Construction of Multishelled Binary Metal Oxides via Coabsorption of

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Construction of multi-shelled binary metal oxides via co-absorption of metal cations and anions as superior cathode for sodium-ion battery Xiaoxian Zhao, Jiangyan Wang, Ranbo Yu, and Dan Wang J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b09241 • Publication Date (Web): 15 Nov 2018 Downloaded from http://pubs.acs.org on November 16, 2018

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Journal of the American Chemical Society

Construction of Multi-shelled Binary Metal Oxides via Co-absorption of Positive and Negative Ions as Superior Cathode for Sodium-ion B a t t e r y Xiaoxian Zhao§,‡,⊥,†, Jiangyan Wang§,†, Ranbo Yu‡*, Dan Wang§*. §StateKey

Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, No. 1, Beierjie, Zhongguancun, Beijing, 100190, P. R. China. ‡Department

of Physical Chemistry, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, No. 30, Xueyuan Road, Haidian District, Beijing 100083, P. R. China. Fax: +86-10-62332525; Tel: +86-10-62332525 KEYWORDS: Multi-shelled; hollow sphere; binary metal oxide; co-absorption; sodium-ion battery.

ABSTRACT: Multi-shelled binary metal oxide which can exert a synergetic effect of different oxides, is promising electrochemical electrode material. However, it is challenging to synthesize this kind of binary metal oxides due to the severe hydrolysis and/ or precipitation reactions of the precursors between cations and anions of different metals. Herein, by using citric acid as chelating agent to inhibit the hydrolysis and precipitation, a series of multi-shelled binary metal oxide hollow spheres (Fe2(MoO4)3, NiMoO4, MnMoO4, CoWO4, MnWO4, etc.) were obtained via co-absorption of negative and positive metal ions. In addition, the chelation between metal ion and citric acid is systematically validated by NMR, MS, Raman and UV-vis. In particular, multi-shelled Fe2(MoO4)3 hollow spheres show excellent electrochemical performance as cathode material for sodium-ion batteries benefited from its structural superiorities. Especially, the quintuple-shelled Fe2(MoO4)3 hollow sphere shows the highest specific capacity (99.03 mAh g-1) among all Fe2(MoO4)3 hollow spheres, excellent stability (85.6 mAh g-1 was retained after 100 cycles at a current density of 2.2 C), and outstanding rate capability (67.4 mAh g-1 can be obtained at a current density of 10 C). This general approach can be extended to the synthesis of other multi-shelled multi-element metal oxides and greatly enrich the diversity of hollow multi-shelled structures.

■ INTRODUCTION Hollow multi-shelled structures (HoMSs), due to their large specific surface area and pore volume, low density and high volumetric loading capacity, have been widely considered as promising materials for various application areas1-3. Especially, used as electrode materials for batteries4, HoMSs show outstanding advantages as follows: a) The abundant pores on the shells enable the electrolyte’s access to the inner part of hollow structures; b) The larger specific surface area increases the electrode/electrolyte contact area, thus increases storage sites, combining with the reduced diffusion path benefited from the thin shell composed of 20-40 nm nanoparticles, the overall specific capacity of electrode is significantly improved at high current density;5,6 c) The inner free volume of hollow sphere between shells can alleviate expansion during charging/discharging processes.7 On account of above reasons, the synthesis of HoMSs for electrode materials has developed vastly in recent years, using various methods such as hard templating method8-10, soft templating method11,12 and selfassembly method13. Distinct from other methods, sequential templating approach (STA) does not require the formation of all the target shells before template removal, and is general and widely usable for the synthesis of diverse HoMSs.14 Since the delicate multi-shelled (1-4 shells) Co3O4 hollow spheres were

