Bouquet-like Mn2SnO4 nanocomposite engineered with graphene

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Bouquet-like Mn2SnO4 nanocomposite engineered with graphene sheets as an advance lithium-ion battery anode Wasif ur Rehman, Youlong Xu, Xiaofei Sun, Inam Ullah, Yuan Zhang, and Long Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04164 • Publication Date (Web): 08 May 2018 Downloaded from http://pubs.acs.org on May 8, 2018

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ACS Applied Materials & Interfaces

Bouquet-like Mn2SnO4 nanocomposite engineered with graphene sheets as an advance lithium-ion battery anode Wasif ur rehman1, 2, Youlong Xu1, 2*, Xiaofei Sun1, 2*, Inam Ullah 2, Yuan Zhang2, Long Li 2 1

Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education & International

Center for Dielectric Research, Xi’an Jiaotong University, Xi’an, China 2

Shaanxi Engineering Research Center of Advanced Energy Materials & Devices, Xi’an Jiaotong University,

Xi’an, China KEYWORDS: tin oxide, graphene sheets, anode materials, ternary Mn2SnO4, lithium-ion battery

ABSTRACT

Volume expansion is a major challenge associated with tin oxide (SnOx) which caused the poor cyclibility in lithium-ion batteries anode. A bare tin dioxide (SnO2), tin dioxide with graphene sheets (SnO2@GS) and bouquet-like nanocomposite struture (Mn2SnO4@GS) are prepared via hydrothermal method followed by annealing. The obtained composite material presents a bouquet structure containing manganese and tin oxide nanoparticles network with graphene sheets. Benefiting from this porous nano structure in which graphene sheets provide high electronic pathways to enhance the electronic conductivity, uniformly distrubuted particles which offers accelerated kinetic reaction with lithium ion and reduced volume deviation in the particle of tin dioxide (SnO2) while charge-discharge testing. As a consequence, ternary composite Mn2SnO4@GS has showed a high rate performance and outstanding cyclability of anode material for lithium-ion batteries. The

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electrode is achieved a specific capacity about 1070 mA h g-1 at current density of 400 mA g-1 after 200 cycles, meanwhile electrode is still delivering a specific capacity about 455 mA h g-1 at high current density of 2500 mA g-1. Ternary Mn2SnO4@GS material could facilitate a fabriction of unique structure and conductive network as an advance Lithium-Ion Batteries.

1. INTRODUCTION Out of all commercialized energy storage devices, Lithium-Ion Batteries (LIBs) are still developing as most promising of all for their energy, long life cyclic stability and friendly environmental advantages 1-3. However, they suffer from pronounced challenges like, limited rate capability and low specific capacity in the range ~ 372 mA h g⁻1 mainly due to unfavorable use of graphite as anode material. Therefore, a ominous requirement existed of utilizing advanced technology to develop novel anode materials with promising high performance for improved LIBs 4-6. Low cost tin oxides (SnO and SnO2) are promise to theoretical capacity of 756 mA h g-1 (about twice greater than commercial available graphite), as they received increasing attention as progressive anode matrials 7-10. On the other hand there are some serious problems with tin oxide, (І) the volume expansion during charging-discharging of lithium-ion which boost the electrode cracking and reduce efficiency with a deteriorated effect on capacity fading, and (ІІ) a poor electronic and ionic conductivity causing slower charged -discharged rates in SnO2 electrode. Recent times has seen three affective ways towards improved performance of tin oxides as anode material; (І) unique structure of tin oxide with outstanding properties for anodes is introduced, such as SnO2 nanoparticles, nanotubes, hollow spheres and 2D nanosheets11, for elevated electrochemical performance for LIBs anode. (ІІ) To focus on fabricating hybrid nanostructure by engneering with carbon, can be post and direct coating and graphene dip-coating 12. (ІІІ) Ternary materials of Sn-based anode materials are mostly wrote as the formula of MxSnOy (M = Mn, Zn, Sr and Co). The role of these ternary oxides (addition of Mn, Zr, Sr) during chargingdischarging mechansim in the Li+ cycling process to buffer the crystal structre and taking part in lattice amorphization of the mixed oxide 13. Unfornunately Mn2SnO4 is seldom used as anode material due to quick capacity fading during cycling test, as result disruption within struture because of large volume change and assembling of inorganic nanoparticles with high surface energy14. Still the main problem in experimental Sn-


