Porous rod-shaped Co3O4 derived from Co-MOF-74 as high-performance anode materials for lithium ion batteries

Accepted Manuscript Porous rod-shaped Co3O4 derived from Co-MOF-74 as highperformance anode materials for lithium ion batteries

Jinxi Chen, Xixi Mu, Mengjuan Du, Yongbing Lou PII: DOI: Reference:

S1387-7003(17)30608-1 doi: 10.1016/j.inoche.2017.09.005 INOCHE 6761

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

25 July 2017 29 August 2017 1 September 2017

Please cite this article as: Jinxi Chen, Xixi Mu, Mengjuan Du, Yongbing Lou , Porous rod-shaped Co3O4 derived from Co-MOF-74 as high-performance anode materials for lithium ion batteries, Inorganic Chemistry Communications (2017), doi: 10.1016/ j.inoche.2017.09.005

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ACCEPTED MANUSCRIPT Porous rod-shaped Co3O4 derived from Co-MOF-74 as high-performance anode materials for lithium ion batteries

Jinxi Chena,b,*, Xixi Mu a,b, Mengjuan Dua,b, Yongbing Loua,b a

School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R.

China.

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Jiangsu Key Laboratory of Advanced Metallic Materials, Nanjing 211189, P. R. China.

*Corresponding Author. Tel: (86) 25-5209-0618; Fax: (86) 25-5209-0620;

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E-mail: [email protected] (Prof. Chen)

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Abstract Porous rod-shaped Co3O4 has been successfully synthesized by one-step thermal annealing of the as-prepared Co-MOF-74 precursor and tested as anode materials for lithium ion batteries. The porous rod-shaped Co3O4 is found to be very attractive for lithium-ion batteries. It demonstrates a

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reversible capacity of 683 mAh/g after 80 cycles at 100 mA/g and an excellent rate performance

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with high average discharge specific capacities of 1231, 1026, 733 and 502 mAh/g at 50, 100, 200 and 400 mA/g, respectively. The excellent electrochemical performance should be due to the porous structural and composition characteristics.

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Keywords：Metal-organic frameworks; Rod-shaped Co3O4; Anodes; Lithium ion batteries

ACCEPTED MANUSCRIPT The lithium ion batteries (LIBs) are promising energy-storage devices whose applications have dramatically increased in areas such as various electric vehicles, smart electricity grids and portable electronics due to their long cycle life, light weight, large energy density, and no memory effect[1–3]. These favorable properties have attracted considerable attention toward LIBs in recent years. Numerous efforts have been made to investigate LIBs, such as silicon-based

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materials[4,5], carbon materials[6,7] and transition metal oxides[8–10]. Among the transition

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metal oxides, Co3O4 is considered to be one of ideal anode materials for LIBs owing to its low cost, environmental protection, and high theoretical capacities (890 mAh/g)[11]. Thus, several attempts have been made to controlled synthesis of cobalt oxide materials over the past two decades. For example, Feng et al. prepared Co3O4 nanowires by an ammonia-evaporation-induced method followed by calcination, which exhibited 855.1 mAh g-1 of initial capacity at a current

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density of 100 mA g-1[12]. In particular, it is reported in the literature that 3D mesoporous network of Co3O4 could be prepared via a general ultrathin-nanosheet-induced strategy and used

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as electrodes, displaying high capacity and long-life stability[13]. To achieve much higher capacity as well as better excellent cycling stability for Co3O4 electrodes, hollow porous Co3O4

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electrode materials with rational design of morphology and structure have been synthesized since they have the ability to provide larger Brunauer-Emmett-Teller (BET) surface area and accessible

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channels that facilitate to ion diffusion and transfer, which are critical for improving the electrochemical performance of LIBs[14,15].

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Recently, Metal-Organic Frameworks (MOFs) with exceptional specific surface areas and pore volumes have been used to generate porous metal oxide materials by solid-state thermolysis.

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This strategy is interesting because the obtained metal oxide materials can basically retain a similar morphology and porous structure characteristics of the MOFs precursors, which are conducive to improving the electrochemical performance. Considering the excellent electrochemical performance of cobalt oxides (CoO or Co3O4), several cobalt oxides derived from MOFs precursor have been widely applied in ion battery in recent years[16-21]. For instance， Porous Co3O4 hollow dodecahedra with nanometer-sized building blocks have been synthesized via two-step thermal decomposition from Co-containing ZIF-67 template, and it displayed high lithium storage capacities and excellent cycling performance in LIBs[22]. Kaneti and co-workers

ACCEPTED MANUSCRIPT have been reported that Ni-Co-ZIF was used as precursor for fabricating microporous Ni-doped Co/CoO/NC hybrid with rhombic dodecahedral morphology. The materials exhibited good cycling stability with good rate performance when it employed as an anode material for sodium-ion batteries[23]. In addition to cobalt oxide, other oxide materials (Fe2O3[24], NiO[25], MnO[26], ZnO[27],etc) are also widely applied in this field. A comparison of recently reported

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different electrode materials deride from MOFs and their electrochemical performances is

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summarized in Table S1.