synthesized in high yield with high purity by STA in 201315, this approach has been successfully applied to prepare a number of metal oxide multi-shelled hollow spheres such as a-Fe2O316, NiO17, CuO18, ZnO19, etc. through positive metal ion absorption, and has been extended for V2O5, MnO2, MoO3, Cr2O3 and WO3 hollow spheres through negative ion absorption20, LiMn2O4 hollow sphere through dual positive metal ion absorption21, and for YVO4 hollow spheres through two-step absorption method 22. However, this approach has never been used for synthesizing hollow sphere through co-absorption of positive and negative metal ions (such as Fe3+ and MoO42-) in one solution system, which is powerful for the synthesis of binary metal oxide materials for lithium battery23, supercapacitor24 or catalyst25, etc26-30. The key reason is that the hydrolysis is increased vigorously, and/ or the precipitation reactions happen once metal acid radical anions and metal cations (weak acid and weak base) are mixed together, making precursors solidified and difficultly to be absorbed into the inner of template31, resulting in failing to synthesize multi-shelled hollow sphere. In this paper, by taking advantage of chelation between citric acid and transition metal ion, the hydrolysis and precipitation reactions are efficiently restrained during the co-absorption of negative and positive metal ions (Figure 1). Several binary

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metal oxide HoMSs (BM-HoMSs) have been successfully achieved through this method, including Fe2(MoO4)3, NiMoO4, MnMoO4, CoWO4 and MnWO4, etc. In particular, multi-shelled Fe2(MoO4)3 hollow sphere as cathode material for sodium-ion batteries delivered high specific capacity, good cycling stability and impressive rate capability. ■ RESULTS AND DISCUSSION

Synthesis of BM-HoMSs. Actually, when the negative ion and positive ion (MoO42- and Fe3+) are mixed in deionized water, precipitation reaction happens as shown in equation (1) even the pH of solution was decreased to be about 0.23 by adding HCl solution (Figure S1a,b): 2Fe3+ + 3 MoO42- ↔ Fe2(MoO4)3 (s) (1) Thus, the binary metal oxide (Fe2(MoO4)3) precursor nucleates and precipitates on the surface of carbonaceous microsphere (CMS) template (Figure S2). Besides, according to the theories of acids and bases32, the hydrolysis of Fe3+ and MoO42- could be enhanced when mixed together. Therefore, very limited positive and negative metal ions can be absorbed into CMS, inducing the formation of irregular single shelled hollow sphere after calcination. When the citric acid was added into the system, the precipitation reaction was efficiently restrained due to the chelation between citric acid and metal ion, exhibiting a clear aqueous solution and enabling the deep penetration of precursors into the inner part of CMS template (Figure 2). It’s also worth noting that the pH of mixture solution of FeCl3 and (NH4)2MoO4 after adding citric acid is decreased to be about 0.23, such low pH can also restrain the hydrolysis of Fe3+ ions (bronzing Fe(OH)3 precipitate can be observed when pH is increased to 1.0 by adding ammonia solution, Figure S1c,d). By further enhancing the absorption temperature and duration, the absorption amount and penetration depth can be further increased. As a result, multi-shelled Fe2(MoO4)3 hollow sphere with controlled shell number range from 1 to 5 can be obtained by the STA (Figure 3 and S9). The detailed process for synthesizing BM-HoMS was shown in Figure 1 and Table S2.

