Bing Liab,
Hongyou Zhangab,
Dabin Wangab,
Hong Lv*ab and
Cunman Zhang*ab
aClean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, China. E-mail: zhangcunman@tongji.edu.cn; lvhong@tongji.edu.cn; Fax: +86 21 69589355; Tel: +86 21 69589355
bSchool of Automotive Studies, Tongji University, Shanghai 201804, China
First published on 1st August 2017
Activated carbon (AC) derived from the most common agricultural waste, corncob, has been synthesized through a simple chemical activation process. Furthermore, high energy density lithium-ion capacitors (LICs) were fabricated using corncob-derived AC as the cathode and commercially available Li4Ti5O12 as the anode. The optimized LIC achieves a maximum energy density of 79.6 W h kg−1 and is also capable of delivering high power density of 4 kW kg−1, which is much higher than that of similar constructions employing commercial AC as the cathode. In addition, the corncob-based LIC exhibits great cycle performance with 85.2% retention of the initial capacitance value after 2000 cycles. The present research offers a new approach for the development of high performance LICs employing carbonaceous electrodes of biomass precursors. These results make the corncob-derived activated carbon the most promising candidate for future energy storage applications.
However, many obstacles remain to be tackled before the large-scale applications of SCs can be envisaged. Above all, improving the energy density of SCs is a task of top priority. LICs combining a battery-type electrode and a capacitor-type electrode are considered to be the most promising route to achieve the abovementioned goal. Normally, LICs demonstrate the integrated advantages of both SCs and LIBs; this means that they can deliver higher energy density than SCs and higher power density than LIBs. LICs bridge the gap between SCs and LIBs and they have been given widespread attention since the concept was first proposed by Amatucci et al. in 2001, who employed nanostructured Li4Ti5O12 (LTO) as the anode and AC as the cathode, and the LICs offered an energy density of over 20 W h kg−1.2 Since then, several Li-insertion materials have been proposed for LICs, but LTO remains the most promising candidate due to its outstanding properties such as zero-strain insertion, no solid electrolyte interface (SEI) formation, low-cost, and safety. Considering that research on battery-like electrode materials has made great progress, there is pressing need to explore applicable carbonaceous materials to ensure the high power density of LICs.
High-performance electrode materials that can be easily mass-produced are the prerequisites for supercapacitors to be widely accepted by the market. In the last decade, carbon-based materials from AC to CNTs have been widely investigated as electrode materials for application in electrochemical supercapacitors.3,4 Recently, R. Gokhale et al.5 used oligomer-salt as a precursor to prepare porous carbon as an electrode material for LICs, and many other researchers6,7 synthesized various carbon materials by adopting different kinds of polymers. However, most activated carbons derived from various sources including biomass and organic polymers demonstrate relatively low capacity (∼50 mA h g−1) in non-aqueous electrolytes.8–10 However, most of the researches on carbon derived from polymers involves expensive polymers and the tedious processes are usually detrimental to health. Practically, these low-capacity carbonaceous materials show little potential for commercialization.
Recently, several studies have reported graphene-based materials that have been employed as a cathode along with the LTO anode, and the LICs prepared using them achieved high energy densities of over 40 W h kg−1.11,12 However, the scalability, reproducibility, and high-cost would hold back graphene-based materials from commercialization. Therefore, because of their easy accessibility, low-cost, good chemical stability, and non-toxicity, high surface area porous carbons derived from bio-waste have attracted significant attention. For example, Sennu et al.13 used Prosopis juliflora-derived activated carbon as a cathode to fabricate the high-energy LIC with a maximum energy density of ∼80 W h kg−1 with 76% retention after 10000 cycles. Agricultural waste-derived AC tends to have rich surface functional groups, enhancing the capacity.14,15 Moreover, these kinds of activated carbons demonstrate a wide range of pore size distribution, which enables more active sites for charge accumulation.
In this study, we first demonstrated the large surface area AC with high capacity derived from corncob through simple steps of pyrolysis and activation at high temperatures for the LIC application. More specifically, with the corncob-derived activated carbon (AC) applied as the cathode in LIC assembly along with commercially available spinel phase Li4Ti5O12 as the anode, the as-obtained AC is competitive in future energy storage applications.
