It is vital to quantify the diffusion of Na atom on the surface of SnS 2. The structural anisotropy plays an important role in the migration of Na atom on its surface, and the Na ion may migration within the surface, other than perpendicular direction, which can avoid a higher barrier between two layers. The migration barrier along IS-TS-FS direction of SnS 2 is about 65 mev, which is much smaller than that of other 2D electrode materials, such as 110 mev for MoS 2, 220 mev for TiS 2, and 70 mev for NbS 2. 10, 11 The temperature-dependent molecular transition rate can be evaluated by the Arrhenius equation 12, 13 from which the diffusion constant (D) of Na follows: D = D 0 exp( E a/(k BT)), where D 0, E a and k B are the pre-exponential factor, the activation energy (diffusion barrier) and Boltzmann s constant, respectively, T is the environmental temperature. According to the equation, the diffusion mobility of Na on SnS 2 surface is very fast. Therefore, a high diffusion kinetics of SnS 2 is expected for SIB. 12

13 Figure S10. a) Rate profiles of Na 3(VO) 2(PO 4) 2F cathode between 4.2 and 2.0 V. b) Full cell demonstration of Na 3(VO) 2(PO 4) 2F//B-SnS 2 between 1.0 and 4.0 V at a current density of 0.1 A g -1 (black lines) for activation and 0.5 A g -1 for the following cycling. The specific capacity was calculated based on the mass of the cathode material. 13

14 Figure S11. Raman spectrum of prepared B-SnS 2 nanoarray electrode tested in air. 14

15 Table S2. A survey of electrochemical properties of anodes in top performance sodium ion batteries. Electrode material Mass loading (mg/cm 2 ) Reversible capacity (mah/g@a/g), (mah/cm 2 ) Rate Capability (mah/g@ma/g) (mah/cm 2 ) References B-SnS (910@0.2),(3.7@0.8) (400@10),(1.6@40) (this work) SnO 2@SnS Heterostructure 14 Sn-based electrode 1.2 (729@0.03),(0.87@0.04) (300@7.29),(0.36@8.7) SnS 2@rGO (649@0.1),(1.49@0.23) (337@1.28),(0.78@30) Angew Chemie 2016, 55, 3408 Adv Funct Mater 2015, 25, 481 SnGeSb thin film (833@0.09),(0.05@0.005) (381@8.5),(0.02@0.5) ACS Nano 2014, 8, 4415 Sn-P Composites 17 Not provided (550@0.1) (60@10) Adv Mater 2014, 26, 4037 SnS 2-rGO (630@0.2),(0.63@0.2) (544@2),(0.54@2) Adv Mater 2014, 26, 3854 SnS-G (1037@0.03),(1.04@0.03) (308@7.3),(0.31@7.3) ACS Nano 2014, 8, 8323 Sb@TiO 2 x Nanotubes 20 Other metal/alloy electrode 1.5 (700@0.13),(1@0.2) (488@13),(0.73@20) Sb nanorod (710@0.1),(0.28@0.04) (558@20),(0.22@8) P@G hybrid (1171@0.05),(0.58@0.03) (209@26),(0.15@13) Se-C 23 Not provided Adv Mater /adma Energy Environ Sci 2015, 8, 2954 Nat Nanotechnol 2015, 10, 980 (500@0.068) (170@3.39) Acs Nano 2013, 7, 8003 Ge nanowire (375@0.185),(0.05@0.02) (103@3.7),(0.01@0.44) Nano Lett 2014, 14, 5873 Other metal oxide/sulfide electrode TiO 2@G nanocomposites (265@0.05),(0.66@0.13) (90@12),(0.23@30) Nat Commun 2015, 6, 6929 MoS 2 nanoflower 26 Fe 2O 3@C nanocomposite 27 Not provided (350@0.05) (195@10) 1.0 (740@0.2),(0.74@0.2) (317@8),(0.32@8) Angew Chemie 2014, 126, Adv Energy Mater 2015, 5, FeS@C (621@0.1),(1.24@0.2) (452@2.5),(0.9@5) Nat Commun 2015, 6, 8689 Carbonaceous electrode N-Graphene (1050@0.1),(1.1@0.1) (140@5),(0.14@5) Adv Mater 2015, 27, 2042 C quantum dot (356@0.1),(0.25@0.07) (90@20),(0.06@14) Adv Mater 2015, 27, 7861 Expanded graphite (284@0.02),(0.14@0.01) (184@0.1),(0.09@0.05) Nat Commun 2014, 5,

