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Graphene-Roll-Wrapped Prussian Blue Nanospheres as a HighPerformance Binder-Free Cathode for Sodium-Ion Batteries Jiahuan Luo,† Shixiong Sun,† Jian Peng, Bo Liu, Yangyang Huang, Kun Wang, Qin Zhang, Yuyu Li, Yu Jin, Yi Liu, Yuegang Qiu, Qing Li, Jiantao Han,* and Yunhui Huang State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China S Supporting Information *
ABSTRACT: Sodium iron hexacyanoferrate (Fe-HCF) has been proposed as a promising cathode material for sodium-ion batteries (SIBs) because of its desirable advantages, including high theoretical capacity (∼170 mAh g−1), eco-friendliness, and low cost of worldwide rich sodium and iron resources. Nonetheless, its application faces a number of obstacles due to poor electronic conductivity and structural instability. In this work, Fe-HCF nanospheres (NSs) were first synthesized and fabricated by an in situ graphene rolls (GRs) wrapping method, forming a 1D tubular hierarchical structure of Fe-HCF NSs@GRs. GRs not only provide fast electronic conduction path for Fe-HCF NSs but also effectively prevent organic electrolyte from reaching active materials and inhibit the occurrence of side reactions. The Fe-HCF NSs@GRs composite has been used as a binder-free cathode with a capacity of ∼110 mAh g−1 at a current density of 150 mA g−1 (∼1C), the capacity retention of ∼90% after 500 cycles. Moreover, the FeHCF NSs@GRs cathode displays a super high rate capability with ∼95 mAh g−1 at 1500 mA g−1 (∼10C). The results suggest that the 1D tubular structure of 2D GRs-wrapped Fe-HCF NSs is promising as a high-performance cathode for SIBs. KEYWORDS: Prussian blue, nanospheres, graphene rolls, binder-free, sodium-ion batteries
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INTRODUCTION Energy crisis and environmental pollution caused by massive combustion of fossil fuels make it an urgent need to develop clean and renewable energy sources, such as wind and solar energy. Electric energy storage (EES) technologies with low cost, high safety, and long lifetime are indispensable for utilization of renewable energy sources.1−5 Sodium-ion batteries (SIBs) have attracted intense attention in recent years because of their desirable advantages including environmentally friendliness, low-cost sodium resources, and high storage efficiency, which make them a favorable candidate for EES.6−12 Sodium iron hexacyanoferrate (Fe-HCF) Prussian blue and its analogues (PBAs), a type of materials allowing a reversible insertion/extraction of sodium ions in their lattices, has been investigated as a promising cathode material for SIBs with a high theoretical capacity (∼170 mAh g−1).13−42 The general chemical formula of PBAs is AxM′[M″CN)6]y□1−ynH2O (0 < x < 2, 0 < y < 1, A stands for alkali cations, M signifies transition metal ions, □ means the [M″(CN)6] vacancies occupied by coordinated H2O. The double-perovskite framework of PBAs is constructed by the M′ and M″ coordinating alternately with CN− ligands, which is beneficial for facile diffusion of electro-active ions. However, the practical application of PBAs cathode still suffers from a poor inferior electronic conductivity and some side reactions with organic electrolyte during sodium-ion © XXXX American Chemical Society
insertion/extraction processes, which results in a variety of serious issues, such as continuous dissolution, structural collapse, and rapid degradation of interparticle electrical connection. To address these challenges, several novel nanostructures of Fe-HCF composites with soft materials, such as graphene-oxide (GO),30 reduced graphene-oxide (RGO),32,42 Ketjen black (KB),35 polypyrrole (PPy),37 and carbon nanotubes (CNTs)39 have been developed. But there still exist problems of capacity fading and deadly poison CN− releasing. In our previous work, a type of Fe-HCF microcubes coated by PPy have been successfully prepared, which deliver an improved cycle and rate performance. For above these FeHCF@C composites, the electrical contact with suppressed mechanical fracture of electrode can be effectively improved. However, the PBAs side reactions with organic electrolyte still limit their sodium storage performance due to full/part surface exposure of Fe-HCF particles, which motivates us to fabricate a highly conductive matrix to encapsulate Fe-HCF particles impeding the Fe-HCF from contacting the electrolyte. As reported, graphene rolls (GRs), which consist of 1D tubular structure of 2D graphene nanosheets wrapping, are considered an effective strategy to guarantee material electroactivity.43−45 Received: May 5, 2017 Accepted: July 10, 2017 Published: July 10, 2017 A
