Hierarchical SnO2@PC@PANI composite via in-situ polymerization towards next-generation Li-ion capacitor by limiting alloying process with high energy, wide temperature performance, and cyclability
Graphical abstract
Introduction
Greenhouse gas emission is increasing tremendously due to increased fossil fuel consumption, escalating global warming, and other environmental impacts [1]. In this context, innovative steps should be taken to reduce its effect on the environment by exploring alternative renewable energy sources. We have different clean, renewable, and environmentally friendly energy sources such as solar, wind, tidal, etc. However, the storage of these forms of energy is a big challenge. Electrochemical energy storage is the most promising among the different energy storage devices. Since Sony commercialized the first Lithium-ion battery (LIB) in 1991, the research on batteries has increased exponentially to improve their performance. They have been significantly explored and are used in several electrical devices, including mobile phones, laptops, medical applications, etc. However, they still lack the power density required for high-end applications. Meanwhile, electrical double-layer capacitors (EDLCs) have a high power density but decreased energy density. In this context, there came the necessity for a single device with energy and power density. Hence, there arose the idea of Lithium-ion capacitors (LICs).
LIC is a hybrid supercapacitor that consists of a battery-type (faradaic reaction) anode paired with a capacitive-type (non-faradaic reaction) cathode. This hybrid device has a higher energy density than EDLCs and a high power density than LIBs. Hence, they can bridge the gap between EDLCs and LIBs [2], [3], [4], [5], [6]. The performance of LICs majorly depends on the battery type electrode, i.e., anode. Therefore, most of the research activities in LICs are carried out on battery-type electrodes [7], [8], [9], [10], [11], [12], [13], [14]. The exploration started with the insertion type [15] electrodes such as Li4Ti5O12, graphite, etc. However, the lack of energy density for these insertion anodes makes people think of high-capacity alloying and conversion anodes [5,[16], [17], [18], [19], [20]]. The theoretical capacities of alloy/conversion-type anodes are more than (>600 mAh g–1) that of the abovementioned insertion types [21]. Moreover, the operational potentials are moderate and have good safety characteristics. Among the different electrode materials, SnO2 is one of the guaranteed candidates due to its high theoretical capacity (>750 mAh g–1), abundance, and lower redox potential (∼0.3 V vs. Li) [22], [23], [24], [25]. Nevertheless, one of the main challenges to overcome is the volume variation (up to 300%) caused during cycling, which could lead to the instability of the cell. Many research efforts are being reported in which morphology-controlled nanoparticles are synthesized at various dimensions to alleviate the pulverization of electrodes during cycling [26], [27], [28], [29], [30]. In our work, we synthesized hierarchical flower-shaped SnO2 nanostructures by a simple hydrothermal method and utilized them as anodes for LIC applications. The stability is improved by hybridizing with palmyra fruit-derived activated carbon (PC) and in-situ polymerized polyaniline (PANI). The polymer PANI enhanced the conductivity and flexibility of the SnO2 electrode by stabilizing its volume variation and thereby provided better stability [31]. Mass loading between the battery and capacitive-type electrodes was optimized based on the half-cell performance (vs. Li) and subsequently pre-lithiated prior to the fabrication of the LIC. The better electrochemical performance was exhibited by both half-cell, and full-cell configurations with superior energy density, power density, and long-term cyclic stability even at different temperature conditions are discussed in detail. Moreover, while comparing with previously reported SnO2-based LICs, our AC/SnO2@PC@PANI LIC exhibits superior performance in terms of energy and power density [32], [33], [34], [35], [36].
Section snippets
Material preparation
Synthesis of Urchin structured SnO2: SnCl2.2H2O and NaOH were selected as starting materials. All the reagents purchased from Sigma-Aldrich were of analytical grade and needed no further purifications. 6 mM SnCl2·2H2O was dissolved into 15 mL water and 5 mL ethanol. Then 0.4 mol L−1 NaOH solution was dropped into SnCl2 solution until pH=13 under continuous magnetic stirring. The obtained mixture was transferred into a 100 mL Teflon-lined stainless-steel autoclave, sealed and maintained at 180
Results and discussion
Powder XRD measurements were carried out to analyze the crystalline structure, phase purity, and chemical composition of the synthesized SnO2 nanoparticles and the SnO2@PC@PANI composite (Fig. 1(a)). The diffraction peaks of SnO2 correspond to the Cassiterite, syn phase with lattice parameters a = b = 4.7365 Å and c = 3.201 Å and 136 : P42/mnm space group (DB Card Number: 01–070–6153). The diffraction peaks of SnO2@PC@PANI are also indexed to Cassiterite, syn phase with the same 136 : P42/mnm
Conclusion
We designed a LIC with a battery type SnO2@PC@PANI anode and a capacitive type PC cathode. The high surface area carbon used in both anode and cathode is derived from the palmyra fruit by carbonization, activation, and followed by devolatilization. It is then polymerized with polyaniline and made composite with synthesized hierarchical SnO2 to use as the anode for LIC. The interfacial properties were studied using in-situ impedance, which substantiates the SEI layer formation process in the
CRediT authorship contribution statement
Manohar Akshay: Conceptualization, Formal analysis, Validation, Writing – original draft, Writing – review & editing. Selvarasu Praneetha: Conceptualization, Formal analysis, Validation. Yun-Sung Lee: Formal analysis, Validation, Writing – original draft, Writing – review & editing. Vanchiappan Aravindan: Conceptualization, Formal analysis, Validation, Writing – original draft, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
YSL acknowledges the financial support from the National Research Foundation of Korea (NRF) grant funded by the Korean government (Ministry of Science, ICT&Future Planning) (No. 2019R1-A2C1007620). VA acknowledges financial support from the Science and Engineering Research Board (SERB), a statutory body of the Department of Science and Technology, Govt. of India, through Start-up Research Grant (SRG/2020/000002) and Swarnajayanti Fellowship (SB/SJF/2020-21/12).
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