An inorganic–organic nanocomposite calix[4]quinone (C4Q)/CMK-3 as a cathode material for high-capacity sodium batteries

Shibing Zhenga, Jinyan Hua and Weiwei Huang*ab
aCollege of Environmental and Chemical Engineering, Yanshan university, Qinhuangdao 066000, China. E-mail:; Tel: +86 335 8387743
bKey Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China

Received 1st August 2017 , Accepted 3rd September 2017

First published on 6th September 2017

Based on the concept of grid-scale energy storage systems (ESSs), organic sodium-ion batteries (OSIBs), combining the merits of SIBs and the advantages of organic materials, are promising candidates for the new stage of commercial batteries. Organic cathode materials of calix[4]quinone (C4Q) in LIBs have delivered a high initial discharge capacity of 422 mA h g−1. However, its sodium storage property remains unclear. Here, a series of C4Q/ordered mesoporous carbon (CMK-3) nanocomposites have been firstly prepared by simple perfusion methods and employed as cathode materials for rechargeable sodium batteries. Systematic characterization including scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) analysis has been carried out, which demonstrated that C4Q was almost completely infused in the nano-pores of CMK-3 when its content was lower than 66 wt%. The optimized nanocomposite with 33 wt% C4Q exhibits a superior initial discharge capacity up to 438 mA h g−1 at 0.1C rate and a capacity retention of 219.2 mA h g−1 after 50 cycles. The enhanced cycling stability and high-rate capability are attributed to the nanosize effect and the good conduction of CMK-3. This constrains the dissolution of the embedded active materials. Our results enrich the family of inorganic–organic nanoconfinement cathode materials for high capacity sodium batteries.

1. Introduction

Sodium-ion batteries (SIBs) have recently been regarded as a valid alternative to lithium-ion batteries (LIBs) for their decent electrochemical performance. In particular, considering the increasing development of large energy storage stations such as electric vehicles (EVs) and smart grids, the potential weaknesses of high cost and rarity of lithium resources push conventional Li-ion batteries to a bottleneck.1–5 The inexhaustible and widely distributed sodium element is adjacent to Li on the periodic table, and also shares similar alkali metal chemistries with Li.6,7 To date, plenty of studies have focused on the development of advanced transition metal oxide cathode materials. These cathodes/anodes possess the advantages of good cyclability and high voltage, while their electrochemical reactions mainly rely upon the valence change of the depletable metal, thus demonstrating low theoretical capacity.8–14 As another choice, organic-based electrode materials without transition metals with properties of higher capacity, feasible structure designability, environmental benignancy and infinite availability are also potential candidates for sodium batteries.15–18

In fact, the use of organic electrode materials in SIBs can be traced back to the 1980s.19–21 Until now, most reported organic materials are mainly based on doping reactions, C[double bond, length as m-dash]N bond forming reactions and C[double bond, length as m-dash]O forming reactions. Among them, carbonyls based on the C[double bond, length as m-dash]O forming reaction have been most widely studied as electrodes of SIBs owing to their better cycling stability.22–24 In particular, quinone compounds such as simple quinones,25 quinone-derivatives,25–28 quinone-based polymers,29–31 and benzoquinonyl sulfide polymers32,33 are promising. Typically, simple anthraquinone (AQ) as a cathode material for sodium-ion batteries delivered a fast discharge capacity of 214 mA h g−1.34 Zhou's group reported that a large molecular weight polymer with a small quinone monomer poly(anthraquinonyl sulfide) (PAQS) shows a capacity of 198 mA h g−1.35 The above studies illustrate that the capacity superiority is unapparent compared to conventional inorganic materials mainly in virtue of the lower active site density. Thus, quinones with more quinone units can be obtained by combination in view of the increase of quinone amount corresponding to capacity. However, researchers have proved that the practical utilization of the available active sites is still low due to the steric hindrance of planar molecules. For instance, nonylbenzo-hexaquinone (NBHQ) has six paratactic quinone units with a high theoretical capacity of 489 mA h g−1, but the practical capacity is 125 mA h g−1 (26% active material) because of the large steric hindrance affecting the process of Li-ion insertion/extraction,36 let alone Na-ion with greater ionic radius. Studies indicated that quinone electrodes are hindered by either inadequate capacity or irrational space structure. Inspired by this finding, the development of compounds that contain a high density of effective quinone structure units and have low steric hindrance to ensure their high capacity is very urgent. Calix[4]quinone (C4Q) is a derivative of calix[n]arene, which bears four p-quinone units connected by four methylenes at the meta-position to form an annular macromolecule. Less steric hindrance facilitates the redox reaction and the process of insertion–extraction of metal ions. Four quinone units with eight active centers made it exhibit the second-highest capacity of 442 mA h g−1 (Ctheo = 446 mA h g−1) among carbonyl compounds for LIBs.37 Does it show the same specific capacity in SIBs?