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based anode material is the poor cycling performance due to their several volume expansion and simultaneously solid electrolyte interfance (SEI) layer formation during cycling test15-16. To resolve this problem, many approaches (for ternary oxide) have been adopted like, doping of elements (Mn, Co, Ni Al, C) has been a consistent study in recent reports for the important the electronic conductivity of anode materials, with additive inceptive of absorbing structural strain by volume changes

17-19

. Secondly, to devloped some

uniques structures which can provide extra free space, might be hollow, hierarchical and porous, to help in term of volume expansion alleviate the large volume changes and protect structural damages

16, 20

. Including

unique sturatural materials with porousity or hollows, which possess inhernet large surfaces can dramatically shorten the diffusion path and take part to improve kinetic movement of lithium ion migration between the electrode materials and electrolyte 21-22, thus contributing towards improved rate capacity and cycling stability of the storage devices 23-24.

For the first time, here, we have used a triangle network among among SnO2, SnO2@GS and bouquet-like nanocomposite (Mn2SnO4@GS) structure and demonstrated a promising advantage of unique structure in the fabrication of anode for LIBs. Mn2SnO4@GS have to addressed the volume expansion problem as it reduced the transportation distance between ions and electrons during the cycling process. Furthermore, the graphene network in different phases of charge-discharge process plays an influential role to enhance the electronic conductivity of anode. It also helps to form a stable (SEI) plateform which suppresses the decomposition of the electrolyte and facilitates a stable cycling performance. A comparative morphology and performance analysis of SnO2, SnO2@GS and Mn2SnO4@GS as prospective engineered adoptions, explains the importance of utilizing ternary system, unique structure, and graphene sheets coating towards developing exotic anode materials for LIBs.

2. EXPERIMENTAL SECTION 2.1. Preparation of Tin dioxide, SnO2@GS and Mn2SnO4@GS The Graphene oxide (GO), was prepared via modified Hummer’s route 2. Mn2SnO4@GS was synthesized in two-steps, hydrothermal and annealing method. To homogenous desperation of graphene oxide, synthesis 0.25 GO was used in 60 mL DI water and sonicated about 2 hours (we call it as solution 1). After first sonication,



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1.0 g SnCl2.2H2O, added in the suspension, followed by another round of ultrsonication for about half an hour. Then, kept on stirring machine for 30 min. Meanwhile prepared Hexamethylenetetramine (HMT) 1.5 g, and KMnO4 (0.35 g) solutions in 10 mL water separately followed by the addition of ethylene glycol (EG) 20 mL dropwise under vigorous stirring for 1 h (named solution 2). Finally, solution(2) mixed slowly into (1), along with uninterrupted stir at room temperature about 24 h. Further, the mixture shifted to autoclave bottle and keep the temperature of 180 ⁰C for 360 minutes. Sample was allowed to cool down till room temperature and washed three times with DI water. It was put again in the oven at 60 ⁰C for overnight for drying. During the last stage the final material Mn2SnO4@GS was obtained by annealing process at 400 ⁰C for 4 hours under Argon (Ar) condition. For bare SnO2, sample synthesised same as above procedure except that GO and KMnO4 was not added (brief experimental schematic diagram in Figure 1 and Figure S1). 2.2. Charactrization Surface morphology characterization was performed, as usual scanning electron microscopy. To characterized the phase sturcture properties X-ray diffraction (XRD) data was collected using a X’Pert pro “PANalytical”, provided along Cu/Kalpha radiation (λ). For surface analysis X-Ray Photo-Electron Spectroscopy (XPS) test, conducted through Nova (AXIS) ULtrabld Japan using Al Kalpha (1486.6 eV) source. TEM, JEOL, JEM2100Plus, Tokyo, Japan. To invistigated frequency modes, using Raman scattering with Jobin LABRam high resolution spectrometer French made using 514 nm irradiation. Thermogravimetric experiment (TG, TGDSC1) performed with evolutionary of bare tin dioxide, Mn2SnO4, GS, while heat value of 10 degree per minute at air atmosphere from room temperature to 800 ºC. NICOLETTM iS10 (US), fourier transform infrared spectrum (FT-IR) experiment is recorded with the wave from 400 cm-1 to 4000 cm-1 .


