Graphene Microflowers Fabricated via a Selective

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Hierarchical Mn3O4/graphene microflowers fabricated via selective dissolution strategy for alkali-metal-ion storage Chen Tang, Fangyu Xiong, Xuhui Yao, Shuangshuang Tan, Binxu Lan, Qinyou An, Ping Luo, and Liqiang Mai ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 25 Mar 2019 Downloaded from http://pubs.acs.org on March 25, 2019

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ACS Applied Materials & Interfaces

Hierarchical Mn3O4/Graphene Microflowers Fabricated via Selective Dissolution Strategy for Alkali-Metal-Ion Storage Chen Tang1,#, Fangyu Xiong2,#, Xuhui Yao2, Shuangshuang Tan2, Binxu Lan1, Qinyou An2,*, Ping Luo1,*, Liqiang Mai2,* 1

Hubei Provincial Key Laboratory of Green Materials for Light Industry, Collaborative Innovation

Center of Green Light-weight Materials and Processing, School of Materials and Chemical Engineering, Hubei University of Technology Wuhan 430068 P. R. China 2

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan

University of Technology, Wuhan, 430070 P. R. China

Abstract Mn3O4 is a potential anode for alkali-metal (Li/Na/K) ion batteries because of the high capacity, abundant resources, and eco-friendliness. However, its ion storage performance is limited by poor electronic conductivity and large volume expansion during charging/discharging process. In this study, we presented a facile dissolution strategy to fabricate ultra-thin nanosheet-assembled hierarchical Mn3O4/graphene microflowers, realizing enhanced alkali-metal-ion storage performance. The synthetic mechanism was proven as the selective dissolution of vanadium via controlled experiments with different reaction times. The as-synthesized composites showed high lithium storage capacity (about 900 mAh g−1) and superior cycliablity (~ 400 mAh g−1 after 500 cycles). In addition, when evaluated as NIB anode, the reversible capacity of about 200 mAh g−1 was attained, which remained at 167 mAh g−1 after 200 cycles. Moreover, to the best of our knowledge, the potassium storage properties of Mn3O4 were evaluated for the first time and a reversible capacity of about 230 mAh g−1 was achieved. We believe that our findings will be instructive for future investigations of high-capacity anode materials for alkali-metal-ion batteries. Keywords ： Selective dissolution, Mn3O4, hierarchical nanostructure, alkali-metal-ion battery, anode, graphene

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Introduction Currently, the increasing demand for new green energy sources is promoting the development of large-scale energy storage systems (LSESSs). Lithium-ion battery (LIB) is a promising choice for LSESSs depending on its high energy efficiency, energy density, and discharge voltage.1-6 Recently, Na-ion battery (NIB) and K-ion battery (KIB) systems have attracted much attention and are expected to replace LIBs as they operate using similar mechanism, while Na and K are more abundant than Li.7-14 However, further development of all such battery systems requires the development of high-capacity anode materials.10, 15, 16 Among a serious of anode materials, Mn3O4 has attracted much attention according to its high capacity (936 mAh g−1), high earth abundance, and eco-friendliness.17-21 Unfortunately, its application is astricted by poor cycling stability and underutilized capacity caused by the large volume change during the cycling process, along with low electrical conductivity. Constructing hierarchical structures can efficiently elevate the cycling stability by accommodating the volume change in the voids between substructures.22-24 On the other hand, introducing graphene to efficiently increase the electrical conductivity has been demonstrated in many instances.15,

25-28

Therefore,

Mn3O4/graphene composites with hierarchical structures hold high promise to realize high-rate and long-life lithium storage, and exploiting a facile and simple strategy to obtain such composite is significant.29, 30 Furthermore, Mn3O4 is hopeful to achieve high sodium/potassium storage capacity, but to our best knowledge, the literatures about its sodium storage performance are rare and its potassium storage performance has not been investigated yet. In this work, a facile selective dissolution strategy was utilized to produce ultra-thin nanosheet-assembled hierarchical Mn3O4/graphene microflowers (Mn3O4-G). The structure evolution during the dissolution process was investigated and the synthetic mechanism was demonstrated as the selective dissolution of vanadium. Benefiting from the ultra-thin nanosheet-assembled hierarchical structure and graphene decoration, the Mn3O4-G displayed high lithium storage capacity and outstanding cycling performance. Moreover, the Mn3O4-G also displayed attractive sodium/potassium storage performance. Results and Discussion The Mn3O4-G was obtained from the MnV2O6/graphene composite (MVO-G) by a NaOH solution treatment process. The structural evolution and reaction mechanism for the transformation from