As described above, many efforts have been made in this field especially the application of Co3O4 material due to its excellent electrochemical performance. However, some formed Co3O4 failed to maintain original morphologies of the precursors[17,28]. Therefore, facile, inexpensive and controlled synthesis of porous Co3O4 electrode materials with high electrochemical

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performance derived from prepared Co-based MOFs is still in its infancy. And it still remains a huge challenge to synthesize porous Co3O4 materials with specific morphology and high specific

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surface area.

In this work, porous rod-shaped Co3O4 was fabricated via directly annealing rod-shaped

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Co-MOF-74 precursors under air atmosphere. The rod-shaped Co3O4 retain similar morphology and porous structure characteristics of the MOF-74 precursors, respectively. When used as anode

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materials in LIBs, the as-synthesized porous rod-shaped Co3O4 delivers high capacity, excellent cycling stability and good rate capability.

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Fig. 1(a) presents XRD patterns of the successful synthesis of Co-MOF-74. The diffraction peaks of MOF-74 in the 2 range of 5–45° match well with the simulated results, which are also

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in agreement with previous reports[29,30]. Fig. 1(b) shows the XRD patterns of the product after one-step calcination. The well-resolved diffraction peaks of the metal oxide sample can be assigned to the standard product of Co3O4 (PDF Card No. 42-1467). No other obvious peaks from precursor compounds were observed, indicating the complete transformation of MOF-74 to metal oxides.

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Fig. 1. XRD patterns of (a) MOF-74, and (b) Co3O4.

The thermal stability of the MOF-74 was measured by TGA. As shown in Fig. S1, the

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weight loss in the range of 50 to 150 oC is related to the removal of the absorbed solvent molecules. The next weight loss between 260 and 310 oC could be assigned to the decomposition

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of 2,5-dihydroxyterephthalic acid ligands. The residual weight percent can be assigned to the metal oxides. Based on this result, 350 oC was used to carry out the transformation from MOF-74

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to metal oxide materials. As shown in Fig. S2, the specific surface area and pore volume of Co3O4 was estimated to be 93 m2 g-1 and 0.40 cm3g-1.

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The sizes and morphologies of the as-prepared MOF-74 precursor and the metal oxides were examined by SEM and TEM. As shown in Fig. 2(a), several rod-shaped Co-MOF-74 can be

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observed with smooth surface under electron imaging. The metal oxide sample showed a similar morphology with the corresponding Co-MOF-74 precursor (Fig. 2(b)), but the diameters of Co3O4 sample decreased slightly, which is primarily due to the structure contraction caused by the removal

of

molecules

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the

thermal

decomposition.

Meanwhile,

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2,5-dihydroxyterephthalic acid ligands are decomposed completely while the Co-O secondary building units are retained, therefore the morphology could be retained. Besides, the decomposition of the 2,5-dihydroxyterephthalic acid ligands is accompanied by the release of gas molecules, which eventually results in the formation of porous structure. So as to gain deep insight into the morphology of the metal oxide sample, the particular structures of the porous

ACCEPTED MANUSCRIPT rod-shaped Co3O4 was further investigated by TEM (Fig. 2(c) and (d)). The rod-shaped Co3O4 is composed of numerous Co3O4 nanoparticles and these primary nanoparticles can further aggregate to form the porous structure. The feature of porous structures Co3O4 with a larger surface area and pore volume are helpful, particularly for effective penetration of the electrolyte and fast Li+ ion insertion/extraction into the electrode material. Meanwhile, such porous

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structures could provide more extra spaces for the storage of lithium ions and efficiently buffer

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the stress caused by volume expansion during the discharging and charging processes. The selected area electron diffraction (SAED) pattern was shown in Fig. 2(e). d values could be calculated from the SAED pattern which are in accordance with the XRD results. The values of 0.28, 0.24, 0.20, 0.15 and 0.14 nm, corresponding well with the (2 2 0), (3 1 1), (4 0 0), (5 1 1) and (4 4 0) planes of the spinel Co3O4, respectively. Furthermore, the high-resolution TEM image

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shown in Fig. 2(f) displays distinct lattice fringes with d spacing 0.29 nm, which is in good

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agreement with the (2 2 0) lattice plane of Co3O4 phase.

