One-step solvothermal process of In2O3/C nanosheet composite with double phases as high-performance lithium-ion battery anode
Graphical abstract
In2O3/C nanosheet composite electrode exhibited a high lithium storage capacity of 869 mAh g−1 after 100 cycles at 100 mA g−1, excellent rate and long-term cycling performance.
Introduction
In2O3 is an important n-type semiconductor with wide band gap of 3.55–3.75 eV, high optical transparency, high electrical conductivity and excellent luminescence, which holds potential applications in transparent electronics [1], light-emitting diodes [2], solar cells [3], [4], gas sensors [5], [6] and lithium-ion batteries [7], [8], [9]. In2O3 typically exists in cubic bixbyite (c-In2O3) and hexagonal corundum (rh-In2O3) forms. In2O3 is potential anode material in lithium-ion batteries with high theoretical capacity of about 580 mAh g−1 [10].
Previous research has indicated that c-In2O3 thin films, single crystal In2O3 nanoparticles and vertically aligned In2O3 nanoblades exhibited large capacity of 1083 mAh g−1 [9], 1195.8 mAh g−1 [11], 3900 mAh g−1 [8] at the first cycle, respectively, but the capacity dropped to 504 mAh g−1 after 30 cycles at 71 mAh g−1, 107 mAh g−1 after 20 cycles at 100 mA g−1, and 580 mAh g−1 after 100 cycles at 250 mA g−1, respectively. Developing oxide-carbon composites is an effective strategy to overcome the low conductivity and poor structural stability of pure oxide as an anode material [12], [13], [14], [15]. Recently, it has been reported that graphene-encapsulated mesoporous In2O3 exhibited reversible capacity of about 480 mAh g−1 after 100 cycles at 0.1 C [10], Sn/In2O3/C nanocomposites exhibited charge capacity of about 600 mAh g−1 after 100 cycles at 100 mA g−1 [16], and In2O3/C core–shell nanospheres had an initial discharge capacity as high as 1607 mAh g−1 and the discharge capacity of 569 mAh g−1 after 50 cycles at 0.1 C [17]. However, much research attention focuses on electrochemical performance of the most stable c-In2O3. There are only few reports on the reversible lithium storage performance of the meta-stable rh-In2O3 [7], [18]. D. Liu et al. reported that rh-In2O3 exhibited an enhanced and stable capacity of 390 mAh g−1 (after 50 cycles) compared with c-In2O3 (49 mAh g−1, after 30 cycles) at 30 mA g−1 [7], and rh-In2O3/carbon nanocomposites exhibited an initial discharge capacity of 1360 mAh g−1, a stable reversible capacity of 867 mAh g−1 at 30 mA g−1 and 450 mAh g−1 at 300 mA g−1 [18]. To our knowledge, the reversible lithium storage performance of an anode composed of carbon and double phases of c-In2O3 and rh-In2O3 has not been reported.
Otherwise, most of the reported methods for synthesizing carbon coated In2O3 nanocomposites needed an elevated temperature or complex reaction conditions such as two-step process. Therefore, a simple, one-step, and large scale synthesis route should be developed. In our previous study, nanosheet-based rh-In2O3 microflowers were obtained by d-fructose-assisted hydrothermal process [5]. In this study, we report the synthesis of single porous In2O3 nanosheets and In2O3/C nanosheet composite with mixed phases of c-In2O3 and rh-In2O3 by d-fructose-assisted one-step solvothermal process in water–ethanol mixed solution. This approach involves none of the toxic organic solvents or surfactants and is simple, inexpensive and efficient.
Section snippets
Preparation and characterization of material
All reagents were of analytical grade and were used without further purification. In a typical preparation procedure, 0.1058 g In(NO3)3·xH2O, 0.432 g d-fructose and 0.064 g urea were added to 16 mL water–ethanol mixed solution in a 50 mL Teflon-lined stainless steel autoclave, and stirred for 5 min. The autoclave was then sealed and maintained at 160 °C for 16 h in an oven. After being cooled, the prepared precipitates were collected, washed with distilled water for several times and then dried in air
Results and Discussion
The XRD patterns of the samples calcined at 450 °C for 6 h in air are shown in Fig. 1. The peaks of the samples prepared with 0–6 mL ethanol were well index to the standard rh-In2O3 (JCPDS 22-0336). The sample prepared with 14 mL ethanol was the mixed crystal structure of rh-In2O3 (JCPDS 22-0336) and c-In2O3 (JCPDS 06-0416). The peaks of the sample prepared with 16 mL ethanol were well index to the standard c-In2O3 (JCPDS 06-0416).
Fig. 2 shows SEM images of samples calcined at 450 °C for 6 h in air.
Conclusion
We reported a novel In2O3/C nanosheet composite with double phases of c-In2O3 and rh-In2O3 anode material for high performance lithium-ion batteries which were fabricated by a facile one-step solvothermal treatment of a mixture of d-fructose and In(NO3)3 using urea as a precipitating agent in water–ethanol mixed solution followed by calcination. This simple method is expected to be used for the fabrication of other metal oxides and composites with controllable phase and morphology. The prepared
Acknowledgements
This work was funded by the National Natural Science Foundation of China (No. 51402252, 21276220), the Natural Science Foundation of Jiangsu Province (No. BK20140463, BK20141262), National Key Technology R&D Program of China (Grant no. 2013BAC13B01) and sponsored by Qing Lan Project.
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