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MVO-G to Mn3O4-G were also studied. The X-ray diffraction (XRD) pattern (Figure S1a) of MVO-G was indexed to MnV2O6. As shown in Figure 1a and Figure S1b, the MnV2O6 had nanorod-bundle morphology and was wrapped by graphene. In the high-resolution transmission electron microscope (HRTEM) image (Figure S1c, d), the lattice fringe spacing of 0.322 nm accords with the d-spacing of (110) facets in MnV2O6. In addition, all the bands in the Raman spectrum (Figure 1d) originate from the vibration of VO3− units.31 After dissolution treatment in a NaOH solution for 30 min, some nanosheets were formed on the nanorod bundle (Figure 1b). In the corresponding Raman spectrum (Figure 1e), a new band appeared at ~650 cm−1, which was the characteristic band of Mn3O4, indicating that the composition of the nanosheets on the nanorod bundle was Mn3O4.32 After dissolution treatment for 180 min, the nanorod bundle was completely transformed to nanosheet-assembled microflowers (Figure 1c). Meanwhile, the bands of VO3− disappeared in the Raman spectrum, testifying the complete dissolution of metavanadate (Figure 1f). A schematic illustration of structural evolution mechanism during the selective dissolution treatment is shown in Figure 1g. The dissolution of MnV2O6 nanorod bundles was accompanied by the growing of Mn3O4 nanosheets on the nanorod bundles, which can be considered as a process of selective dissolution of vanadium. After complete dissolution of MnV2O6 nanorod bundles, the Mn3O4 nanosheets formed microflowers. The possible reaction mechanism of selective dissolution is described as follows: (Dissolution) MnV2O6(s) → 2VO3− + Mn2+

(1)

(Precipitation) 6Mn2+ + O2 + 12OH− → 2Mn3O4(s) + 6H2O

(2)

(Overall) 6MnV2O6(s) + O2 + 12OH− → 12VO3− + 2Mn3O4(s) + 6H2O

(3)

Oxygen dissolved in solution participates in the reaction and facilitated the oxidation of Mn2+ to Mn3+. Meanwhile, the reaction shown by Equation (2) will enhance the dissolution of MnV2O6 (Equation (1)).



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Figure 1. TEM images of (a) MVO-G precursor, (b) sample obtained from MVO-G precursor by selective dissolution treatment for 30 min and (c) 180 min. The Raman spectrum of (d) MVO-G precursor, (e) sample obtained from MVO-G precursor by selective dissolution treatment for 30 min and (f) 180 min. (g) Schematic illustration of the process of structural evolution from a MnV2O6 nanorod bundle to Mn3O4 microflower during the selective dissolution treatment.

The crystalline composition of Mn3O4-G was identified using XRD (Figure 2a). All XRD peaks were indexed to Mn3O4. In addition, the Raman spectrum of Mn3O4-G (Figure S2), the bands situated at 1350 and 1610 cm-1 were belonging to the D and G band of graphene, respectively.25 It was clearly indicated the presence of graphene in the Mn3O4. Besides, in the -ray photoelectron spectroscopy (XPS) spectrum of Mn3O4-G (Figure 2b), the energy gap between Mn 2p3/2 and 2p1/2 levels was 11.7 eV, conforming to that of Mn3O4.33 In addition, a similar spectrum was obtained for Mn 2p for the


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Mn3O4 microflowers without graphene (Figure S3). FESEM (Field-emission scanning electron microscope) and TEM were employed to analyze the microstructure of Mn3O4-G. The FESEM images (Figure 2c) showed that the Mn3O4-G sample was composed of nanosheet-assembled microflowers with a diameter of 1–2 μm. The TEM images of Mn3O4-G (Figure 2d) revealed that the microflower was composed of ultra-thin nanosheets with thickness of below 10 nm. Some interstices were observed between nanosheets, corresponding well with the FESEM images. In Figure 2e, mesopores in the nanosheets were observed. In addition, distances of lattice fringes in the HRTEM image of Mn3O4-G (Figure 2f) are

