Li-ion battery studies on nickel oxide nanoparticles prepared by facile route calcination

Polyhedron 179 (2020) 114360

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Li-ion battery studies on nickel oxide nanoparticles prepared by facile route calcination Aliakbar Dehno Khalaji a,⇑, Marketa Jarosova b, Pavel Machek b, Kunfeng Chen c, Donfeng Xue c,⇑ a

Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran Institute of Physic of the Czech Academy of Sciences, v.v.i., Na Slovance 2, 182 21 Prague 8, Czech Republic c State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China b

a r t i c l e

i n f o

a b s t r a c t NiO nanoparticles (NiO-1 and NiO-2) were synthesized by the calcination of NiCl2
6H2O/benzoic acid and salicylic acid, respectively, with weight ratio 1:1 at temperature 600 °C. They were characterized by Fourier transform infrared (FT-IR), UV–Vis and photoluminecence spectroscopy, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Their electrochemical properties were evaluated using cyclic voltammetry, galvanostatic charge/discharge measurement and electrochemical impedance spectroscopy. The final products have good electrochemical reversibility and show large specific capacitance of about 479 mA h g1 and 388 mA h g1 after 50 cycles at 100 mA g1. The NiO nanoparticles electrodes exhibit also excellent rate capability. Nearly 37% and 40% specific capacity retention were observed after the current density had increased from 100 to 1000 mA g1. Ó 2020 Elsevier Ltd. All rights reserved.

Article history: Received 24 August 2019 Accepted 11 January 2020 Available online 13 January 2020 Keywords: NiO nanoparticles Calcination Cyclic voltammetry Galvanostatic charge/discharge Electrochemical

1. Introduction Nickel oxide is extremely attractive material for lithium ion battery anodes due to its high theoretical capacity of about 718 mA h g1, high chemical and thermal stability, low cost, and environmentally friendly character [1–15]. It is also used for adsorption of organic dyes [16–19]. NiO particles with various structures such as nanopowders, microspheres, nanosheets, nanoflakes, microtubes and etc have been developed to achieve high reversible capacity, enhanced cycling performance and good rate capability [1–19]. The NiO nanostructures can be prepared by various techniques such as microwave route, spray pyrolysis, sol-gel technique, heat treatment, calcination hydrothermal method and etc [1–19]. There are several reports focused on the Li-ion battery performance of different NiO based nanostructures [1–19] with a specific capacitance 250–950 mA h g1. For example, Vijayakumar et al., reported maximum specific capacitance (401 mA h g1) of NiO nanoflakes fabricate by microwave route at a current density of 0.5 mAcm1 [8]. Ultrathin NiO nanosheets prepared by Zhu et al., exhibited a high reversible Li storage capacity of 715.2 mA h g1 at 200 mA g1 current density in 130 cycles [4]. ⇑ Corresponding authors. E-mail (D. Xue).

addresses:

[email protected]

(A.D.

https://doi.org/10.1016/j.poly.2020.114360 0277-5387/Ó 2020 Elsevier Ltd. All rights reserved.

Khalaji),

[email protected]

NiO microtubes obtained by calcination of Ni(DMG)2 showed maximum specific capacitance of about 640 mAh g1 after 200 cycles at 1 A g1 [5]. Sun et al., synthesized NiO nanospheres by ultrasonic method that exhibited high specific capacitance of 260 F g1 at 1 A g1 current density [7]. An et al., reported the synthesis of NiO nanowires by hydrothermal method with a maximum specific capacitance of 1349 mAhg1 at a current density of 5 A g1 [13]. Flowerlike NiO fabricated by Fan et al., [11] displayed good electrochemical reversibility and superior capacitance performance with large capacitance (619 F g1). In this paper, we report synthesis of NiO (NiO-1 and NiO-2) nanoparticles (Scheme 1) prepared by facile route calcination of new nickel precursors and characterized by FT-IR, UV–Vis, PL, XRD, SEM and TEM. The electrochemical performance of NiO electrodes that can serve as Li-ion battery anodes is also reported and discussed. 2. Experimental 2.1. Synthesis of NiO nanoparticles The nickel oxide nanoparticles (NiO-1 and NiO-2) were synthesized by solid-state thermal decomposition of a mixture of NiCl2
6H2O/salicylic acid or benzoic acid with weight ratio 1:1 at 600 °C. Typically, 1 g of NiCl2
6H2O was at first dissolved in 5 mL

