A high-performance, all-textile and spirally wound asymmetric supercapacitors based on core–sheath structured MnO2 nanoribbons and cotton-derived carbon cloth
Graphical abstract
Introduction
Promptly growing energy consumption coupled with critical issues of climate change has become an unquestionable threat for the planet and the quality of human life [1]. Also, these issues have motivated significant efforts to develop multitudinous novel forms of sustainable and renewable energy-conversion and storage devices [2,3]. Among various novel energy storage systems, supercapacitors are of special importance due to their fascinating capability of bridging the power/energy gap between traditional dielectric capacitors and batteries/fuel cells [4]. In addition, their high power density, fast rates of charge–discharge, reliable cycling feature and safe operation are also highly regarded [5].
Textile supercapacitors are an important category of flexible supercapacitors and have attracted widespread attention because of their potential to develop green flexible and wearable electronics for some advanced future applications like high-tech sportswear, health monitoring systems and military camouflages [[6], [7], [8]]. For instance, Yuksel and Unalan [9] reported flexible solid-state textile-based supercapacitors with ternary nanocomposite electrodes containing manganese oxide (MnO2), single-walled carbon nanotubes and polyaniline or poly(3,4-ethylenedioxythiophene)‒poly(styrenesulfonate), which were layer-by-layer deposited onto cotton substrates. The measured maximum power and energy density and maximum capacitance were 746.5 W kg−1, 66.4 W h kg−1 and 294 F g−1, respectively. Laforgue [10] synthesized poly(3,4-ethylenedioxythiophene) nanofiber mats by the combination of electrospinning and vapor-phase polymerization, and the mats were then incorporated into all-textile flexible symmetric supercapacitors (SSCs) whose maximum capacitance reached 20 F g−1 at the current density of 2 mA cm−2. Meng et al. [11] prepared an all-graphene core–sheath fiber composed of graphene fiber core with a sheath of three-dimensional (3D) graphene networks via the combined method of hydrothermal and electrolytic routes. This as-prepared fiber supercapacitor was woven into a textile for wearable electronics. Besides aforesaid materials, some other types of carbon materials [12,13], conductive polymers [14] or metallic oxides/hydroxides [15,16] were also utilized to develop textile supercapacitors. However, it needs to be pointed out that the cost of some electrochemical active substances used for the preparation of textile supercapacitors is prohibitive. More seriously, a number of synthetic pathways require eco-unfriendly chemicals, specific equipment or elaborate procedures, which create a barrier to their large-scale industrial promotion. As a result, it is significative to explore faster, cheaper and simpler approaches to develop high-performance textile supercapacitors.
Cellulose is the most abundant nature polymer on Earth and consists of a linear chain of several hundred to many thousands of β(1 → 4) linked d-glucose units (see Fig. S1 in SI). As a main structural component of the cell wall of green plants and algae, cellulose has widely served as the feedstock of papermaking, skincare products, biofuel, textile industry and building products. In addition, owing to good flexibility, abundant pores and effortless conversion to conductive carbon counterparts, cellulose products (e.g., 1D fibers, 2D films and 3D hydrogels or aerogels) have been verified experimentally as promising candidates for development of environmentally benign energy storage devices (like supercapacitors [[17], [18], [19]], lithium-ion battery [20,21], zinc–air battery [22,23] and solar cells [24,25]). Actually, plant-derived cellulose is usually found in a mixture with lignin, hemicellulose, pectin and other substances. Therefore, some purification processes of cellulose are generally involved. However, common chemical purification consumes a good deal of chemicals (like benzene) [26], and greener physical separation (like steam explosion) usually needs energy-extensive consumption [27]. Recently, bacterial cellulose serving as a substrate for energy storage has also been highlighted [17,28], but its production is still complex and lengthy. Undoubtedly, more direct, facile and green utilization ways of cellulose resource are high-profile.
Considering these issues, herein, we report an easily-operated and rapid approach to prepare a flexible, high-performance and self-supported textile electrode. For achieving high-efficient utilization of cellulose resource, common jean cloth (100% cotton) was directly used as the feedstock to undergo a pyrolysis treatment for the conversion to its carbon counterpart (namely cotton-derived carbon cloth, coded as CDCC). CDCC was subsequently used as a flexible and free-standing substrate for the in-situ growth of MnO2 nanoribbons via a simple immersion treatment in the solution of potassium permanganate (KMnO4) with strong oxidizing property. MnO2 is a kind of well-known pseudocapacitance materials and featured with high specific capacitance, low cost and toxicity, abundance and high theoretical capacitance of 1387 F g−1 based on a one-electron redox reaction per Mn atom (the calculation is available in SI). The as-prepared MnO2/CDCC with a core–sheath structure served as the positive electrode and was assembled into an all-textile and spirally wound asymmetric supercapacitor (ASC) using CDCC as the negative electrode and thin cotton woven as the separator. Results of the electrochemical evaluation demonstrate that both the electrode and the ASC possess favorable electrochemical properties.
Section snippets
Materials
Common old jean (100% cotton) served as raw material of CDCC after being washed repeatedly with distilled water and ethyl alcohol and then dried at room temperature. Chemicals including NaOH, KMnO4 and Na2SO4 were supplied by Shanghai Aladdin Industrial Inc. (China). Nickel foam was obtained from SXLZY Battery Material Co., Ltd. (Taiyuan, China).
Preparation of cotton-derived carbon cloth (CDCC)
The preparation of CDCC was carried out by transferring the clean and dried jean into a tubular furnace for pyrolysis under a flow of nitrogen. The
Graphical illustration of the design concept of MnO2/CDCC
For the purpose of realizing more high-efficient and green use of cellulose resource and seeking a more facile and economical synthesis process of textile supercapacitors, we design an easily-operated and cost-effective combined technique of pyrolysis and immersion to fabricate a high-performance and free-standing MnO2/CDCC electrode. As illustrated in Fig. 1, a piece of flexible cotton woven was firstly pyrolyzed into the electrically conductive CDCC under the protection of nitrogen. After the
Conclusions
In summary, we have demonstrated a simple and rapid approach (i.e., pyrolysis and immersion) to prepare a core–sheath structured electrode based on MnO2 nanoribbons and CDCC. The ribbon-like nano-MnO2 was well dispersed on the surface of carbon fibers of CDCC by virtue of an in-situ redox reaction between KMnO4 and CDCC during the immersion process. This synthetic strategy primarily creates three merits, namely (1) this good interface connection between MnO2 nanoribbons (sheath part) and CDCC
Acknowledgements
This study was supported by the National Natural Science Foundation of China (grant no. 31470584 and 31530009) and Overseas Expertise Introduction Project for Discipline Innovation, 111 Project (No. B08016).
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