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Figure 1. Schematic diagram the growth mechanism (before and after) cycling of SnO2, SnO2@GS and Mn2SnO4@GS composites. 2.3. Electrochemical characterization For active material a homogenous, and compact sulurry (Mn2SnO4@GS, SnO2, and tin dioxide, 70 wt%), conductive carbon (acetylene black, 20 wt%) and PVDF (binder 10 wt%) in N-methyl-2-pyrrolidone (NMP) solution pasted carefully on copper (Cu) foil. Further, covered in clean page for drying, temperature can be 120 ⁰C in vacume for 12 h. Next, the weight of electrode material was about 0.7-1.3 mg cm-2, CR2025 coin cells assembled in argon-filled glovebox . The Li-metal used as an anode for LIBs, a solution of 1 mol L⁻1 LiPF6 in EC /DMC (1 : 1 wt ratio) liquid solvent . The electrode was tested Land CT2001A Battery Testing System (BTS), where Cycling Voltammetry (CV), and electrochemical impedance spectra (EIS) experiment observed at frequency limt of 10-2 Hz to 102 kHz.

3. Results and Discussion Scanning electron microscopy (SEM) to extract for a comparative morphological analysis of materials. The images are showed in Figure 2(a-c). SEM images of bare SnO2, it is clear that SnO2 particles shows poriferous 3D morphology in which the nanoparticles have seemed to position themselves well at different magnification. In Figure 2(d-f) shows graphene sheet encapsulate tin oxide particles, and the particles are very small in size.



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Figure 2(g-i) is composite nanoparticles Mn2SnO4 bouquet-like structure, which shows a low magnification SEM images of Mn2SnO4@GS. The images are exhibited, the composite particles has sandwiched in graphene sheets, there are no such irrugualr particles attachment, which are found in SnO2 sample. Further that Figure. 2f, the nanocomposite particles, has decorated splendidly with the graphene sheets, as a result particles are stick with the flower stigma. The selected area describes a homogenous distribution of the required elements mapping (of Mn, C and Sn). Moreover, energy dispersive spectroscopy of Mn, Sn, C, O element, shows the existence of particles in composite material Mn2SnO4@GS (seen Figure S2). These images are in small-size nanoparticles, could provide cushion, put force to keep away from volume change, also beneficial to keep the SEI unity while cycling experiment, which is good binding agreement between particles and Li-ions transportation.

Figure 2. Surface morphology images, (a-c) SnO2. (d-f) SnO2@GS. (g-i) Mn2SnO4@GS and elemental mapping of Mn2SnO4@GS. TEM image in Figure 3a exhibits SnO2@GS, graphene sheets are wrapped the SnO2 nanoparticles, forming the hierarchical structure SnO2@GS. In Figure 3b, a high magnified TEM scan of SnO2@GS, reveals that the


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graphene sheets consisting of few layered sheet. It is worth mentioning that after strong ultrasonication for TEM characterization, the SnO2 nano-particles were found attached with graphene sheets, attributing a powerful inter-action between nanoparticles and GS. These images study hinting, GS acts important role in the particles growth process, for not only they help reducing the size of the particles but also took care of the extensive aggregation SnO2 offered free space within nanostructures 25. Figure 3c a high magnification TEM image shows SnO2 nanoparticles anchored into the graphene sheets with distinct fringe spacing of about 0.258 and 0.175 nm, corresponding to (101) and (211) planes of SnO2, respectively. Further from Figure 3d a low magnification, selected area describes a homogenous distribution of the required elements (Mn, Sn, O, C) mapping in Figure 3(g-j). For Figure 3e, a high maginfication image shows graphene sheets highly embedding the Mn2SnO4 crystalinic particles unitedly. Figure 3f complete image to present Mn2SnO4 nanoparticles, showed with distinct spacing of (almost 0.312 nm, other space 0.254 nm respectively), which lead (220) and (222) planes matching to Mn2SnO4. It is observed that graphene sheets could restrict the growth of Mn2SnO4 nanoparticles and serves as conductive path.

Figure 3. TEM exhibition of the SnO2@GS and Mn2SnO4@GS; (a-c). Under different magnifications, SnO2@GS, (d-f) Mn2SnO4@GS and (g- j) elemental mapping of Mn2SnO4@GS selected area in Figure 3d.