Fig. 2. SEM images of (a) Co-MOF-74 precursor, (b) Co3O4; TEM images of (c), (d) Co3O4; (e) SEAD patterns; (f) HRTEM lattice images.

The element valences of the prepared Co3O4 were investigated by XPS. As Shown in Fig.

ACCEPTED MANUSCRIPT 3(a), the typical characteristic peaks of Co and O elements are observed on the full patterns clearly, indicating their existence in porous nanostructure. However, the survey spectrum also indicates that the existence of C elements since lower peak for C 1s binding energy (284.8 eV) can be observed. This phenomenon is attributed to a small amount of residue of the decomposition of organic ligands[17, 31]. The O 1s spectrum in the inset of Fig. 3(a) exhibit two peaks at 530.2 eV and 531.8 eV, which are ascribed to the lattice oxygen of spinel Co3O4[17, 31].

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From Fig. 3(b), both Co2+ (peaks at 781.4 eV and 796.6 eV) and Co3+ (peaks at 779.8 eV and 794.9 eV) and their four satellites (denoted as “sat” ) were measured, indicating the presence of Co2+ and Co3+[32,33]. Moreover, the two peaks at 780.0 eV and 795.1 eV in original spectrum are assigned to the Co 2p1/2 and Co 2p3/2 peaks, respectively. The energy separation between the Co 2p3/2 -2p1/2 is approximately 15 eV, which also indicates the presence of both Co2+/Co3+ species in

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the Co3O4 sample[34,35]. Thus, we reasonably speculate that the XRD patterns, the SEAD

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O 1s

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Co 3s Co 3p

C 1s

Binding Energy (eV)

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(b)

Co 2P

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3+

3+(sat) 2+(sat)

3+(sat) 2+(sat)

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Binding Energy (eV)

Binding Energy (eV)

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Co 2p3/2

Co 2p1/2

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Intensity(a.u.)

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Intensity(a.u.)

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patterns, combined with the result of XPS confirm the successful synthesis of Co3O4.

Fig. 3. XPS of the Co3O4 sample: (a) survey spectrum (inset: O 1s), (b) Co 2p

The electrochemical performance of porous rod-shaped Co3O4 was investigated as an anode material for LIBs by assembling coin cells. As shown in Fig. 4, the initial four consecutive CV curves of Co3O4 electrode at a scan rate of 0.5 mV/s in the potential range of 0.01 - 3.00 V, respectively. Consistent with previous reported Co3O4 anodes, several redox current peaks can be clearly

identified

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CVs,

suggesting

the

similar

electrochemical

reaction

mechanism[16,36-38]. In the first cycle, there is an obvious cathodic peak at 0.6 V with the reduction current increases, which can be ascribed to the reduction of Co3O4 to metallic Co

ACCEPTED MANUSCRIPT accompanying with the formation of Li2O and the formation of the solid electrolyte interphase (SEI) film on the contact surface between electrolyte and nano-rods.[39-41]. In the following anodic scan, the primary anodic peak appeared at 2.2 V, corresponding to the oxidation of Co to Co2+ and Co3+[42-43]. However, during the subsequent cycles, the intensity of cathodic peak was significantly decreased. Simultaneously, the cathodic and anodic peak potentials were positively

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moved. The results indicated the irreversible oxidation reduction processes during the initial

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charge/discharge cycle. It is worth noting that the CV curves overlap very well from the second

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cycle onwards, indicating good reversibility of the electrochemical reactions.

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Fig. 4. CV curves for the Co3O4 electrode at a scan rate of 0.5 mV/s.

Fig. 5 (a) exhibits the voltage - specific capacity diagram of different charge - discharge cycling

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at constant current density of 100 mA/g in the voltage range of 0.01 – 3.00 V (vs. Li+/Li). The initial discharges and charge capacities of Co3O4 electrode are found to be 989 and 739 mAh/g, respectively.