To further understand the critical role of citric acid in preparation of BM-HoMSs (taking the preparation of multishelled Fe2(MoO4)3 hollow sphere as an example), the nuclear magnetic resonance (NMR) was applied to characterize the chemical shift of 13C before and after adding (NH4)2MoO4 (Figure 2a). The chemical shift of characteristic peak and appearance of new peaks at 183.52 and 84.64 ppm proved the chelation happens between citric acid and MoO42-.33 In additional to NMR, the mass spectrometer (MS) was used to characterize the relative molecular mass before and after adding (NH4)2MoO4 and FeCl3. The peaks (m/z 191.0164, 383.0418) corresponding to citric acid (Figure 2b and Table S3) were observed for bare citric acid aqueous solution, while the peaks (m/z 460.7749) corresponding to C6H5Mo2O12 appear after adding (NH4)2MoO4, it proves that one citric acid chelates with two MoO42-, which was further verified by the enlarged part from m/z 450 to 472.5 (Figure S3). After adding Fe3+, the C6H5Mo2O12 peaks disappear, meanwhile, the peaks corresponding to C6H5O7FeCl- and FeMoO3Cl4- show up, demon-strating that citric acid can chelate with Fe3+ more strongly. The Raman and UV-visible spectroscopy are also used to explore the important role of citric acid in synthesis of BMHoMS. As shown in Figure 2c, the peak 897 and peak 942 corresponding to valence oscillations of M=O34 shift after adding (NH4)2MoO4, indicating the chelation between citric acid and MoO42-, while the chelation relieves after adding FeCl3 as the peak position turns back. In UV-visible spectroscopy (Figure 2d), the absorption band between 200 to 300 nm is corresponding to ligand-to-metal charge transfer O2−→ Mo6+, which depends on the size of the agglomerated Mo oxide species35,36. Compared to citric acid solution, the wavelengths from 200 to 300 nm changes after adding (NH4)2MoO4 and turns back after further adding FeCl3. Meanwhile, after adding FeCl3 into citric acid solution or into the mixture of citric acid and (NH4)2MoO4 solution, the absorption band between 300 and 350 nm is greatly improved, indicating the formation of FeC6H5O7 according to equation (2)37. Fe3+ + C6H5O73- → FeC6H5O7 (2)

Figure 1. The process for synthesizing multi-shelled binary metal oxide hollow sphere. (I) With citric acid, the precipitation reaction was restrained extremely due to the chelation of citric acid, thus metal ions can penetrate into the inside of CMS templates, resulting in multi-shelled hollow spheres. (II) Without citric acid, the precursor of binary metal oxide will be precipitated on the surface of carbon microspheres, resulting in nanoparticle and irregular single-shelled hollow spheres.


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Journal of the American Chemical Society Figure 2. The (a) NMR, (b) MS, (c) Raman, (d) UV-visible spectroscopy and (e)optical images of different kind of aqueous solutions (A: (NH4)2MoO4; B: citric acid; C: FeCl3).

Therefore, the citric acid and Cl- can chelate with both MoO42- and Fe3+. To sum up, citric acid will chelate with MoO42- after mixing with (NH4)2MoO4 aqueous solution, while the chelation relieves after FeCl3 is added into the above solution because citric acid chelates with Fe3+ more strongly. The chelation reactions are shown in equation (3) and (4): C6H8O7 + 2 MoO42- + 3 NH4+ ↔ C6H5Mo2O12- + 3 NH3H2O (3) C6H5Mo2O12- + Fe3+ + Cl- + 3 H2O ↔ C6H5O7FeCl- + 2 (4) MoO42- + 6 H+ 3+ Fe + 4 Cl ↔ FeCl4 (5) C6H5O73- + Fe3+ + Cl- ↔ C6H5O7FeCl(6) 23+ + MoO4 + Fe + 4 Cl + 2 H ↔ FeMoO3Cl4 + H2O (7) Consequently, precipitation reaction and hydrolysis of MoO42- and Fe3+ is efficiently hindered. Meanwhile, the coordination reactions shown in equation (5), (6) and (7) is reversible. The free Fe3+ and MoO42- which are smaller and own higher valence state than their coordination compounds, can be absorbed into CMS more easily, making reaction (5), (6) and (7) occur in the reverse direction. Thus we demonstrate that during absorption process, the negative (MoO42-) and positive (Fe3+) ions can be co-absorbed into CMS rather than their coordination compounds. By further increasing the absorption duration and temperature, the penetration depth and absorption amount of metal ion into CMS are increased (Figure S4), resulting in the synthesis of closed quintuple-shelled Fe2(MoO4)3 hollow sphere. Besides, we found that the structure of Fe2(MoO4)3 transformed from nanoparticles to triple-shelled hollow sphere as the adding amount of citric acid increased. It indicates that the enough citric acid should be added to chelate with MoO42and Fe3+, thus fully restrain precipitation and hydrolysis during synthetic process of Fe2(MoO4)3 hollow sphere (Figure S5). The adding molar ratio of (NH4)2MoO4 to FeCl3 is another key factor affecting the crystal structure and morphology of the products. As shown in Table S1, products with Mo/Fe molar ratio of around 1.5 can be obtained when the adding molar ratio of (NH4)2MoO4 to FeCl3 is around 0.3. When the molar ratio of Mo/Fe of product is larger than 1.5, two phases corresponded to MoO3 (PDF#47-1320) and Fe2(MoO4)3 (PDF#83-1701) are obtained (Figure S6). In addition, according to the cyclic voltammetry (CV) test result and cycling life of Fe2(MoO4)3 products obtained at different Mo/Fe ratio (Figure S8), we can find that no redox peaks of MoO338 is observed and good stability is achieved only when the molar ratio of Mo/Fe is around 1.5. Thus, pure multi-shelled Fe2(MoO4)3 should be obtained by adjusting the adsorption conditions (Table S2). The morphology of multi-shelled Fe2(MoO4)3 hollow spheres were characterized by SEM (scanning electron microscope) and TEM (transmission electron microscope), as shown in Figures S9a-d and Figures 3a-c. The shells are composed of nanoparticles with pores observed in the shells, which benefits the permeation of electrolyte into inside. TEM images (Figure S9e to 9i, Figure 3b and Figure 3c) clearly show that multishelled hollow spheres with 1 to 5 shells around 800 nm to 1000 nm were obtained. The high-resolution TEM (HRTEM) (Figure 3d), powder X-ray diffraction (XRD) patterns (Figure 3f) and refinement (Figure S10, Table S4 and S4) confirm the typical