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Figure 4a, followed the hydrothermal route to prepare the material and follwed by annealing at 400 ⁰C for 4 h. No distinct diffrences in XRD pattern were observed for SnO2 and SnO2@GS indicated similar phase composition and structure of two materials. However, with the addition of Mn the phase structure changed to Mn2SnO4 nanocomposite material

26

. XRD pattern of Mn2SnO4 well matches with a typical Mn2SnO4@GS

phase (JCPDS # 75-1516) along with characteristic peaks at 2θ value of (26.2⁰, 34.1⁰, 36.6⁰, 41.1⁰, 48.2⁰, 53.9⁰, 58.8⁰, 62.1⁰, 66.8⁰, 71.2⁰) indexed as (220), (311), (222), (400), (422), (511), (440), (531), (620) and (533 ) respectively. Meanwhile, all the peaks have well characterized , suggesting Mn2SnO4 elements seen well nano-crystalic. Figure 4b, TG and DSC curves, presented the carbon content, thermal analysis of Mn2SnO4@GS composites was performed by thermal gravimetric analysis. To characterized this experiment, temperature was fixed at range of 50 to 800 ⁰C under air atmospheric. A small amount of weight lost was recorded from 50 to 150 ⁰C, is indicating the wetness of the particles. Relatively large weight loss was detected from a large exothermic peak from 250 ⁰C to 475 ⁰C, attributing a complete combustion of GS in the air flow after, which the material hasn’t suffered further weight lost. Thus, weight percentage of graphene is 14.8 % in composite Mn2SnO4@GS. To further analyze the residual GS in SnO2@GS and Mn2SnO4@GS we used Raman experiment in the range from 400 to 2400 cm-1 as indicated in Figure 4c. Raman spectra show several characterized broad peaks (called bands) of about 650 cm-1, attributed to the characteristic peak of SnO2, there are two bands at about 1360, 1579 cm-1, corresponding to D and G-band respectively

27

.

Tradtionaly D-band is indicating the dis-ordered graphene structure, meanwhile the G-band exhibits tangent vibrational, in graphene atoms with graphite layer (seen in Figure S4). FTIR spectra of SnO2, SnO2@GS and Mn2SnO4 were charactrized, get information the affects of SnO2 on pyrolytically with graphene sheets shown in Figure 4d. For this experiment limited range was from 400 to 2000 cm-1, FT-IR spectra about 1715 and 1267 cm-1 are corresponded to the oxygen in containing groups on GO sheets the peaks 26. The dis-appearance of such peaks in SnO2 and Mn2SnO2@GS indicates the effective conversion from GO to RGO. As compared with bare SnO2, the typical peaks at 495 and 670 cm-1 in SnO2@GS and Mn2SnO4@GS are ascribed to the symmetric and anti symmetric O-Sn-O stretching, which indicates the good combination of SnO2, Mn2SnO4 nanoparticles and reduce graphene oxide 28.


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Figure 4. (a) XRD patterns, (b) TGA curve for the Mn2SnO4@GS nanocomposite, (c) Raman shift of SnO2@GS and Mn2SnO4@GS and (d) FTIR spectrum of bare tin oxide, SnO2@GS and Mn2SnO4@GS. To invesitigate the elemental composition and the chemical state on the surface of Mn2SnO4@GS composite were carried out, with the XPS experiment., XPS spectra is exhibited, binding energy values belonging to Mn 2p, Sn 3d, O 1s, and C 1s, shown in Figure 5a. For Figure 5(a, b) XPS spectra is presented the information about (Mn 2p and Sn 3d ) respectively. For Figure 5a, there are two peaks observed at 652.7 and 640.6 eV, matching with spin orbit peak of the Mn 2p1/2 as well as Mn 2p3/2 of Mn2+. In addition, small window for Mn after 200 cycles, the Mn spectra have high intensive level about the metal oxides (641.1 eV), onwards Li2CO3 (642.3 eV) indicating very thin surface profile

29

, where it is same before cycling Mn2+ systems

30-31

. From

Figure 5b, Sn 3d spectrum can be divided into four main peaks; 495.0, and 486.5 eV belong the Sn 3d3/2 and Sn 3d5/2 of Sn4+, the fitting peaks at about 492.9 and 484.5 eV are ascribed to Sn 3d3/2 and Sn 3d5/2 of Sn⁰ 32-33 . Furthermore, Mn2SnO4@GS anode material surface were investigated after 200 cycles . In Figure 5b small window shows, having high intensity of the tin oxide (484 eV) closer to a before cycling, suggests a smaller morphology changes after cycling electrode

34

. XPS peaks presents almost equal shifting information, these

results confirm that partial Sn4+ ions reduced to Sn⁰ by carbothermal reduction, a 284.4 eV peak corresponds to



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carbon element associated with oxygen in the carbonate ions as shown in Figure 5c 35. The other two peaks originate at 286 eV (C-O-C), onwards 288.5 eV (O-C=O) respectively, suggesting that almost all GO is successfully reduce to rGO sheets after annealing. XPS spectra for oxygen in Figure 5d, the high resolution small window for O 1s, the photoemission spectrum indicates three different oxygen species on the surface. Furthermore, the three peaks in the metal oxide region at 529.2 eV, 531.2 eV, and 532.2 eV corresponding to manganese oxide, SnO2 and C=O aromatic groups respectively 36 .