DOI: 10.1021/acsami.7b06334 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
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ACS Applied Materials & Interfaces
indicating that upon reducing and annealing treatments, no reaction occurs between Fe-HCF NSs and graphene rolls as well as Fe-HCF NSs themselves. Whereas, the characteristic peak of graphite (2θ = 26°, corresponding to the (002) crystal face of graphite) is not detected and there is no additional peak being scrutinized. In addition, Rietveld Refinements are executed to study the crystal structure of Fe-HCF NSs and Fe-HCF NSs@GRs, which are crystallized in the Pm3̅ pace group with lattice parameters a = 10.2056(0) and 10.2070(7) Å, respectively, as shown in Figure S1. Figure 1b shows the Raman spectroscopies of two samples, Fe-HCF NSs and Fe-HCF NSs@GRs, respectively. The peaks located at ∼2057 and ∼2099 cm−1 belong to cyanogen of Ferro-cyanide group. Both materials exhibit these two diagnostic peaks as a matter of course. For Fe-HCF NSs@ GRs, the marked D and G bands located at ∼1348 and ∼1588 cm−1, respectively, are assigned to graphene rolls, which delivers a low peak intensity ratio (ID/IG = 1.25). The low ratio of ID/IG indicates a higher electronic conjugation after reduction, which should be a basis of high rate-performance for Fe-HCF NSs@GRs. Figure 2 shows the morphology of Fe-HCF NSs and FeHCF NSs@GRs. The as-prepared Fe-HCF presents a sphere
Meanwhile, the typical tubular shape of GRs could effectively prevent electrolyte from reaching active materials. Therefore, such an encapsulation of the Fe-HCF NSs into GRs (Fe-HCF NSs@GRs) would greatly improve the electrochemical performance of Fe-HCF cathode, especially in long-life cycling stabilities. In this work, a typical hydrothermal method was employed to prepare Fe-HCF NSs, and then a mixture suspension of GO and Fe-HCF NSs was quenched in liquid N2, and followed by hydrazine-reduced GO nanosheets and a thermal annealing process to achieve a Fe-HCF NSs@GRs hierarchical structure. Moreover, the Fe-HCF NSs@GRs composite can be used as a binder-free cathode for a suitable assemble and a highperformance cathode material.
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RESULTS AND DISCUSSION Figure 1a shows the XRD patterns of Fe-HCF NSs synthesized by coprecipitation with surfactant Pluronic F-127 (short for F-
Figure 2. SEM and TEM images of (a, c) Fe-HCF NSs, and (b, d) FeHCF NSs@GRs.
shape with smooth surface and a ∼200 nm particle size (see Figure 2a, c), which is much smaller than that of the reported nanocubic synthesized by coprecipitated method or decomposition reaction. As shown in Figure 2b, the Fe-HCF NSs@ GRs demonstrates 1D microsized lengths of GRs with smooth and wrinkled surface morphology. The formation of 1D tubular structure is due to roll-up of flexible GO nanosheets quenched by liquid nitrogen immediately. In a typical TEM image, Figure 2d shows that Fe-HCF NSs, covered by a thin carbon shell layer, are encapsulated into GRs, forming such a 1D hierarchical structure. In addition, as shown in Figures S3 and S4, the EDX mapping images of Fe-HCF NSs@GRs confirm that the 1D hierarchical structure has been successfully fabricated with a uniform distribution of Fe element along the backbone of GRs. From the TG test, the GR content is ∼14% in Fe-HCF NSs@GR (see Figure S5).
Figure 1. (a) XRD patterns and (b) Raman spectra of the Fe-HCF NSs and Fe-HCF NSs @GR, respectively.