Cyclic voltammetry (CV) was carried out at a scan rate ranging from 5 to 100 mV s−1. Galvanostatic charge/discharge cycling (GCD) was conducted in the current density range from 0.1 to 2 A g−1. Electrochemical impedance spectroscopy (EIS) was tested in the frequency range from 0.1 Hz to 100 kHz with a potential amplitude of 10 mV. All the tests were performed using a CHI 760E electrochemical workstation. Cycling performances were determined using a LAND battery tester (Wuhan Jinnuo Electronics Co., Ltd) under ambient temperature conditions.
Fig. 2 (a) N2 sorption–desorption isotherms of the corncob-based activated carbon at 77 K; (b) pore-size distribution of the corncob-based activated carbon. |
FT-IR spectroscopy (Fig. 3a) an XPS (Fig. 3b) were employed to evaluate the surface chemistry properties of the as-prepared AC. Basically, the FT-IR spectrum displays two main bands located at 1545 cm−1 and 1060–1095 cm−1, which may have resulted from highly conjugated C–O in a quinone/carbonyl structure21 and the C–O stretching vibration of various functionalities,22,23 respectively. Based on the XPS spectra, we can easily draw a conclusion that the AC derived from corncob is rich in quinone/carbonyl groups, which can further improve the wettability of the carbon surface and reduce the charge transfer resistance and will finally contribute to the improvement of the electrochemical performance of the AC electrode.24
To determine the mass loading of each electrode in the LIC assembly, it is essential to evaluate the single-electrode performance along with metallic lithium in half-cell configurations. Considering the decomposition potential of the electrolyte, the AC cathode was tested in a half cell from 3 V to 4.6 V vs. Li (current density ranging from 100 mA g−1 to 1000 mA g−1), and the corresponding results are presented in Fig. 4. The sample shows a linear increase in potential with time; this clearly suggests the perfect desorption/adsorption process of PF6− anions and the formation of an electrostatic double layer across the electrolyte/electrode interface. The profiles show the typical characteristic of capacitors and reveal an initial discharge capacity of 75.9 mA h g−1 at 100 mA g−1, and the 91.7% capacity is retained after 1000 cycles. In the same voltage range, this value is much higher than that previously reported for various activated carbons.8,25,26 Detailed data were obtained and compared with the as-obtained results in Table 1; the half-cell performance of the commercially available LTO under the same testing conditions is also given in Fig. 4.
Materials | Testing conditions | Current density | Specific capacity | Ref. |
---|---|---|---|---|
Corncob based AC | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 75.9 mA h g−1 | This work |
ZHTP | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 71 mA h g−1 | 9 |
ZP | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 58 mA h g−1 | 9 |
HTP | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 44 mA h g−1 | 9 |
NORIT (commercial AC) | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 33 mA h g−1 | 9 |
Oligomer-salt derived carbon | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 56 mA h g−1 | 5 |
HSPC | LiPF6, 3–4.6 V vs. Li | 0.1 A g−1 | 54 mA h g−1 | 8 |
3D-CNS | LiPF6, 3–4.5 V vs. Li | 0.1 A g−1 | 70 mA h g−1 | 25 |
Based on the half-cell performance of the activated carbon, the optimized mass ratio of AC to LTO was about 2:1. However, during the course of the experiment, mass loading was indirectly controlled by altering the thickness of the electrode coating. Thus, it was unpractical to accurately determine the mass loading of the electrodes with materials that have different mass densities. To obtain the optimum electrode matching, a series of LICs with the thickness ratio of AC to LTO ranging from 1:1 to 4:1 (thickness ratios were converted to the corresponding mass ratios of AC to LTO in the following explanations) were fabricated and tested between 1 and 3 V under various conditions. The GCD curves at a current density of 100 mA g−1 (in the case of the full-cell, all the current density values are based on the total mass of the active material of both electrodes) and cyclic voltammetry curves at a sweep rate of 5 mV s−1 of the LICs are profiled in Fig. 5a and b, respectively. The results show that the LIC with AC to LTO mass ratio of 1.5:1 displays the greatest performance; considering the experimental limitations and the dissimilarity between full-cell and half-cell performance, the result is in accordance with the anticipated value based on the half-cell performance within experimental error. Fig. 5c represents the GCD curves at various current densities of the optimized LIC (AC:LTO = 1.5:1). The curves are neither linear like those of capacitors nor inflected like those of batteries; this is attributed to the integrated reaction mechanism of the LICs. Briefly, during the charge process, lithium ions intercalated into the lattice of LTO (faradaic reaction) along with the PF6− anions simultaneously accumulated on the interface of the electrolyte/electrode (non-faradaic reaction),2,27 and the reaction was completely reversed in the discharge process. Thus, the synergistic effects of both capacitors and batteries are demonstrated by the GCD curves. This can also be validated from the CV profiles displayed in Fig. 5d. A combination of CV characteristics of both AC and LTO in the half-cell configurations in Fig. 6 and sharp increase/decrease in current response are observed at the critical point of ∼1.5 V at low sweep rate, which indicates that the Li-insertion/de-intercalation occurs at the anode during cycling and the corresponding formation of an electric double layer across the AC electrolyte/electrode interface.10 In addition, the curves at high sweep rate exhibit severe distortion, which results from the polarization of the electrodes, and the faradaic reaction limits the charge storage/release rate under high power conditions.