Figure 5. XPS spectra of (a) Mn 2p small window after 200 cycles Mn information, (b) Sn 3d before and after cycling, (c) C 1s and (d) O 1s for Mn2SnO4@GS. To investigate the potential lithium storage performance, the electrochemical properties of SnO2, SnO2@GS and final composite material Mn2SnO4@GS role as anodes were tested in battery testing system (BTS). Electrochemical reaction information was acquired using cyclic voltammetry (CVs) measurement shown in Figure 6(a-c). For bare SnO2 and SnO2@GS reduction process shows a distinct peak ~ 0.89 V, first cycle, expectedly dis-appears in the following cycles. It shows for the irreversible reactions of the SnO2 anode (SnO2


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+ 4Li+ + 4e- ↔ 2Li2O + Sn) during lithium reaction, further SEI film formation and Li2O formation with the reduction of SnO2 into Sn metallic phase as shown in the following equation37. Sn + xLi+ + xe⁻ ↔ LixSn (0 x 4.4)

The strong peaks ~ 0.61 and 1.31 V during the oxidation peaks of SnO2, respectively . The relative intensity and position of the reaction peaks overlapping in second and third cycles, suggesting good reversibility. CV curves profile of Mn2SnO4@GS, attributing for the first cycle and three reduction peaks, clearly identified in Figure 6(c). It shows the decomposition of Mn2SnO4 within Mn and Sn (0.89 V), the formation of SEI film that leads to formatting amorphous Li2O (0.4 V) at second cycle following by an alloyed-reaction between tin and Li (0.14 V)

14, 38

. Three other oxidation peaks observed at region 1( 0.61 V), other (1.32 V) and region 2

(2.05 V) typically corresponded to dealloying of LixSn and oxidation of Sn and Mn respectivelly

39-40

. Here,

second and third cycle peaks overlapping each others, indicating the excellent reversiblity of the nanocomposite Mn2SnO4@GS electrode. The correlated plateau realms were observed in Figure 6d for the

initial three charged-discharged profiles of the mentioned electrodes.



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Figure 6. (a, b, c) the Cv profiles of SnO2, SnO2@GS and Mn2SnO4@GS respectively, (d) initial dischargecharge voltage profiles of SnO2, SnO2@GS and Mn2SnO4@GS, (e) charging-discharging cycles with current density of 500 mA g-1 (f) comparison storage capacities at different current .

Galvanostatic measurements were used to probe the electrochemical cycling performance for the dischargingcharging process as shown in Figure 6d at a current density of 500 mA g-1 in the voltage limit from 0.01 to 3.00 V. Three samples SnO2, SnO2@GS and Mn2SnO4@GS showed similar discharged profiles, in addition pointing three plateaus (1.2, 0.8 and 0.7 V respectively) and a slope below 0.7 V which is attributing alloying relation of Sn to lithium and the reversible reaction between lithium and graphene sheets

41-44

. The intial

charge-discharge capacities of Mn2SnO4@GS are found to be 1946/1195 in comparison to the much lower specific capacities of 1750/1060 and 1546/965 mA h g⁻1 for bare SnO2 and SnO2@GS respectively indicated in Figure 6e. Mn2SnO4@GS formidably reaches an intial coulombic efficiency of 61.3 %, significantly is high than that of bare SnO2 (57 %) and SnO2@GS (59.1 %) respectively. Low initial coulombic efficiencies are common problem for LIBs anodes, therefore, this initial coulombic efficiency improvement of Mn2SnO4@GS cannot bear a mark for its use as an anode in a full cell. Irreversible capacity loss due to formation of SEI and various side reactions at low potential is another major aspect to be considered here

45-48

. For this problem

resarchers focused on the minimizing the electrode and electrolyte contact area and surface modification which is in form of Al2O3 coating