127) and Fe-HCF NSs@GRs composite. All the diffraction peaks were indexed a face-centered cubic phase (FCC, space group Fm3m, JCPDS no.73−0687), thus it is expected that the synthesized Fe-HCF NSs@GRs shows a same crystal structure with the cubic phase of bare Fe-HCF NSs. The diffraction pattern of Fe-HCF NSs exhibit sharp and well-defined peaks for each diffraction plane, indicating a high crystallinity. The XRD pattern of Fe-HCF NSs@GRs shows a little higher background than that of bare Fe-HCF NSs, but the diffraction peaks, indicative of remaining a high crystalline structure, were still very clear. On the other hand, no additional peaks is observed, B
DOI: 10.1021/acsami.7b06334 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces Figure 3 illustrates the synthetic strategy of Fe-HCF NSs and the forming process Fe-HCF NSs@GRs. The Fe-HCF NSs
Figure 4. Charge−discharge curves at various rates of (a) Fe-HCF NSs and (b) Fe-HCF NSs@GRs; the capacity retention for (c) FeHCF NSs and (d) Fe-HCF NSs@GRs; (e) the rate performance and (f) long-term cycling stability 1C rate for Fe-HCF NSs and Fe-HCF NSs@GRs.
Figure 3. Schematic illustration of (a) the synthesis of Fe-HCF NSs@ GRs and (b) the forming mechanism of Fe-HCF NSs@GRs 1D tubular hierarchical structure.
have been synthesized using a hydrothermal route with FeCl2 reacting with Na4Fe(CN)6 in F-127 aqueous solution. The color of Fe-HCF NSs changes from light blue to bluish violet during centrifuging with DI water and methanol, which may be caused by oxidation of Fe-HCF NSs surface when exposed to air. This phenomenon has ever been reported by the previous reports.34,37 The assembling process of Fe-HCF NSs@GRs refers to a method reported elsewhere43,46 (see Figure 3b), including two key steps: a, the solution consisting of Fe-HCF NSs and GO is heated to near boiling and transferred into a plastic tube, and quickly dropped into liquid N2 for quenching; b, the frozen sample is freezing-dried to get blue Fe-HCF NSs@GO sample, both of which are of critical importance for forming above 1D tubular structure. Within a GO sheet, isolated pockets of graphene are surrounded by amorphous regions of oxygen-containing functional groups. Therefore, FeHCF NSs could be facilely anchored onto GO sheets by the linkage of the oxygen-containing groups on the sheets. Meanwhile, these oxygen-containing groups bind and some water molecules. When the solution consisting of Fe-HCF NSs and GO is quenched, the surface tension of absorbed water on GO sheet surface increases rapidly with decreasing temperature, which drives GO sheets self-scrolling forming 1D nanoroll structure. Importantly, Fe-HCF NSs have been encapsulated into the GO sheet rolls in a second during quenching.43,44 Figure 4 shows the electrochemical performance of Fe-HCF NSs and Fe-HCF NSs@GRs electrodes within coin-type halfcells. The rate performances of two electrodes were tested at different current densities from 0.2C to 10C. With increasing current density, Fe-HCF NSs@GRs show a much better rate capability than that of Fe-HCF NSs, with a capacity retention of ∼70% (95 mAh g−1) and 40% (50 mAh g−1) at current densities of 10C, respectively, which indicates a better rate capability of Fe-HCF NSs@GRs. In addition, the polarization
of Fe-HCF NSs@GRs is much smaller than that of Fe-HCF NSs especially at high current densities (see Figure 4a, b). Figure 4f shows the cyclic performances of Fe-HCF NSs and Fe-HCF NSs@GRs electrodes evaluated at a current density of 1C (∼150 mA g−1). After 500 cycles, the specific capacity of FeHCF NSs is 68 mAh g−1 with capacity retention of ∼60%. By contrast, Fe-HCF NSs@GR gives higher capacity (110 mAh g−1) and capacity retention of ∼90% after 500 cycles, which suggests that the electrochemical performance of Fe-HCF NSs has been significantly improved by such special 1D tubular structure of graphene-wrapping. Furthermore, the Coulombic efficiency of Fe-HCF