16 C banana peel ACS Nano 2014, 8, 7115 High areal capacity electrode in Li-ion batteries Si pomegranate Nat Nanotechnol 2014, 9, 187 Co 3O 4 nanosheet (1058@0.18),(4.4@0.74) (542@1.78),(2.25@7.4) Nano Energy 2014, 5, 91 Si-SHP/CB (2600@0.06),(4.16@0.1) (2188@0.3),(3.5@0.3) Si/CNT nanofiber (3316@0.84),(1.16@0.3) (989@42),(0.35@14.7) Adv Energy Mater 2015, 5, Energy Environ Sci 2014, 7,

17 DFT calculations First-principle plane-wave calculations within density-function theory (DFT) using projector-augmented wave (PAW) potentials were performed using the Vienna ab initio simulation package (VASP). 37, 38 The exchange and correlation potential was approximated by generalized gradient approximation (GGA), we considered the Perdew-Burke-Ernzerhof (PBE) exchange and correlation functional. After energy convergence analysis, a plane-wave basis set with kinetic energy cutoff of 500 ev and Brillouin Zone (BZ) sampling with Monk horst Pack (MP) method of k-points were chosen. All the parameters including the exchange and correlation functional and the E cut are checked to make sure our calculation was creditable. The super cells are large enough to ensure the vacuum space is at least 10 Å in any direction so as to avoid the interaction between two SnS 2. The convergence threshold was set as 10-4 ev in energy and 10-3 ev/å in force. The positions of all the atoms in the super cell were fully relaxed during the geometry optimizations. On the basis of the equilibrium structures, the edge energy is calculated and which is the critical parameter to determine the equilibrium shape of a SnS 2. Since the stability of quantum dot can evaluate as the function of formation energy, we use the edge formation energy to judge the stability of the SnS Take a triangle quantum dot as an example, the total energy composed by the E atom, E corner and E edge (See Figure 3f), thus the expression of the system energy can describe as following, E total = 3lE * edge + 3E corner + E atom (1) where, E * edge, E corner are the edge formation energy and corner formation energy respectively, show in the Figure 3f, while the E atom is the total energy of the atoms in the system. Here we consider the difference energy between two different triangular SnS 2 with side length of l 1 and l 2, because the E edge is not only influenced by the edge formation energy E * edge, but also by E corner the corner formation energy. We find the effect of corner can be eliminated by taking the difference between two side length of l 1 and l 2. The edge formation energy can be described as, E * edge = ( E tot n SnE SnS2 nµ S)/3(l 1 l 2) (2) E tot = E tot(l 1) E tot(l 2) (3) n Sn = n Sn(l 1) n Sn(l 2) (4) n = n S(l 1) n S(l 2) 2(n Sn(l 1) n Sn(l 2)) (5) where, E * edge is the edge formation energy without the contribution of E corner, E tot is the difference of total energy between different triangular SnS 2 models with the side length of l 1 and l 2. n Sn is the number of SnS 2 unit in the model. Then what we address is how large must a size of the triangle is in order to eliminate the effect of corner. Obviously, the best choice is to construct a large enough model, but realistic condition does not allow to do so. We calculate the largest size is n = 8, but it can be still not large enough and the main problem is E tot(a,n) contains the energy of corner. So we choose the n = 7 and n = 8 sizes to calculate their formation energy and the length of their edges, then calculate their difference to obtain the edge formation energy. Moreover, this model described here is also practicable to a size in nano dimension. This method gets a more accurate edge energy by calculate the different between two structures of adjacent sizes because reduce the effect of corner. So we can find the most stability structure in different edges. Four possible edges are considered: Sn edge with or without S coverage and S edge with or without Sn edge, i.e. Sn edge with S coverage (Sn-S edge), pure Sn edge (Sn edge), S edge with Sn coverage (S-Sn edge), pure S edge (S edge). S-Sn edge is not stable and would transfer into S edge, then three possible edge are list in Figure 3f. Because the energy of edge with incomplete S coverage must be intermediate value, the edge energy as a function of the chemical potential of sulfur is showed in Figure. 3g. 17

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