49-51

. We found a good cycling performance and discharge capacity discharge

capacity of ~1042 mA h g-1 is obtained after 500 cycles for composite Mn2SnO4@GS material (seen in Figure S5) as compared to the inferior capacities of 200 mA h g⁻1 and 890 mA h g⁻1 for SnO2 and SnO2@GS after 100 cycles at 500 mA g⁻1 of current density, can seen at Figure 6e. This capacity decay in SnO2 and SnO2@GS could be attributed to volume expansion and the formation of aggregated large-sized particles during charging and discharging process. Figure 6f, illustrates a comparative analysis of the performance of Mn2SnO4@GS, and SnO2@GS at different current densities. At high current density 2500 mA g⁻1, the Mn2SnO4@GS still retains a capacity of 455.2 mA h g⁻1, but for SnO2@GS results in 300 mA h g⁻1 of capacity at the equal current density supply. Furthermore, Mn2SnO4@GS mantains a superior performance throughout also offers much stable electrochemical performance than bare SnO2 and SnO2@GS via hydrothermal route


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and annealing process. On behalf of electrochemical performance of Mn2SnO4 with graphene sheets exceeds, where using tin oxide encouraging of LIBs anode materials for advanced applications

52-54

. For Figure 7a the

composite material (Mn2SnO4@GS) exhibits first 100 cycles specific capacity charge-discharge performance, after first cycle discharge curves of nanocomposite material are different from first, suggesting structural or textural modifications durning the first cycle and after few cycles becomes much stable

41, 55

. The result of

galvanostatically discharged and charged experiments is in good agreement with the CVof Mn2SnO4@GS (seen in Figure. 6(c)). Figure 7b exhibits the long term cycling charge and discharge performance at a current rate of 400 mA g-1. Impressively, Mn2SnO4@GS has showed a reversible capacities of 1070 mA h g-1 and 1042 mA h g-1 at current density of 500 mA g⁻1 achieved after 200 and 500 cycles respectively which is high to compare with tin dioxide as well as SnO2@GS (seen in Figure S5). The following Table 1 can describes recent works on Sn-based ternary with unique structures composite as anode for LIBs.

Table 1. Sn-based materials with unique structures nano-composite for LIBs anode Current density(mA g-1)

Specific capacity (mA h g-1)

50

537 for 50 cycles

Years with references 2013 56

75

566 for 100 cycles

2013 57

SnO2Graphene sheets

200

700 for 400 cycles

2014 58

Sn-Ni@PEO nanotube

500

545for 200 cycles

2014 59

SnO2@Sn Graphene

100

901 for 500 cycle

2015 60

Sn-Ni-Cu-@Carbon

450

455 for 400 cycles

2016 61

Sn(MoO4)2 DNA

50

400 for 200 cycles

2016 62

Cu6Sn5/Sn

100

605.8 for 100

2016 63

M(HPO4)2 M=Zr, Sn,Ti

100

302 for 80 cycles

2018 13

Sn-M (M=Fe,Ni)@C

100

441.6 for 100 cycles

2018 64

Sn Nanoparticles@C

200

740 for 200 cycles

2017 65

Ni3Sn2/C alloy bowl

500

732 for 200 cycles

2017 66

Ultrasmall MoS2, SnOx

300

725.3 for 800 cycles

2017 67

SnO2@GS

500

890 for 100 cycles

In this work

Bouquet-Mn2SnO4@GS

400

1070 for 200 cycles

In this work

Sn-based anode composition GrapheneTiO2/SnO2 ternary Core-shell Sn@C



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Electrochemical impedance spectroscopy (EIS) experiments were characterized by the resistance evolution, providing additional information of charge transformation into electrochemical performance of material intended to be used as an anode for LIBs. In Figure 7c, all the spectra present typical Nyquist plot of SnO2, SnO2@GS and Mn2SnO4@GS electrodes. Ternary material Mn2SnO4@GS exhibited a smaller semicircle at high medium frequency, meaning a smaller charge transfer resistance Rct (~60 Ω), comapred with SnO2@GS (~120 Ω) and SnO2 (~250 Ω), indicates improved kinetic transport for the good electrical contact and electrode reactions at Mn2SnO4 anode. At low frequency area, the Sloped curve line corresponds to ion-diffusion called (Warburg impedance). Larger Rct of SnO2 and SnO2@GS might be responsible for the lower capacity. The mechanism in Figure 7d, the process of battery operation during charge-discharge the ternary anode Mn2SnO4@GS result might due to the synergetic effect. The Mn2SnO4@GS and the covalent mechanism on the graphene substrates could provide large electrode and electrolyte interface area which inhibit particle aggregation, suggesting high reversible capacity. This ternary anode material is expected to curtail the diffusion for Li+ ions plus electrons (e⁻) which would efficiently transfer between the Mn2SnO4@GS and the current collector based on graphene sheets with high electronic conductivity. The bouquet-like structure (Mn2SnO4@GS) helps the easy admission and much fast diffusion of the electrolytes, capable the whole process superior and stable performance.


