Electrochimica Acta 54 (2009) 6161–6165

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Preparation and electrochemical performance of micro-nanostructured nickel
Xiaoyan Han, Feng Zhang, Jiangfeng Xiang, Caixian Chang, Jutang Sun ∗
Department of Chemistry, Wuhan University, Wuhan 430072, PR China

a r t i c l e

i n f o

a b s t r a c t
Micro-nanostructured nickel has been prepared as anode materials for Li ion batteries, via a rheological phase reaction method. Ni2 C2 O4 ·xH2 O (x = 2 or 2.5) as precursors are obtained from the solid–liquid rheological mixture of (NH4)2 C2 O4 ·H2 O and Ni(NO3 )2 . The nickel powders are prepared by thermal decomposition of the precursors. The structural, morphological and electrochemical performance are investigated by means of thermogravimetry (TG), differential scanning calorimetry (DSC), powder Xray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and typical electrochemical tests. The micro-nanostructured nickel displays an initial discharge capacity of 457 mAh g−1 . It also has a remarkable cycling stability with an average capacity fade of 0.17% per cycle from 13th to 50th cycle in 0.01–3.00 V versus Li at a constant current density of 100 mA g−1 . © 2009 Elsevier Ltd. All rights reserved.

Article history: Received 24 March 2009 Received in revised form 11 May 2009 Accepted 16 May 2009 Available online 27 May 2009 Keywords: Rheological phase reaction method Micro-nanostructured nickel Anode Li ion batteries

1. Introduction Nanosized materials with novel properties present a wide potential application in many fields [1–6]. Constructions of wellordered and realizations of their potential applications have resulted in intensive research for the past few years. The demands of superfine metal powders have increased dramatically in the electronics, biotechnology, powder metallurgy and energy sources fields. Micro-nanostructured nickel with unique morphology, size and structure may exhibit superior functionality or provide new possibilities due to the composite structure, porosity, stability and the inherent properties of nanosized materials. So far as we know, there are many researches on nickel including alloy used as anode materials [7–12]. However, a well-known fact is that the pulverization, which brings the fast capacity fade during cycling, is the key issue to restrict metal or alloy being widely used as the anode materials for Li ion batteries. There have been many attempts to resolve the cracking and crumbling problems of metal or alloy materials for Li ion batteries. Nanosized particles or composite materials have been considered. Nevertheless, just reducing the particle size or synthesizing simple composite materials cannot effectively improve the cycleability or capacity of the anode materials [10]. Various methods have been used to prepare superfine nickel powders such as mechanical milling, chemical reduction, evaporation, polyol process, spattering and atomize method [13–18].

However, some of the above-mentioned methods need rigorous reaction conditions such as high temperature or high pressure, some need organic solvent, and some need the addition of extra precipitator to the reaction system, which cause the safety problem, complicated manufacture equipment, high production cost, poor quality, low production efficiency and so on. As a result, the design and synthesis of nanosized materials is the current subject of intense research. In this study, micro-nanostructured nickel was prepared via a rheological phase reaction method. Rheological phase reaction is a simple, economical and effective route to prepare functional materials [19–25], which does not need complicated processes. The thermal decomposition of the precursors carried out at 300–400 ◦ C in a self-assembly device without protective gas. 2. Experimental 2.1. Material preparation (NH4 )2 C2 O4 ·H2 O, Ni(NO3 )2 ·6H2 O and anhydrous ethanol were all analytical-grade reagents. Solutions were prepared by use of deionized water. (NH4 )2 C2 O4 ·H2 O (48.87 g) was added in 5.0 M nickel nitrate solution [Ni(NO3 )2 ·6H2 O (100 g), H2 O (20 mL)] at 70–90 ◦ C to form a rheological body with viscoelasticity. The ropy rheological body was fully dispersed with an appropriate amount of deionized water added, then filtered, washed, dehydrated with anhydrous ethanol and dried at 80–90 ◦ C to yield NiC2 O4 ·2H2 O (Precursor A), the overall yield was 99.76%. The nickel nitrate was added in supersaturated ammonium oxalate solution to give NiC2 O4 ·2.5H2 O (Precursor B), the overall yield was 97.98%.