NSs@GR is higher than that of Fe-HCF NSs, as shown in Figure S7. Figure S8 shows the CV curves of the two electrodes tested between 2.0 to 4.2 V at a scan rate of 0.2 mV s−1. In the initial scan, the well-defined redox couple located at 3.14/2.66 V can be attributed to high-spin Fe2+/Fe3+, which are bonded to nitrogen atoms of CN− ligands, whereas the peaks located at 3.65/3.31 V are ascribed to low-spin Fe2+/Fe3+, which are connected with carbon atoms of CN− ligands. The redox polarization for the first redox couple of Fe-HCF NSs@GRs is ∼0.48 V, lower than that of Fe-HCF NSs (0.55 V), which means that Fe-HCF NSs@GRs electrode has a smaller polarization due to its higher internal electronic conductivity. What’s more, the XRD, SEMm and TEM of the electrode slices have been tested at the 50th and 100th cycle, respectively, as shown in Figures S9−S11, the results show that the crystal structure of cathode material was stable upon the charge/ discharge process. Actually, a space confinement effect of GR plays a critical role to guarantee the high electrochemical performance, such as high-rate capability and long cycle life.42 C
DOI: 10.1021/acsami.7b06334 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
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spectroscopy and elemental analysis, which was Na1.1 Fe[Fe(CN)6]0.9·□0.1·3.8H2O. For the synthesis of Fe-HCF NSs@GRs, 400 mg of as-synthesized Fe-HCF NSs were added into 150 mL GO (0.5 mg mL−1) suspension and stirred magnetically for 4 h. The obtained mixture was heated to near boiling, and rapidly transferred into a plastic tube and then put into a liquid nitrogen container. After liquid−solid separated and freezing-dried, the Fe-HCF NSs@GO with dark blue color was collected. Subsequently, the resulting Fe-HCF NSs@GO were chemically reduced by exposing them to hydrazine gas at 60 °C overnight to obtain a gray Fe-HCF NSs@GRs composite. Materials Characterization. The lattice structures of samples were characterized by XRD with Cu Kα radiation (Panalytical X’pert PRO MRD). The morphology of products was observed by a scanning electron microscope (FE-SEM, JEOL, Japan) and Transmission electron microscopy (JEM-2100 electron microscope, TEM). Thermogravimetry (TG) measurement was carried out on a Netzsch STA 449F3 analyzer in air at a scan rate of 10 °C min−1. Raman spectra were obtained from a LabRAM HR800 (Horiba JobinYvon) using an argon ion laser with a wavelength of 532 nm. Elemental compositions of Na and Fe were determined by ICP-OES (IRIS Intrepid II XSP, Thermo Elemental, USA). The C/H/N was tested on elemental analyzer (Vario Micro cube, Elementar). Electrochemical Measurements. The electrochemical properties of all samples were performed using CR2032 coin half-cells. The working electrode of Fe-HCF NSs was made by reeling a mixture of 70 wt % Fe-HCF NSs, 10% Ketjen black carbon, 10% Super P, and 10 wt % polytetrafluoroethylene (PTFE) binder. However, the Fe-HCF NSs@GRs was pressed into a thin film to be used as electrode without any binder and conductive agent. The average electrode loading mass of the Fe-HCF NSs and Fe-HCF NSs@GR were approximately 3.2 and 1.8 mg cm−2, respectively. All coin cells were assembled in an Ar-filled glovebox by using a roundish sheet of sodium with diameter of ∼9 mm as counter electrode, 1 M NaClO4 in ethylene carbonate/diethyl carbonate (1:1 by volume) as electrolyte with 5 wt % fluoroethylene carbonate (FEC), and Whatman glass fiber (GF/A) as separator. Cyclic voltammetry (CV) was measured on a Princeton electrochemical workstation between 2.0 to 4.2 V with a scan rate of 0.2 mV s−1. EIS was also attained on the Princeton electrochemical workstation over the frequency range of 0.01−100 kHz with an amplitude of 10 mV. The charge/discharge tests were performed on a battery testing system (Land Electronics and Neware Electronics, China) at room temperature between 2.0 and 4.2 V versus Na+/Na.