monoclinic structure of multi-shelled Fe2(MoO4)3 hollow sphere which is consistent with PDF#83-1701. Meanwhile, the Raman spectrum of multi-shelled Fe2(MoO4)3 hollow sphere confirms that there is no MoO3 (Figure 3i and Figure S11)39. The inductively coupled plasma mass spectrometry -MS (ICPMS) test shown in Table S6 demonstrate that the molar ratio of Mo/Fe is around 1.5. Finally, from the element mapping (Figure 3e) by high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) of quintuple-shelled Fe2(MoO4)3 hollow sphere treated by microtomy and X-ray photoelectron spectroscopy (XPS, shown in Figure 3g and 3h), it can be seen clearly that the Fe3+ and Mo6+ are distributed uniformly in quintuple-shelled Fe2(MoO4)3 hollow sphere.

Figure 3. The characterization of multi-shelled Fe2(MoO4)3 hollow sphere. (a) SEM and (b) TEM images of quadruple-shelled hollow sphere; (c) TEM, (d) HRTEM and (e) Mapping images, (f) XRD, (g, h) XPS and (i) Raman spectra of quintuple-shelled hollow sphere.

Impressively, this method is not only fit for Fe2(MoO4)3 hollow sphere, but also for NiMoO4, MnMoO4, CoWO4 and MnWO4 hollow spheres which can be used in supercapacitor, battery, catalyst, etc. As shown in Figure S12, the XRD curves are in accordance with NiMoO4, MnMoO4, CoWO4 and MnWO4 respectively. The XPS results of NiMoO4, MnMoO4, CoWO4 and MnWO4 hollow sphere were shown in Figure S13, which prove that the binary metal oxide hollow sphere is composed of Ni2+ and Mo6+, Mn2+ and Mo6+, Co2+ and W6+, Mn2+ and W6+ respectively. Meanwhile, according to SEM (Figure S14) and TEM (Figure S15) images, the size of binary metal oxide hollow sphere mentioned above is uniform, and the multi-shelled hollow structure can be observed clearly. However, due to the difference on catalytic combustion of binary precursor to CMS (Figure S16), the shell number is different after calcination. The catalytic combustion of Fe and Mo precursor is strongest, resulting in Fe2(MoO4)3 hollow sphere with more shells. Finally, the element mapping (Figure S17) demonstrates that the elements of Ni and Mo, Mn and Mo, Co and W, Mn and W are dispersed uniformly in multi-shelled structure. In a word, it is a universal method to synthesize BMHoMSs by co-absorption of negative and positive ions utilizing chelation of citric acid.