Thus in this paper, we report C4Q as a cathode material for sodium-ion batteries. Similar to C4Q lithium-ion batteries, sodium-ion batteries were fabricated with a discharge capacity of 438 mA h g−1 at the first cycle, which is associated with the reversible eight electron reaction. However, as with C4Q in LIBs, it also decays immediately in SIBs because of the dissolution of C4Q. Thus we systematically studied the encapsulation of C4Q in CMK-3 at different ratios. C4Q/CMK-3 as a novel cathode for rechargeable sodium batteries reveals a better cycling retention of 50% after 50 cycles at 0.1C. Furthermore, the electrical insulation, rate performance and appreciable solubility in electrolytes have been improved.

2. Experimental

2.1 Materials synthesis

All reagents for synthesis were purchased and used without further purification except for dimethyl sulfoxide (DMSO), which was dried with CaH2 and then distilled in reduced pressure. C4Q was synthesized as described previously.38 The C4Q/CMK-3 nanocomposites were prepared by a simple impregnation method. First, different contents of C4Q were dissolved in treated DMSO. CMK-3 (purchased from Nanjing JiCang) was added to the above solution. After ultrasonic treatment for 30 min, the sample was dried under vacuum at 100 °C to remove the solvent and the C4Q/CMK-3 nanocomposites were eventually obtained. The composites with different ratios of C4Q to CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]3, 1[thin space (1/6-em)]:[thin space (1/6-em)]2, 1[thin space (1/6-em)]:[thin space (1/6-em)]1, 2[thin space (1/6-em)]:[thin space (1/6-em)]1 and 3[thin space (1/6-em)]:[thin space (1/6-em)]1) have been obtained.

2.2 Materials characterization

The structure of C4Q was characterized by various methods. Fourier transform infrared spectra were recorded on a FTIR-650 spectrometer in the wavenumber range of 400–4000 cm−1 with KBr pellets at room temperature. 1H NMR and 13C NMR measurements were performed on a Varian UNITY-plus 300 (300 MHz) spectrometer. Mass spectrometry was performed on an ESI-MS (LCQ Finnigan, produced by ThermoFinnigan) and elemental analysis was carried out (German, Vario EL). The C4Q/CMK-3 nanocomposites were characterized by XRD in a wide 2θ range of 10–80° at a sweep speed of 5° min−1 (D-max-2500/PC, CuKα radiation). TG measurements were performed under an air atmosphere with a NETZSCH TG 209 at a heating rate of 5 °C. Morphologies and microstructures were observed by SEM (JEOL JSM7500F). TEM images were obtained using a TEM (HT7700, 100 kV). The surface area and pore volume were analyzed by using N2 adsorption–desorption isotherms at 77 K on a BELSORP-mini instrument.