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The corresponding coulombic efficiency (CE) of the Co3O4 electrode is about 74.7%. The relatively low initial irreversible capacity loss mainly results from the formation of SEI and incomplete decomposition of electrolyte and the organic conductive polymer, which is common in most anode materials[44-47]. From the 2nd cycle, the discharge profiles present a similar shape, showing a steeper discharge plateau between 1.45 V and 0.8 V, which are in accordance with the CV curves. From Fig. 5 (b), porous Co3O4 electrode performs a good cycle retention and high reversible capacity, apparently. The initial discharge and charge capacities of Co3O4 electrode are 989 and 739 mAh/g and a high charge capacity of 683 mAh/g can still be retained after 80 cycles. The excellent

ACCEPTED MANUSCRIPT electrochemical performance is mainly attributed to the special rod-like porous structure, which contribute to the diffusion and storage of lithium ions, as well as buffer the volume variations during charge/discharge processes. Besides, it can be observed that the reversible capacity gradually increased from the second cycle. There are two possible reasons for this phenomenon. On one hand, the gradual decomposition of Li2O matrix were irreversibly formed in the first charge and discharge

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process[40,48]. On the other hand, the polymer gel-like films were formed on the surface of the

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Co3O4 electrode during the charging and discharging process, and the formation and decomposition of

Fig. 5.

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these covers may also lead to a slow rise of capacity[11,49,50].

Electrochemical performance of the Co3O4: (a) Charge-discharge profiles at constant current density of 100 mA/g. (b) Cycling

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performance at a current density of 100 mA/g. (c) Rate capabilities at different current densities. (d) Nyquist plots. All measurements were conducted in the voltage range of 0.01–3.0 V vs. Li+/Li.

The rate performance is another key measure of battery performance. The rate performance of the Co3O4 electrode is further evaluated under various current densities. As presented in Fig. 5(c), with the increase of the current densities, the capacities of Co3O4 remain stable and decrease regularly, that is, the average discharge capacity of the Co3O4 are 1231, 1026, 733 and 502 mAh/g at the current densities from 50 to 100, 200 and 400 mA/g, respectively. In addition, when the current density was finally turned back to 50 mA/g, the reversible capacity of Co3O4 electrode

ACCEPTED MANUSCRIPT still could recovers back to 1002 mAh/g and maintains this value without any obvious attenuation, showing a significant increase of rate capability performance. This also further clearly demonstrates that the unique porous structure of rod-shaped Co3O4 contribute to the diffusion and storage of lithium ions. To better investigate the electrical conductivity and the charge transfer efficiency of

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porous Co3O4, electrochemical impedance spectroscopy (EIS) measurements of metal oxide

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electrodes were performed in the frequency range from 1 Hz to 100 kHz. It is discernible that the Nyquist impedance plots of Co3O4 are composed of a depressed semicircle at the high-medium frequency region and a sloping straight line in the low frequency region in Fig. 5(d). The former corresponds to the charge transfer resistance (Rct) between electrodes and electrolyte and the straight line represents Warburg impedance (Zw) which is associated with the Li+ diffusion

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resistance in the electrodes[9,51-53]. Apparently, the cell demonstrates a larger diameter semicircle after 80 cycles, compared with the fresh cell, which is due to the charge transfer

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resistance increased.

In summary, porous rod-shaped Co3O4 was simply prepared by calcining Co-MOF-74. The

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resulting porous rod-shaped Co3O4 was used as a superior anode material for lithium ion batteries. The electrochemical results showed that porous Co3O4 exhibited an initial discharge capacity as

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high as 989 mAh/g. In addition, the nanostructure displayed excellent rate performance. The good electrochemical performance is related to the unique porous rod-shaped structure. Furthermore,

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this method can be easily expanded to fabricate other metal oxides using suitable precursor MOFs

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with promising applications in electrochemical devices such as LIBs and supercapacitors.

Acknowledgments

This work was supported by the Fundamental Research Funds for the Central Universities, and we are still grateful for the National Natural Science Foundation of China (NSFC21475021, 21427807), also the Natural Science Foundation of Jiangsu Province (BK20141331) as well as the Jiangsu provincial financial support of Fundamental Conditions and Science and Technology for people's livelihood for Jiangsu key laboratory of Advanced Metallic Materials (BM2007204). Appendix A. Supplementary data

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Supplementary data to this article can be found online at http://dx.doi.org/xxx.

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Graphical abstract

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Porous rod-shaped Co3O4 was simply fabricated via annealing Co-MOF-74 precursor. The similar morphology and porous structure of precursor were retained after calcining. The as-synthesized sample exhibited high-performance tested as anode materials for lithium ion batteries due to the unique porous rod-shaped structure.

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Porous rod-shaped Co3O4 was simply fabricated via annealing Co-MOF-74 precursor The similar morphology and porous structure of precursor were retained after calcining It exhibited high-performance tested as anode materials for lithium ion battery due to the unique porous rod-shaped structure

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