The electrochemical performance. Fe2(MoO4)3 is Na+

superionic conductor (NASICON) with an ideal open threedimensional (3D) framework for Na+ transportation40, making it more suitable for sodium-ion battery compared to layered



(NaxCoO2) or olivine (NaFePO4) structure materials. Nevertheless, its further development is limited by the sluggish electrochemical kinetics caused by the poor electronic conductivity and the long Na+ diffusion path41. The multishelled structure which provides large electrode/electrolyte contact area, enables the penetration of electrolyte from outside to inside and shortens the diffusion length of electrons and Na+ ions, has been widely accepted as a promising electrode material for sodium -ion


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Figure 4. The electrochemical performance of Fe2(MoO4)3 NS and multi-shelled Fe2(MoO4)3 hollow sphere as cathode materials for sodiumion battery (a: cyclic voltammetric curves; b: galvanostatic charge-discharge voltage curves of the second cycle; c: cycling life test; d: rate performance; e: charge-discharge curves at different rates; electrochemical impedance spectra).

battery42,43. The electrochemical properties of Fe2(MoO4)3 HoMSs as cathode material for sodium-ion battery were measured using a standard Fe2(MoO4)3 half-cell configuration, the nanosheets (NS) synthesized according to Figure S18 was taken as reference. The cyclic voltammograms of Fe2(MoO4)3 HoMSs and NS samples for the second scan shown in Figure 4a display two cathodic peaks and two anode peaks of 2.50 V, 2.64 V and 2.66 V, 2.74 V at a scan rate of 0.1 mV s−1, indicating phase transformations from Fe2(MoO4)3 to Na2Fe2(MoO4)3 and from Na2Fe2(MoO4)3 to Fe2(MoO4)3, respectively, which is consistent with previous reports44. The electrochemical reaction corresponding to CV can be described as follow equation44. Fe2(MoO4)3 + 2 Na+ + 2e- ↔ Na2Fe2(MoO4)3 (9) Besides CV, the sodium-storage property of multi-shelled Fe2(MoO4)3 hollow sphere was evaluated by charge-discharge process. Figure 4b shows the second-cycle charge-discharge voltage profiles of HoMS Fe2(MoO4)3 and nanosheet at a current density of 0.1 C (1 C = 91 mA g-1) in a potential range from 1.5 to 4.0 V. In the discharge process, the potential quickly falls to the 2.74 V and 2.59 V plateau and then declines to the cut-off voltage of 1.5 V, similar to previous reports45. The second-cycle specific capacity of NS, single-shelled, doubleshelled, triple-shelled, quadruple-shelled and quintuple-shelled hollow spheres were 90.46 92.21, 93.96, 94.73, 95.10 and 99.03 mAh g-1 respectively. The larger specific capacity than the theoretical value of 91 mAh g-1, could be contributed by the capacitive behavior46. As shown in Figure 4c, all Fe2(MoO4)3 HoMSs exhibit a good cycling stability, specially the quintupleshelled hollow sphere material which can retain 85.6 mAh g-1 after 100 cycles at a current density of 2.2 C. Although the firstcycle specific capacity of NS is comparable to that of quintupleshelled Fe2(MoO4)3 hollow sphere, it fades quickly, with only 54.6 mAh g-1 retained after 100 cycles. Besides capacity and stability, the rate capability is also critical for practical applications. Figure 4d and 4e compared the specific capacity of Fe2(MoO4)3 nanosheet and HoMSs at different current densities. Even at a high current density of 10 C, the quintupleshelled Fe2(MoO4)3 hollow sphere can still deliver a capacity of at least 67.4 mAh g-1, which is much higher than the 40 mAh g-1 observed for Fe2(MoO4)3 nanosheet. It means the discharge or charge process of quintuple-shelled Fe2(MoO4)3 hollow sphere could be completed within 5 min while attaining a relatively high capacity. Remarkably, a stable high capacity of 95.4 mAh

g-1 can recover when the current density is decreased back to 1 C, which suggests that the elastic multi-shelled structures might indeed be very “breathable”.13