The excellent electrochemical performance of Fe-HCF NSs@GRs electrode has been further understood by Electrochemical impedance spectroscopy (EIS). Figure 5 shows Fe-
Figure 5. EIS plots of Fe-HCF NSs and Fe-HCF NSs@GRs after CV measurement (inset is the equivalent circuit diagrams).
HCF NSs@GRs electrode exhibits a smaller Rct (∼232 Ω) than that of Fe-HCF NSs (∼700 Ω). In brief, there are three key points guaranteeing the enhanced cycling performance: (a) the structure collapsing of Fe-HCF NSs are prevented by graphene rolls wrapping; (b) the side reactions between Fe-HCF NSs and organic electrolyte are reduced by graphene shell-layer; (c) the 1D fast electronic conducting path of graphene rolls are connected closely to form 3D fast electronic conducting networks (see Figure 3b). The EIS of Fe-HCF NSs@GRs electrode after 50th cycle and 100th cycle was tested, respectively, which reveals that the electrode structure is robust (Figure S12).42
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CONCLUSION In summary, 1D tubular hierarchical structure of Fe-HCF NSs@GR has been successfully fabricated by wrapping Fe-HCF NSs into graphene rolls. The Fe-HCF NSs@GRs composite has been used as a binder-free cathode with a capacity of ∼110 mAh g−1 at a current density of 150 mA g−1 (∼1C), the capacity retention of ∼90% after 500 cycles. Moreover, the FeHCF NSs@GRs cathode displays a super high rate capability with ∼95 mAh g−1 at 1500 mA g−1 (∼10C). The results show that the method of graphene rolls wrapping Fe-HCF NSs is an effective to enhance the electronic performance of the Fe-HCF NSs, and Fe-HCF NSs@GRs is a candidate cathode material for high-performance sodium-ion batteries.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b06334. XRD Rietveld refinements (Figure S1), SEM images, (Figure S2); FEI-SEM mapping images (Figure S3 and S4), TGA curves (Figure S5), digital photographs (Figure S6) and CV profiles of Fe-HCF nanospheres and Fe-HCF nanospheres@GRs, columbic efficiency data (Figure S7), CV curves (Figure S8), XRD patterns/SEM images/TEM images/EIS data after 50th cycle and 100th cycle (Figures S9−S12) (PDF)
EXPERIMENTAL SECTION
Materials Synthesis. The Fe-HCF NSs were synthesized by a coprecipitation method as described elsewhere with a little modification.47−49 Briefly, 2 mmol Na4Fe(CN)6·10H2O was dissolved in 15 mL deionized water, 4 mmol FeCl2·4H2O and 50 mg F-127 were dissolved in 20 mL deionized water. The solution containing 15 mL of Na4Fe(CN)6 was slowly added into the mixture solution of FeCl2· 4H2O in a Teflon-lined stainless-steel autoclave. Following this, the autoclave was kept at 80 °C for 20 h and then naturally cooled down to room temperature. The obtained light-blue precipitates were centrifuged, washed with deionized water and methanol, and dried overnight at 120 °C under vacuum. The precise chemical composition of the Fe-HCF NSs has been calculated by use of the ICP-OES
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected] (J.H.). Author Contributions †
J.L. and S.S. contributed equally to this work.
Notes
The authors declare no competing financial interest. D
DOI: 10.1021/acsami.7b06334 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
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ACKNOWLEDGMENTS This work was supported by the Natural Science Foundation of China (Grants 2016YFB010030X, 319 2016YFB0700600, 2015AA034600) and the China Postdoctoral Science Foundation (2016M590691). The authors also thank the Analytical and Testing Centre of HUST and the State Key Laboratory of Materials Processing and Die & Mold Technology of HUST for XRD, SEM, TEM, Raman, TGA, and other measurements.
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DOI: 10.1021/acsami.7b06334 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
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DOI: 10.1021/acsami.7b06334 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