2.3 Electrochemical investigation

CR 2032 coin-type cells with a sodium plate anode, diaphragm and cathode film were assembled in an Ar-filled glove box (water and oxygen levels <0.1 ppm). The C4Q electrodes were fabricated by adding 15 wt% of polyvinylidenedifluoride (PVDF) binder in N-methyl-2-pyrrolidone (NMP) to a mixture of 60 wt% C4Q and 25 wt% of conductive carbon (super p). The C4Q/CMK-3 composite electrodes are made by mixing 80 wt% of C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]1), 5 wt% of super p, and 15 wt% of PVDF/NMP. All these ingredients were first milled in an agate mortar for 1 h. Then the slurry was coated onto the aluminum-foil current collector and dried at 80 °C for 10 h in a vacuum. The electrolyte of sodium batteries is 1 M NaClO4[thin space (1/6-em)]:[thin space (1/6-em)]ethylene carbonate (EC)/dimethylcarbonate (DMC) (v/v = 1[thin space (1/6-em)]:[thin space (1/6-em)]1) with 5% fluoroethylene carbonate (FEC). Glass microfiber filters (0.7 μm) were used as separators for sodium batteries. The discharge–charge experiments were carried out on a Land CT2001A cell testing system within the potential range of 1.2–4.2 V at different current densities. All of the electrochemical tests are performed at 25 °C.

3. Results and discussion

3.1 Materials characterization

The FTIR, ESI, 1H and 13C NMR spectra of the obtained sample are in agreement with the literature data,37 clearly indicating the successful synthesis of C4Q. Fig. 1a shows the XRD patterns of C4Q, CMK-3 and C4Q/CMK-3 composites. C4Q shows multiple peaks of varying intensity, indicating a good crystal state. After impregnating in CMK-3, there is only a broad peak at about 25° with the increase of C4Q, which is different from previous reports.39,40 Thus we assumed that the morphology of C4Q may be changed in the process of preparation. To confirm the above speculation, under the same conditions C4Q was directly dissolved in DMSO, ultrasonically treated for 30 min, and dried under vacuum for obtaining C4Q without CMK-3. As shown in Fig. 1b, the treated C4Q has only a peak at about 25°, which is the same as the C4Q/CMK-3 composites.
image file: c7qi00453b-f1.tif
Fig. 1 X-ray diffraction patterns of (a) C4Q, CMK-3, different proportions of C4Q/CMK-3 composites, (b) different treatment methods of C4Q.

Then the TG/DTA curves (Fig. 2) present that C4Q has a relatively high decomposition temperature of 260 °C, indicating that the active materials didn't degrade during the treatment process, which guarantees the thermostability during the discharge–charge course. Meanwhile, SEM was used to further investigate the surface morphology of C4Q, CMK-3 and C4Q/CMK-3 composites (Fig. 3). The configuration of the recrystallized C4Q is needle-like (Fig. 3a) and that of the treated C4Q is non-crystalline particles (Fig. 3b), which are shown in Fig. 3a and b. Fig. 3c–h show pure CMK-3 and C4Q/CMK-3 nanocomposites at different ratios. When the C4Q content is 25%, 33.3% and 50 wt% (Fig. 3d–f), hardly any C4Q particles are observed on the surface of CMK-3, which suggests the incorporation of C4Q into the pores of CMK-3. However, while the C4Q content is 66% and 75 wt% (Fig. 3g and h), there are flakes on the surface of CMK-3, which indicates that the channel of CMK-3 is approximately filled.

image file: c7qi00453b-f2.tif
Fig. 2 TG/DTA curves of C4Q.

image file: c7qi00453b-f3.tif
Fig. 3 SEM images of (a) C4Q, (b) C4Q dissolved in DMSO and dried in vacuo, (c) CMK-3, (d) C4Q (25%)/CMK-3, (e) C4Q (33%)/CMK-3, (f) C4Q (50%)/CMK-3, (g) C4Q (66%)/CMK-3, and (h) C4Q (75%)/CMK-3.

