LiMn2O4 nanorod arrays: A potential three-dimensional cathode for lithium-ion microbatteries

doi:10.1016/j.materresbull.2014.11.020

Materials Research Bulletin

Volume 69, September 2015, Pages 2-6

https://doi.org/10.1016/j.materresbull.2014.11.020 Get rights and content

Highlights

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Self-supported LiMn₂O₄ nanorod arrays are prepared on the Pt substrates.
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LiMn₂O₄ nanorod array cathode exhibits a large areal capacity of 0.25 mAh cm⁻².
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LiMn₂O₄ nanorod array cathode exhibits good cycle performance and rate capability.
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LiMn₂O₄ nanorod arrays are potential cathodes for 3D microbatteries.

Abstract

Although three-dimensional (3D) microbatteries represent great advantage compared to their two-dimensional counterparts, the fabrication of 3D cathode is still a challenge, which holds back the further development of 3D microbatteries. In this work, we present a novel approach for fabrication of LiMn₂O₄ nanorod arrays as 3D cathode for microbatteries. α-MnO₂ nanotube arrays are firstly grown on the Pt substrate as the template, and LiMn₂O₄ nanorod arrays are then prepared by lithiation of α-MnO₂ nanotube arrays in molten salt followed by 800 °C annealing in air. In the half cell test, the 3D LiMn₂O₄ nanorod arrays exhibit both high gravimetric capacity (∼130 mAh g⁻¹) and areal capacity (∼0.25 mAh cm⁻²), while maintaining good cycling stability and rate capability. The facile synthesis and superior electrochemical performance of the three-dimensional LiMn₂O₄ cathode make it promising for application in microbatteries.

Graphical abstract

Introduction

The rapid development in microelectronic industry have led to a variety of small-scale autonomous devices including microsensors, drug delivery systems, “smart” cards and microelectromechanical systems (MEMS) [1]. To operate independently, these microelectronic devices require on-board power sources, which make thin film microbatteries the ideal power delivery choice. However, the reduced area available on microscale devices limits the areal footprint for microbatteries, thus leading to the insufficient power for two-dimensinoal (2D) microbattery configurations [2]. By utilizing the third dimension-height, 3D microbattery architecture, comprising a 3D matrix of components (cathode, anode and electrolyte) arranged in either a periodic array or an aperiodic ensemble, has been proposed to increase the energy and power for microbatteries. Recently, several configurations have been proposed for 3D microbatteries, including the interdigitated geometry, the concentric arrangement, the inverse opal structure, the “sponage” design, and the perforated substrate [3]. One of the most important keys to realize these 3D designs is the fabrication of 3D electrodes. Among various 3D architectures, the self-supported nanorod/nanowire arrays represent several advantages for energy storage, including fast axial electron transport between active material and conductive substrate, large surface area with more electrochemical active sites, and shortened pathway for fast lithium ion diffusion [4]. Although numerous works have been done on fabricating metal oxide nanorod/nanowire arrays as 3D anodes for microbatteries, there are very limited reports on self-supported 3D architectures for cathodes [5], [6].

LiMn₂O₄ is one of the most attractive cathode materials for lithium-ion batteries due to its low cost, environmental benignity, and copious resource availability [7], [8]. Various LiMn₂O₄ nanostructures such as nanowires and nanorods have been prepared, showing superior electrochemical performance compared to their bulk materials [9], [10]. However, these nanostructures cannot be utilized in microbatteries and the reports on preparation of LiMn₂O₄ nanostructures directly on conductive substrate are very limited [11], [12]. In a previous work, polystyrene (PS) template was employed in a sol–gel synthesis to prepare 3D LiMn₂O₄ thin films [11]. As single layer PS template was used, the thickness of the porous LiMn₂O₄ film is only about 500 nm, thus resulting in a low areal capacity of about 3 μAh cm⁻².

In the present work, a facile method was developed to prepare 3D LiMn₂O₄ nanorod arrays on the Pt substrates. The α-MnO₂ nanotube arrays grown on the Pt substrates were used as the template. The 3D LiMn₂O₄ nanorod arrays were then prepared by lithiation of α-MnO₂ nanotube arrays in molten salt followed by 800 °C annealing in air. The 3D LiMn₂O₄ nanorod arrays exhibited outstanding electrochemical performance, making them promising as cathode for microbatteries.

Section snippets

Preparation of LiMn₂O₄ nanorod arrays

The synthesis procedure for the 3D LiMn₂O₄ nanorod arrays is illustrated in Fig. 1a. In the first step, α-MnO₂ nanotube arrays were grown on the Pt substrate by a hydrothermal method. In a typical synthesis, 3.6 g KMnO₄ and 8 mmol concentrated HCl were added to 32 mL deionized water to form the precursor solution, which was then transferred into a 50 mL Teflon-lined stainless steel autoclave. A 1 × 1 cm Pt foil was immersed into the solution as the substrate to grow MnO₂ nanotube arrays and the

Results and discussion

Fig. 1b shows the XRD pattern of the Pt-supported α-MnO₂ nanotube arrays. Except for the diffraction peaks from the Pt substrate, all other diffraction peaks can be exclusively indexed as the tetragonal α-MnO₂ (JCPDS no. 44-0141) with no detection of impurity phase. After the molten-salt lithiation and high-temperature annealing, the diffraction peaks from the final product (Fig. 1c) can be perfectly indexed to the cubic spinel LiMn₂O₄ (JCPDS no. 35-0782) with Fd-3 m spacegroup. The calculated

Conclusions

In summary, 3D LiMn₂O₄ nanorod arrays have been successfully prepared on Pt substrates by molten-salt lilthiation to α-MnO₂ nanotubes followed by annealing in air. By using α-MnO₂ nanotubes as the template, the well aligned nano array structure can be well retained after the MnO₂/LiMn₂O₄ phase transition. The current 3D electrode architecture provides both large surface area and shortened Li ion diffusion length, thus enabling high energy density and power density in small footprint with

Acknowledgements

This work was supported by National Natural Science Foundation of China (No. 51102134), Natural Science Foundation of Jiangsu Province (No. BK20131349), QingLan Project of Jiangsu Province, China Postdoctoral Science Foundation (No. 2013M530258), and Jiangsu Planned Projects for Postdoctoral Research Funds (No. 1202001B).

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LiMn2O4 nanorod arrays: A potential three-dimensional cathode for lithium-ion microbatteries

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Preparation of LiMn2O4 nanorod arrays

Results and discussion

Conclusions

Acknowledgements

Prog. Nat. Sci. Mater. Int.

Electrochem. Commun.

Electrochim. Acta

J. Solid State Chem.

J. Power Sources

J. Power Sources

Adv. Energy Mater.

MRS Bull.

Electrochem. Soc. Interface

Adv. Mater.

LiMn₂O₄ nanorod arrays: A potential three-dimensional cathode for lithium-ion microbatteries

Preparation of LiMn₂O₄ nanorod arrays