0.276 and 0.249 nm ,

corresponding to the d-spacings of (103) and (211) planes in Mn3O4, respectively. In addition, energy dispersive X-ray spectroscopy (EDS) elemental mappings showed that Mn, O, and C were distributed uniformly in Mn3O4-G (Figure 2g), indicating a homogenous composite of Mn3O4 and graphene nanosheets. Furthermore, thermogravimetric (TG) analysis of Mn3O4-G was performed. In the TG curve of Mn3O4-G (Figure S4), a mass loss of 18.5% was observed at around 350 °C, indicating a graphene content of 18.5 wt% in Mn3O4-G. The specific surface area and pore structure of as-prepared samples were investigated by nitrogen isothermal absorption/desorption tests. The isotherm of Mn3O4-G is shown in Figure S5a, which was identified as a type-Ⅱ curve with H4 hysteresis loop, implying the existence of narrow slit-like pores. The Mn3O4-G sample had a specific surface area of 113.3 m2 g−1, which was greater than that of MVO-G (21.5 m2 g−1). The large increase in specific surface area implied a drastic structural evolution during the selective dissolution treatment. The pore size distribution plot (Figure S5b) showed that the pores in Mn3O4-G were mainly in the 2–4 and 10–100 nm size ranges, corresponding to the mesopores in the nanosheets and interstices between nanosheets, respectively.



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Figure 2. (a) XRD pattern, (b) XPS spectrum, (c) FESEM image, (d, e) TEM images, (f) HRTEM image, and (g) EDS elemental mappings of Mn3O4-G.

The lithium storage behaviors of Mn3O4 microflowers, MVO-G, and Mn3O4-G were evaluated using CR2016-type half cells. The cyclic voltammetry (CV) curves of Mn3O4-G in 0.01–3 V (vs. Li+/Li) were displayed in Figure 3a. The peak at ~0.8 V in the first cycle was attributed to electrolyte decomposition and the reduction of Mn3O4 to MnO, i.e., Mn3O4 + 2Li+ + 2e- → 3MnO + Li2O.27, 34 In addition, the sharp peak at ~0.15 V was due to the further reduction progress of manganese oxide, i.e., MnO + 2Li+ + 2e- → Mn + Li2O.27, 34 In the second and third cathodic scans, this sharp reduction peak shifted to higher potential (~0.25 V) due to the enhanced reaction kinetics, which corresponded well with results of previous studies.35 In the anodic scans, the peaks at ~1.2 and ~2.1 V were assigned to the oxidation from metallic Mn to MnO and MnO to higher oxidation states, respectively.34, 35 The CV curve at the third cycle almost overlapped with that of the second cycle, indicating the high reversibility of the Mn3O4-G anode. A fully reversible transformation reaction can be expressed as: Mn3O4 + 8Li+ + 8e- ↔ 3Mn0 + 8Li2O. The CV curves of Mn3O4 (Figure S6) display similar with larger overpotential, indicating that the introduction of graphene improves conductivity and reduces polarization. In addition, the lithium storage performances of Mn3O4-G, MVO-G, and Mn3O4 microflowers were further evaluated by galvanostatic charge/discharge tests


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(Figure 3b). At 0.2 A g−1, the Mn3O4-G delivers a high reversible capacity of 893 mAh g−1, outperforming that of Mn3O4 microflowers (502 mAh g−1) and MVO-G (472 mAh g−1). Discharge plateaus at ~0.7 and ~0.3 V were observed in first cycles (Figure 3c), while only one discharge plateau at ~0.4 V appeared in the subsequent cycles, which agreed well with the CV curves. In addition, Mn3O4-G also displayed enhanced rate performance (Figure 3d). At 1 A g−1, Mn3O4-G still showed a capacity of about 615 mAh g−1, while those of Mn3O4 microflowers and MVO-G were only 272 and 427 mAh g−1, respectively. The superior rate performance of Mn3O4-G was attributed to the ultra-thin porous nanosheet-assembled microstructure and graphene decoration. The charge/discharge curves of Mn3O4-G at 0.1 to 1 A g−1 (Figure S7) showed that the overpotentials were similar. In addition, the long-term cycling stability of Mn3O4-G was evaluated at 0.5 A g−1 (Figure 3e). After 500 cycles, a capacity of ~400 mAh g−1 was maintained, which surpasses the theoretical capacity of graphite. This excellent cycling stability was ascribed to the hierarchical structure containing voids between the nanosheets that could accommodate volume changes during the charge/discharge process.

Figure 3. (a) CV curves of Mn3O4-G at 0.1 mV s−1. (b) Cycling performance of Mn3O4 microflowers, MVO-G, and Mn3O4-G at 0.2 A g−1 and (c) the corresponding discharge/charge profiles of Mn3O4-G. (d) Rate performance of Mn3O4 microflowers, MVO-G, and Mn3O4-G. (e) Long-term cycling stability of Mn3O4-G at 0.5 A g−1.