The N2 adsorption–desorption isotherms and the corresponding pore size distribution (PSD) have been analyzed. Fig. 4a and b show that CMK-3 has a specific surface area of 1074.3 m2 g−1 with a pore volume of 1.276 cm3 g−1. After the impregnation of C4Q, the surface area and pore volume of C4Q/CMK-3 composites decrease rapidly. For the C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]1) nanocomposite, the BET surface area decreases to 111.5 m2 g−1 and the corresponding pore volume drops to 0.132 cm3 g−1. When the ratio is 1[thin space (1/6-em)]:[thin space (1/6-em)]2, the BET surface area decreases to 258.0 m2 g−1 and the corresponding pore volume drops to 0.022 cm3 g−1. Whereas the mass ratio of C4Q to CMK-3 further increases to 2[thin space (1/6-em)]:[thin space (1/6-em)]1, the surface areas and pore volumes of composites are basically no longer changed. The results illustrate that CMK-3 is completely filled with C4Q, which is consistent with the results of SEM.

image file: c7qi00453b-f4.tif
Fig. 4 (a) The nitrogen adsorption–desorption isotherms and (b) pore volumes of CMK-3 and C4Q/CMK-3.

In summary, the C4Q was successfully anchored in the pores of CMK-3 as verified through the above results. When the content of C4Q reaches 66%, the pores are almost completely filled. Thus, we choose C4Q/CMK-3 composites (1[thin space (1/6-em)]:[thin space (1/6-em)]2, 1[thin space (1/6-em)]:[thin space (1/6-em)]1 and 2[thin space (1/6-em)]:[thin space (1/6-em)]1) as cathode materials for the electrochemical test.

3.2 Electrochemical performance

The electrochemical performance of C4Q and the composites was studied by discharge–charge tests. For the C4Q metal-half cell, Fig. 5a shows a long discharge voltage plateau at 2.5 V and two charge plateaus at 3.2 V and 3.9 V, respectively. Notably, the electrode exhibited an initial discharge capacity of 440 mA h g−1 (Ctheo = 446 mA h g−1) and recovered a charge capacity of 407 mA h g−1, which proves that all quinone units of C4Q can undergo Na-ion insertion–extraction reversibly. Thus the results further confirm the eight electron transfer reaction of the discharge/charge process (Fig. 5b). However, the capacity fades rapidly to 24 mA h g−1 after 10 cycles at 0.1C because of the serious dissolution. Arcuate discharge/charge curves without apparent plateaus for the C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) composite electrode can be observed in Fig. 5c. The characteristic curves indicate the nanocrystallization of C4Q and the excellent nanosize effect of CMK-3.41,42 More importantly, the specific capacity of C4Q was retained, and a much better stability upon cycling is displayed. Thus, the encapsulation of C4Q into CMK-3 could effectively hinder the dissolution of CMK-3 and enhance its cycling performance. Fig. 5d compares the cycling performance of C4Q and different ratios of C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2, 1[thin space (1/6-em)]:[thin space (1/6-em)]1 and 2[thin space (1/6-em)]:[thin space (1/6-em)]1) composites at 0.1C. It clearly shows that the cycling performances of composites are much improved, especially when the ratio of C4Q/CMK-3 is 1[thin space (1/6-em)]:[thin space (1/6-em)]2. They deliver an initial discharge capacity of 438 mA h g−1, and the capacity is 219.2 mA h g−1 after 50 cycles (with a capacity retention of 50%) at 0.1C. In short, the cycling performance can be greatly enhanced after the encapsulation.
image file: c7qi00453b-f5.tif
Fig. 5 The electrochemical characterization of sodium batteries, (a) discharge–charge curves of C4Q at 0.1C, (b) mechanism of C4Q during the discharge/charge process, (c) discharge–charge curves of C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) at 0.1C, (d) discharge capacities of C4Q and C4Q/CMK-3 composites at 0.1C rate.