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Figure 7. Lithium storage properties of the Mn2SnO4@GS nanocomposite; (a) initial cycle upto 100 cycles discharge-charge voltage profiles, (b) cyclic performance of Mn2SnO4@GS of current density 400 mA g⁻1 (c) Nyquist plots “EIS” of tin oxide, SnO2@GS and Mn2SnO4@GS, (d) schematic function of Li+ interaction and e⁻. To invesitagated surface morphology of electrodes at a current density of 400 mA g-1 after 200 cycles, here acquired their SEM images to reveal their structure stableness, exhibited from Figure 8(a-c) , most of the particles maintained the flower shape without abvious cracks and ruptures (comparison in Figure S2), images exhibits the better particles volume expansion before and after cycling. The networks of Li+ insertion and the flow of electron (e-) much eased shown in Figure 8c. From Figure 8(a, b, c) are comparsion of Mn2SnO4@GS and SnO2@GS (shown in Figure S3). TEM images of Mn2SnO4@GS at different resultions, providing the crystaline highway after 200 cycles, which is much effective for the free transportation of the electron in electrode, where cannot able the crystaline highway in SnO2@GS nanoparticles TEM images

68-70

. These

results further demonstrate that the porous structure can effectively oppose the volume variation of the anode



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during the lithiation and dilithiation process where the network of GS could highly enhance structure stabilty, of anode materials for LIBs.

Figure 8. After 200 cycles SEM; (a-c) Mn2SnO4@GS , TEM images (d, e, f) for Mn2SnO4@GS nanocomposite.

4. Conclusion In summary, through the use of two step method to fabricate bouquet-like Mn2SnO4@GS ternary anode material, which provided a uniform size distribution and well organized network with graphene nano sheets.

Benefiting from this network of GS, we reduce the volume expansion in the prospective electrode which in turn provided an improved lithium storage peformance for their use as anode in LIBs. The Mn2SnO4@GS nanocomposite material delivered high specific capacity of 1070 mA h g-1 could be maintained after 200 cycles. Improved electrochemical properties of our material is due to its attribution of forming a unique layered and interior bouquet-like struture with graphene sheets incorporation. The adopted synthesis strategy is facile, including low cost with a promise to translate in developing transition oxides with graphene composite with unique structures.


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AUTHOR INFORMATION Corresponding author *Prof. Xu Youlong. Email: [email protected] *Assoc. Prof. Sun Xiaofei. Email: [email protected] Tel: +86-13991815083 Fax: +86-29-8266-5161 Author contributions In this work all the authors contributed equally.

Funding Sources The support of National Natural Science Foundation of China (Grant # 51772240, Grant # 21503158), the Key Research and Development Plan of Shaanxi Province China (2017ZDCXL-GY-08-02),the Natural Science Foundation of Shaanxi Province China, (Grant # 2014JQ2-2007), the 111 project (B14040) and the Fundamental Research Funds for the Central Universities of China (Grant # xjj2014044). Notes The authors declare no ﬁnancial interest.

ACKNOWLEDGMENT Experiment of SEM and TEM were done at the International Center for Dielectric Research (ICDR), Xi’an Jiaotong University, Xi’an, China. We are thankful of Miss Yanzhu Dai and Mr. Chuansheng Ma to help us during the TEM and FE-SEM experiments.

RELATED CONTENT Supporting Information Brief Experimental process, the comparison SEM images of before and after 200 cycles of SnO2, SnO2@GS and Mn2SnO4@GS. EDX of Mn2SnO4@GS, and TEM images of Mn2SnO4@GS. Raman spectra of above three samples, information of SnO2 surface vibration. Mn2SnO4@GS after 200 cycles electrochemical performance.



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Bouquet-like Mn2SnO4 nanocomposite engineered with graphene

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