Synthesis of hierarchical NiO microsphere with waxberry-like structure and its enhanced lithium storage performance
Graphical abstract
Introduction
In the past decade, lithium-ion batteries (LIBs) have attracted worldwide attention due to their broad applications in portable electronic devices and the great potential use in the future hybrid electric vehicles (HEVs) and electric vehicles (EVs) [1], [2]. The performances of LIBs mainly depend on the properties of its key components such as anode materials, cathode materials, separator and etc. Owing to its stable cycle ability in the charge/discharge process, graphite has become the most commonly used anode material in the state-of-the-art LIBs [3], [4], [5], [6]. However, its theoretical capacity only 372 mAh g−1 can't satisfy the growing needs for higher energy and higher power LIBs, which are significantly related to the development of HEVs and EVs. New materials with high lithium storage capacity have been looking for endlessly to replace the commercial graphite.
Tarascon et al. have firstly reported that transition metal oxides (TMOs) could be served as anode materials in the next-generation LIBs through heterogeneous conversion reaction: Li + TMO ↔ Li2O + TM (TM = Mn, Fe, Co, Ni, Cu) in 2000s [1]. Among them, nickel oxide (NiO) has attracted intensive interest as a promising anode material because it has many advantages, such as relatively higher theoretical capacity which is 718 mAh g−1 compared with that of commercial graphite, low cost, and environmental-friendliness [6], [7], [8], [9], [10], [11]. These delightful properties benefit the electrochemical performance of NiO when it is applied as the anode material of LIBs. Unfortunately, as the common features of the TMOs, NiO also suffers from drastic volume change and severe capacity fading during battery cycling through conversion reaction. In order to improve the electrochemical lithium storage properties of NiO material for practical application, NiO material with various morphologies and nanostructures have been synthesized, such as plate structures [12], nanofibers [5], [7], nanotubes [13], [14], nanowall array [15], nanosheet networks [10], hollow microspheres [8], [9], urchin-like microspheres [11], [16] and flower-like microspheres [16], [17], [18]. NiO materials with hierarchical porous structure have many intriguing advantages in charge/discharge process, for instance, it can provide a stable structure for lithium ions embedding and guarantee stable cycle ability, it has relatively larger surface area convenient for the contact with electrolyte and the diffusion of lithium ion and electrons to benefit for rate capacity [19].
Hierarchical porous NiO/C composite microspheres have been successfully prepared by Zhang et al. choose natural porous lotus pollen grains as carbon source as well as the template method [20]. The discharge capacity of the hierarchically porous NiO/C composite has been determined to be 352 mAh g−1 at a current density of 4.2C. Li et al. have prepared 3D flower-like NiO hierarchical architectures and compared the electrochemical properties of the as-prepared NiO synthesized at 300 °C with NiO with different morphologies in the literature [17], [21], [22], [23], [24], [25]. It presented an available charge capacity of 713 mAh g−1 at 0.14C after 40 cycles and remained 470 mAh g−1 in the 30th cycle after cycling with diverse current densities from 0.14 to 1.4C. Wang et al. have synthesized prefect urchin- and flower-like hierarchical NiO microspheres [16], but the capacity of those NiO materials decay very fast in charge/discharge process. Consequently, although hierarchical NiO microspheres have many pleasing features, it still needs more improvement to optimize the lithium storage performance of NiO materials.
In this work, hierarchical NiO microspheres with a waxberry-like structure are successfully synthesized by a one-pot hydrothermal reaction followed by thermal annealing, which consist of needle-like nanoparticles and form a hierarchical micro/nanostructure. It is well known that the materials with hierarchical micro/nanostructure can mitigate tremendous volume changes [26]. Therefore, owning to the optimized one-dimension structure, it can further shorten the diffusion lengths of lithium ions and electrons during repeated charge/discharge processes. We have also explored the influence of the annealing temperature on the size of the needle-like nanoparticles in the NiO microspheres, and characterized their structure and electrochemical performance. The results illustrate that NiO by calcination at 300 °C (denoted as NiO-300) can well preserve hierarchical waxberry-like structure and present a good electrochemical properties.
Section snippets
Materials synthesis
All chemical reagents we used were analytical purity and used without further purification. In the first step, 0.015 mol of nickel chloride hexahydrate (NiCl2·6H2O), 0.045 mol of urea (CO(NH2)2) were dissolved in 75 mL deionized water under continuous magnetic stirring. Subsequently, the mixture solution was stirred for 0.5 h to mix homogeneously and then transferred into a Teflon-lined stainless steel autoclave (100 mL) and heated at 100 °C for 20 h. After cooling down to room temperature
Synthesis and characterization of precursor
As illustrated in Scheme 1, the precursor was prepared via a one-pot hydrothermal reaction. During hydrothermal reaction, NiCl2 reacts with urea gradually to form the precursor. After calcination at different temperature, the precursor was transformed into NiO-300, NiO-350 and NiO-450 materials, respectively.
Due to the precursor may be made up of hierarchical micro/nanostructure with lower crystallinity, the XRD of one-dimensional detector can't get the signal obviously. In order to solve this
Conclusions
In summary, we have fabricated a hierarchical micro/nanostructure precursor via a one-pot hydrothermal route. Using two-dimensional X-ray diffraction (XRD2) and TG to identify the composition of the precursor which is mainly consist of Ni2(OH)2CO3 and blend with a few Ni(HCO3)2. The NiO material with hierarchical waxberry-like structure can be obtained after thermal annealing. This unique structure can provide a larger specific surface area and shorter diffusion pathways for lithium ions and
Acknowledgments
This work was jointly supported by the NSFC (Grant Nos. 21273184, 21321062 and 21373008), the “973” Program (Grant No. 2015CB251102), SRFDP (20130121110002), and NFFTBS (No. J1310024).
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These authors contributed equally to this work.