Then the rate performance of bare C4Q and C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) is tested respectively (see Fig. 6). As the current rate increases, the capacities of C4Q decrease much more rapidly than those of C4Q/CMK-3. The discharge capacities of C4Q and C4Q/CMK-3 are 42.2 and 203.2 mA h g−1 at 0.2C, respectively. At a high rate of 1C, the discharge capacities are 13.2 and 130.4 mA h g−1 for C4Q and C4Q/CMK-3 respectively. The discharge capacity of the nanocomposite is 5-fold higher than that of C4Q. Obviously, the composite has better rate capability that is ascribed to the existence of CMK-3 which increased the conduction rate.

image file: c7qi00453b-f6.tif
Fig. 6 Rate discharge capacity of C4Q and C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) from 0.1 to 1C.

The morphology of CMK-3, C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) and C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) after 50 discharge/charge cycles was characterized by TEM. CMK-3 has an extremely high surface area with a highly ordered porous structure, which gives it the appearance of nanochanneled carbon scaffolds (Fig. 7a). After being impregnated, the surface gets smooth and its color turns black, indicating the filling of C4Q into CMK-3 (Fig. 7b). The morphology of CMK-3 after cycling was essentially preserved (Fig. 7c), in agreement with the SEM results. No porous channel structure was observed on the composite sample, implying that the excellent stability of CMK-3 could ensure the integrality of the nanocomposites during the electrochemical test, consequently prolonging the cycle life of the composite electrode.

image file: c7qi00453b-f7.tif
Fig. 7 TEM images of (a) CMK-3, (b) nanocomposites C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) and (c) C4Q/CMK-3 (1[thin space (1/6-em)]:[thin space (1/6-em)]2) after 50 discharge–charge cycles.

Finally, to evaluate the charge transfer and electrolyte diffusion in C4Q and C4Q/CMK-3 for sodium batteries, electrochemical impedance spectroscopy (EIS) were carried out at 2.7 V with a frequency ranging from 10−2 to 105 Hz. A semicircle in the high-frequency region and a straight line in the low-frequency region are observed in all of the profiles (Fig. 8), from which the semicircle can be attributed to the charge-transfer resistances at the electrode surface and the double-layer capacitance between the electrolyte and the cathode.43 The impedance increase during the first 10 cycles is associated with the dissolution process of C4Q, and then it decreases rapidly for only carbon at the electrode (Fig. 8a), while the impedance of the composites increases slowly and steadily (Fig. 8b) for CMK-3, hindering the process of dissolution. Remarkably, the charge transfer resistance of the composites is much lower than the raw material in the same cycle, indicating that CMK-3 can significantly enhance the conductivity of the composites.

image file: c7qi00453b-f8.tif
Fig. 8 The EIS test of (a) C4Q and (b) C4Q/CMK-3 for sodium batteries at the potential of 2.7 V and at a cycling rate of 0.1C.

4. Conclusions

In conclusion, C4Q is a promising candidate for sodium cathode materials, and the inorganic–organic composites have the best cycling stability when the ratio of C4Q/CMK-3 is 1[thin space (1/6-em)]:[thin space (1/6-em)]2. At 0.1C, they can provide an initial discharge capacity of 438 mA h g−1 in sodium batteries, and capacities are maintained at 219.2 mA h g−1 after 50 cycles. Furthermore, C4Q/CMK-3 also delivers high discharge capacities at a high rate (130.4 mA h g−1 at 1C). The strategy of composites combining the specific capacity of C4Q with the fine conductivity of CMK-3 can not only retard the dissolution of active materials but also improve the rate performance. Thus the work provides wide applications of inorganic–organic nanocomposite materials for sodium-ion batteries.

Conflicts of interest

There are no conflicts to declare.


This work was supported by the National Natural Science Foundation of China (no. 21403187), the China Postdoctoral Science Foundation (no. 2014M551053), and the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University.

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