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Furthermore, the electrochemical performances of Mn3O4-G anode in NIB and KIB were evaluated. At 0.2 A g−1, the Mn3O4-G showed a reversible sodium-ion storage capacity of ~200 mAh g−1 (Figure 4a). No obvious plateau was observed at low potential in the discharge curves of Mn3O4-G (Figure 4b). At 1 A g−1, a sodium storage capacity of about 160 mAh g−1 was still attained (Figure 4c). As anode KIB material, the Mn3O4-G displays a reversible capacity of about 230 mAh g−1 at 0.1 A g−1. Similar with that in sodium storage No obvious plateau displays in the corresponded charge/discharge curves (Figure 4e). The rate performance of Mn3O4-G as anode material for KIB also has been evaluated. After current density increasing to 1 A g−1, the potassium storage capacity of Mn3O4-G reduces to 83 mAh g−1. Due to the higher redox potentials of Na+/Na

and K+/K couple

(−2.71 and −2.94 V vs. SHE, respectively) compared to that of Li+/Li couple (−3.04 V vs. SHE),36 the discharge cut-off potential of Mn3O4 are higher in NIBs and KIBs (Figure S8). Meanwhile, the sluggish diffusion kinetics of sodium-ion and potassium-ion results in greater polarization. Thus, the reaction of Mn3O4 in NIBs and KIBs are incomplete, leading to the limited capacity.

Figure 4. (a-c) The sodium storage performance of Mn3O4-G: (a) Cycling performance at 0.2 A g-1, (b) the corresponded charge/discharge curves, and (c) the rate performance. (d-f) The potassium storage performance of Mn3O4-G: (d) Cycling performance at 0.1 A g-1, (e) the corresponded charge/discharge curves, and (f) the rate performance.


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The electrochemical kinetics of Mn3O4-G and Mn3O4 microflowers was investigated by electrochemical impedance spectroscopy (EIS) tests. In the Nyquist plots, the charge transfer resistance of Mn3O4-G (25.77Ω) was clearly smaller than that of Mn3O4 (73.77Ω) (Figure S9, Table S1). This confirms that graphene decoration effectively enhanced the electrical conductivity, which was responsible for the improved rate performance. After 100 cycles, the integrity of Mn3O4-G microparticle was maintained with SEI film on the surface (Figure S10), implying the good electrode robustness. The superior electrochemical performance of Mn3O4-G is attributed to the porous nanosheet-assembled hierarchical Mn3O4/graphene composite structure. The porous ultra-thin nanosheets provide large electrode-electrolyte interface and short ion diffusion pathway, and graphene nanosheets facilitate electronic conductivity, which are benefit for realizing higher capacity and better rate performance. Besides, the pores in nanosheets and interstices between nanosheets can accommodate the volume change during the alkali-metal-ion storage, enhancing the structural stability and cycling performance.

Conclusions Ultra-thin

nanosheet-assembled

hierarchical

Mn3O4/graphene

microflowers

were

obtained

successfully from MnV2O6 nanorod bundle/graphene composite precursors via the selective dissolution strategy. The selective dissolution mechanism was confirmed by investigating the structural evolution during the dissolution process. The Mn3O4-G displayed high lithium storage capacity (about 900 mAh g−1) and outstanding cycling stability at 0.5 A g−1 (about 400 mAh g−1 after 500 cycles). The enhanced lithium storage performance originates from the structural advantages. The ultra-thin nanosheets and graphene provided short diffusion pathways and fast electrical conduction pathway, respectively, which improved the capacity and rate capability. Moreover, the voids between nanosheets could hold volume changes during cycling and enhance the cycling performance. Furthermore, the sodium/potassium storage properties of Mn3O4 were also evaluated. The differences in the Li/Na/K storage performances are attributed to the different discharge cut-off potentials and ion diffusion kinetics in LIB, NIB and KIB.

We believe that the selective dissolution

strategy can be employed to synthesize other hierarchical nanomaterials and this work will contribute to further development of high-capacity anode materials for alkali-metal-ion batteries.



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Author Information Corresponding Author *E-mail: [email protected] *E-mail: [email protected] *E-mail: [email protected] Author Contributions # These authors contributed equally to this work. Notes The authors declare no competing financial interest.

Acknowledgements This

work

was

supported

by

the

National

Natural

Science

Foundation

of

China

(51771071,51602239), the International Science & Technology Cooperation Program of China (Grant No.2016YFE0124300), the National Key Research and Development Program of China (2016YFA0202600), the Hubei Provincial Natural Science Foundation of China (2016CFB267), Hubei Provincial Key Laboratory of Green Materials for Light Industry, Collaborative Innovation Center of Green Lightweight Materials and Processing, Hubei University of Technology (201710A05).

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Graphene Microflowers Fabricated via a Selective

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