The mechanism for excellent electrochemical performance of Fe2(MoO4)3 HoMSs. All multi-shelled

Fe2(MoO4)3 hollow spheres show better electrochemical performance as cathode material for sodium battery than nanosheet. Meanwhile, the specific capacity increases as shell number of hollow sphere increases, wherein the quintupleshelled hollow sphere is clearly superior to the other types of multi-shelled Fe2(MoO4)3 hollow microspheres. The most likely interpretation of these results is based on a combination of observations. Firstly, the specific surface area and pore volume of all multi-shelled structures are larger than nanosheet (Table S7 and Figure S19), and the specific surface area increases along with increased shell number, while the quintuple-shelled hollow sphere owns the largest specific surface area thus able to provide the largest electrode/electrolyte contact area and storage sites. Secondly, the pores on the shells provide a channel for electrolyte to permeate from outside to inside of multi-shelled hollow sphere. Thirdly, the thin shells composed of nanoparticles around 40 nm can shorten the transfer distance for charges and enable a faster kinetics, which is an efficient way to improve rate capability. In another word, the diffusion coefficient of multishelled hollow structured material is higher than nanosheet structured material as shown in Figure S20 and Figure 4f. Fourthly, the superior cycling performance is ascribed to the superior structural stability of multi-shelled Fe2(MoO4)3 hollow sphere which can mitigate the strain during charge/ discharge processes (Figure S21 and S22), and the cavity can buffer the volume change during cycling. ■ Conclusion In summary, by taking advantage of chelation between citric acid and transition metal ion to inhibit hydrolysis and precipitation reactions, multi-shelled binary metal oxide hollow spheres were synthesized by STA through efficient coabsorption of negative and positive metal ions. Using this general method, a series of multi-shelled binary metal oxide hollow spheres including Fe2(MoO4)3, NiMoO4, MnMoO4, CoWO4 and MnWO4 have been achieved, with controlled crystallinity and shell number. Impressively, the multi-shelled



Fe2(MoO4)3 hollow sphere as cathode material for sodium-ion battery exhibits superior electrochemical performance, especially, the quintuple-shelled Fe2(MoO4)3 hollow sphere shows the highest specific capacity (99.03 mAh g-1) among all Fe2(MoO4)3 hollow spheres, excellent stability (85.6 mAh g-1 remained after 100 cycles at a current density of 2.2 C), and outstanding rate capability (67.4 mAh g-1 can be obtained at a current density of 10 C) benefited from the structural superiorities. It is believed that this method can provide a reference for synthesizing other multi-shelled binary metal oxide hollow spheres, and not only greatly promote the STA but also enrich the diversity of HoMSs. ■ ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge via the Internet at http://pubs.acs.org. Additional data and methods; Tables S1-S7; Figures S1-S22; Supporting references (PDF)

■ AUTHOR INFORMATION Corresponding Author *[email protected]; [email protected].

Present Addresses ⊥College

of science, HeBei Agriculture university, No. 289, Ling Yu Si street, Baoding, Hebei, China

Author Contributions †These

authors contributed equally to this work.

Notes Any additional relevant notes should be placed here.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21590795, 21820102002, 51872024, 51072020, 51472025, 21671016), the Scientific Instrument Developing Project of the Chinese Academy of Sciences, Grant No. YZ201623, and Queensland-Chinese Academy of Sciences Collaborative Science Fund (122111KYSB20170001), the Foundation for CAS Interdisciplinary Innovation Team.

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Construction of Multishelled Binary Metal Oxides via Coabsorption of

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