∗ Corresponding author. Tel.: +86 27 87218494; fax: +86 27 68754067. E-mail address: jtsun@whu.edu.cn (J. Sun). 0013-4686/$ – see front matter © 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2009.05.069

EXE procedure (Rietveld analysis of the powder XRD patterns using on a step-scan mode with a step of 2◦ in the 2 range of 20–130◦ ). Chemical analysis was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES. The refined crystal lattice parameters were calculated by the JADE5. Hitachi 400) and transmission electron microscope (TEM.54056 Å) in the range of 10–60◦ (2 ) and 10–120◦ (2 ) with a scanning rate of 4◦ min−1 . A 1 M LiPF6 EC/DMC (1:1.01 and 3.1. 1 presents the TG–DTG–DSC curves of Precursor A (6.2. 3. acetylene black and polytetrafluoroethylene (PTFE) binder. which ensured the precursor was saturated with self-atmosphere. volume ratio) was used as the electrolyte. 2. TG–DTG–DSC curves of Precursor A (a) and B (b) in covered Al crucible. The working electrode was prepared by mixing the nickel powders. The DSC peaks closely correspond to the weight changes observed on the TG curves. model IRIS. The thermal analysis experiments were carried out in covered Al crucible with a Netzsch STA 449C thermal analyzer from 50 to 600 ◦ C at a heating rate of 5 ◦ C min−1 . Analysis shows that the molar compositions of Precursor A and B are NiC2 O4 ·2H2 O and NiC2 O4 ·2. The sample mass was kept about 6. Electrochemical measurements The electrochemical experiments were examined on a Neware cell test system at room temperature.6162 X.0 V versus Li at a constant current density of 100 mA g−1 . respectively. TJA). JEM-2010 FEF). The cells were discharged and charged between 0. respectively. respectively. The nickel obtained from the Precursor A and B was marked as NiA and NiB . The specific temperature and mass losses are labeled on DSC–TG curves. The particle size and morphology were observed using scanning electron microscope (SEM. 1. which consisted of a working electrode and a lithium foil counter electrode separated by a Celgard-2300 microporous membrane. The charge–discharge tests were carried out with the coin-type cell (size: 2016). in a weight ratio of 80:15:5.5H2 O. Material characterization The powder X-ray diffraction (XRD) patterns of the precursors and the products were collected by a Shimadzu model XRD-6000 diffractometer with a Ni filter and Cu-K␣1 radiation ( = 1. compressing the mixture onto a stainless steel current collector. Results and discussion 3.3.0 mg. Han et al. Thermal decomposition reaction Fig. The cells were assembled in an argon-filled glove box (Mikrouna.223 mg) and B (7. China). The air inside expanded and let out slowly when the thermal decomposition was carried out. / Electrochimica Acta 54 (2009) 6161–6165 Fig.620 mg).0–8. The vessel was heated up to 335 ◦ C in air furnace with a heating rate of 5 ◦ C min−1 . kept at 335 ◦ C for 6 h to give a black sample. Super 1220/750. An appropriate amount of nickel oxalate was cased in sealed vessel. The thermal . 2.