Fig. 6 (a) CV curves of AC in the half-cell between 3 and 4.6 V vs. Li at a sweep rate of 1 mV s−1, (b) CV curves of LTO in the half-cell between 1 and 3 V vs. Li at a sweep rate of 1 mV s−1. |
The Ragone plot was obtained from galvanostatic charge/discharge measurements of the as-fabricated AC//LTO LICs along with those reported for similar constructions involving carbonaceous material as the cathode and pure LTO as the anode (Fig. 7a and b). The specific power and energy densities were calculated using the following relations: P = (U × i/m) and E = (P × t), where U = (Umax + Umin)/2, Umax and Umin are the potentials at the beginning and end of discharge curves, respectively, and m is the total active mass of both electrodes.25,27,28 The corncob-derived activated carbon-based LICs delivered the highest energy density of 79.6 W h kg−1, which was much higher (2 times) than that of a similar commercial activated carbon-based system (∼36 W h kg−1).10 The optimized AC//LTO LIC delivered an excellent performance even at high power density (32.7 W h kg−1 at 4 kW kg−1). It is worth noting that our device outperformed most of the similar constructions involving carbonaceous materials as the cathode and LTO as the anode, as well as some other constructions, for instance, AC//carbon-coated-Li4Ti5O12 (35.5 W h kg−1) reported by H.-G. Jung et al.,29 AC//nano-crystalline Li4Ti5O12/CNF (55 W h kg−1) reported by K. Naoi et al.,30 poly(acrylamide-co-acrylic acid) potassium salt-derived carbon//Li4Ti5O12 (55 W h kg−1) reported by D. Puthusseri et al.,10 coconut-derived activated carbon//Li4Ti5O12 (69 W h kg−1) reported by A. Jain et al.,8 AC//Li4Ti5O12 spheres (74.3 W h kg−1) reported by S.-X. Deng et al.,31 and the LICs of AC/TiO2(B) reported by Aravindan et al.32 Moreover, the corncob-based AC//LTO hybrid system is only rivaled by similar graphene-based structures,9 but the introduction of graphene results in much higher cost than that of the biomass-derived carbons employed herein. Thus, the combination of low-cost agricultural waste-derived activated carbon and commercially available Li4Ti5O12 would make the biomass-derived carbons have great potential for large scale stationary and automotive applications.
Fig. 7 (a) Ragone plot of the as-fabricated Li-HECs and (b) comparison with those reported for similar constructions involving carbonaceous material as the cathode and pure LTO as the anode. |
Cycle life is of great significance for practical applications, and hence, the cycling profiles of the as-obtained AC//LTO LIC were determined at a current density of 2 A g−1. As depicted in Fig. 8, the corncob-based AC//LTO LIC retained 85.2% of the original value after 2000 cycles. After 2251 cycles, it reached 79.01% of the original value. These results are tolerable considering that the lithium ion batteries often last for less than 1000 cycles. Moreover, the acceptable attenuation mainly originated from the intrinsic nature of the commercially available Li4Ti5O12.10 This issue can be alleviated through various approaches such as carbon coating29 or integrating LTO with other materials such as graphene9 and carbon nano-fibers.30
Fig. 8 Cycling performance of the corncob-based AC//LTO Li-HEC at a current density of 2 A g−1. The data points were obtained every 50 cycles. |
This journal is © The Royal Society of Chemistry 2017 |