XRD patterns of oxalate nickel precursors (a) and nickel products (b). 25-0581). 2. The particles size and morphology of the Precursor A and B are obviously different from each other.5 ␮m keeps the quadrate morphology of the Precursor B and the single quadrate crystal still consists of many nanospheres with the average particle sizes about 20 nm (Fig. a (Å) b (Å) c (Å) V (Å3 ) Precursor A P2/m (No.9150 NiB 6163 ¯ m(225) Fm3 3. characterized by a small endothermic peak on DSC curves. The mass loss before 200 ◦ C. proving the sole existence of nickel particles.62–0. The partial refined crystal lattice parameters calculated by the JADE5. The results from SEM and TEM images agree well with the observations from the XRD and electrochemical measurements. XRD analysis confirms that the final products of thermal decomposition in Al crucible are nickel powders. 3b2 and Fig. Particle size and morphological characterization Particle sizes and morphology changes throughout the thermal decomposition are shown in Figs. Table S3 and Fig. Powder X-ray diffraction analysis Fig.2. 10) 7. 3a1 ). Parameter S. However.8167 (16) 2.13 Fig. Han et al. Parameter S. Precursor A changes into close-grained spherical heteromorphy with the average particle sizes about 0.5): NiC2 O4 ·xH2 O → NiC2 O4 + xH2 O NiC2 O4 → Ni + 2CO2 (1) (2) But thermal decomposition behaviors of the two precursors are different: the decomposition rate of Precursor B is twice than that of Precursor A (shown in DTG curves).4. 2b. Diffraction relative intensity and peak position of two XRD patterns are different from those reported in the literature (JCPDS File Card No. The reaction mechanism of intercalation of Li ions can be expressed as follows: 1. All characteristic diffraction peaks of two precursors are well indexed to the monoclinic phase of nickel oxalate.73 4 8.1 ␮m (Fig. The Precursor A consists of many irregular block crystals with the particle sizes of 0. 3b1 ).6–1. G.1–0. 3. which is different from the common reports on thermal decomposition of nickel oxalate in air [26. / Electrochimica Acta 54 (2009) 6161–6165 Table 2 Lattice parameters of NiA and NiB . 3. which indicates that the high crystallinities of the products.84 V 0. In order to get an accurate lattice parameters silicon element (internal standard) is added to compensate for sample displacement error (Fig.EXE procedure are presented in Table 1. with the space group P2/m (No.9066 (11) 122. S2. 3 and 4 by SEM and TEM observations. After thermal decomposition.01 V The initial discharge capacity of NiA electrode is 376 mAh g−1 and the coulombic efficiency is 55. Supplementary Information). Results show that lattice parameters and the position of main peaks of face centered cubic nickel are well consistent with the standard file (JCPDS File Card No. No sign of the formation of oxides species could be observed in Fig.9058 indicates that the two precursors are different from each other.78 4 8.5245 (1) 43.27]. the initial discharge capacity of NiB electrode is 457 mAh g−1 and the coulombic efficiency is 62.6607 (6) 5. 3.5671 (47) 266. Supplementary Information. 2b and Table 2.0 V. 04-0850).X. Electrochemical characterization Fig. 10). The Precursor B consists of monodispersed quadrate crystals with the particle sizes of 0. decomposition generally proceeds in two steps: dehydration and decomposition of the anhydrous oxalate. 10) 9.2409 (19) 6. is ascribed to the dehydration of adsorptive water. 3a2 and Fig. S4 and Fig. 5 shows the typical discharge and charge curves of NiA and NiB electrode at a constant current density of 100 mA g−1 between 0. G. 2a 1/3Li + Ni → Li1/3 Ni 1/3Li + Li1/3 Ni → Li2/3 Ni 1/3Li + Li2/3 Ni → LiNi (3) (4) (5) 0.2 ␮m (Fig. All diffraction peaks are very sharp. S5.62 V Table 1 Lattice parameters of Precursor A and B. 4a3 ). the first discharge curve is . More detailed results of the formation and composition of the LiNi alloy are given in Table S1. a (Å) V (Å3 ) Z Dcalc (g cm−3 ) NiA ¯ m(225) Fm3 3. 5.3.4%. XRD patterns and lattice parameters of the products are given in Fig. The thermal decomposition reaction formula of the precursors can be expressed as follows (x = 2 or 2.8874 (40) 4. 4b3 ).60–0. As shown in Fig. The three obvious plateaus in the first discharge curve suggest that there are three Ni atoms and three Li atoms in a unit cell.5232 (1) 43.0 ␮m (Fig. The broken line in Fig. 2a shows the XRD patterns of Precursor A and B prepared via rheological phase reaction method.01 and 3.84 Precursor B P2/m (No.3%. The low initial coulombic efficiency is attributed to the formation of the alloy framework and the solid electrolyte interface (SEI) film.84–0. The product NiB with the average particle sizes about 0.

Therefore.6164 X.5 V corresponded to the irreversible capacity loss. In comparison. / Electrochimica Acta 54 (2009) 6161–6165 Fig. which is much better than NiA electrode. The deintercalation process of Li ions between the layers of the anode is a diffusion process [25]. SEM images of Precursor A (a1 ) and NiA (a2 ). The reason for the higher initial capacity of NiB electrode may be attributed to the particle size and the microstructure. which would lead to a long path for Li ions. After Fig. which disappears in the following cycles. Fig. respectively. . The NiA electrode delivers an initial reversible capacity of 208 mAh g−1 and maintains 87 mAh g−1 in the 50th cycle. 4. TEM images of NiA (a3 ) and NiB (b3 ). the charge capacity still retains 143 mAh g−1 . 6 shows the cycling performances of NiA and NiB electrode. Precursor B (b1 ) and NiB (b2 ). 3. The small plateau at about 1. the NiB electrode delivers an initial reversible capacity of 285 mAh g−1 . the larger or close-grained particles. characterized by four plateaus. In the 50th cycle. Han et al. The NiB electrode delivers higher initial discharge and charge capacity of 457 and 285 mAh g−1 . are not advantageous to deintercalation.

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