2

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Scheme 1.

of distilled water. Then 1 g of benzoic acid (NiO-1) or salicylic acid (NiO-2) was added to the solution under vigorous stirring and stirred for about 0.5 h. The mixture was transferred into a crucible and maintained at 100 °C for 3 h to dry it completely. The dry matter was ground for 5 min and then annealed at 600 °C in air atmosphere for 3 h. The black products of NiO-1 and NiO-2 were several times rinsed with deionized water and ethanol and filtered off. Finally, they were dried overnight at 65 °C in oven.

3. Results and discussion 3.1. FT-IR spectra There is the characteristic band related to the stretching vibration of Ni-O band that appears at 439 cm1 and 436 cm1 in the FTIR spectra of NiO-1 and NiO-2, respectively (Fig. s1a,b). The broad bands related to the stretching and bending vibrations of H


OAH are also observed around 3415 and 1610 cm1 in FT-IR spectra. These results are in agreement with publications [8,20–25].

2.2. Material characterization Fourier transform infrared (FT-IR) spectra were recorded as a KBr disk on a FT-IR Perkin–Elmer spectrophotometer. The UV–Vis absorption spectra were measured on a Jasco UV–Vis spectrophotometer. PL spectra were recorded on Photoluminescence spectrometer Perkin Elmer LS-5. The XRD patterns were measured using Empyrean powder diffractometer of PANalytical in BraggBrentano configuration equipped with a flat sample holder and PIXCel3D detector (Cu Kɑ radiation, k = 1.5418 Å) in order to determine the phases presented in the compounds. Scanning electron microscopy (SEM) images were obtained from Hitachi S-4800 microscope. The TEM images of nanoparticles were recorded on transmission electron microscope Philips CM120 with a LaB6 cathode operating at 120 kV and equipped with CCD camera Olympus Veleta.

3.2. UV–Vis spectroscopy The UV–Vis spectra of NiO-1 and NiO-2 in water solvent are presented in Fig. s2. Only a band at about 360 nm for NiO-1 and 351 nm for NiO-2 is observed that confirms the preparation of NiO nanoparticles [21,22,26–28].

2.3. Electrode preparation The active NiO materials were mixed with carbon black and PVDF at a mass ratio of 70:15:15 to form slurry with NMP as solvent. The slurry was then spread onto Cu foil by doctor-blade, and dried at 80 °C for 12 h. The disc with diameter 1.53 cm was cut from dried Cu foil, and compressed under the pressure of 10 MPa to form a working electrode. The loading of active materials on Cu foil was about 1 mg cm2.

2.4. Electrochemical test method Lithium metal was used as the counter and reference electrode. The electrodes were assembled into a coin cell (CR2032) in an Arfilled glovebox using Celgard 2400 as separator and 1 M LiPF6 in ethylene carbonate/dimethyl carbonate/diethyl carbonate (EC/ DMC/DEC, 1:1:1 vol%) as electrolyte. A galvanostatic cycling test of these assembled half-cells was conducted on a LAND CT2001A system in the voltage range of 0.01–3.0 V (vs. Li+/Li) at different current densities. Cyclic voltammogram (CV) was conducted on CHI 660E equipment at the scan rate of 0.1 mV/s with the voltage window of 0.01–3.0 V (vs. Li+/Li).

Fig. 1. Room temperature photoluminescence spectra of a) NiO-1 and b) NiO-2.

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3.3. Photoluminescence spectroscopy Fig. 1 shows the room temperature photoluminescence (PL) emission spectra of NiO-1 and NiO-2. A strong emission peak located at 323 nm for NiO-1 and at 326 nm for NiO-2 corresponding to 3.65 eV is observed [29,30] and attributed to the recombination between electrons in conductive band (CB) and holes in valence band (VB). In addition, the resulting emission spectrum of NiO-1 shows a shoulder emission peak at 347 nm, while NiO-2 shows a strong emission peak at 345 nm. Finally, there are three weak emission peaks at about 380, 407 and 431 nm observed in both spectra. They relate to the defectsrelated deep level emission [30]. Finally, a broad and weak peak between 630 and 650 nm is observed that is attributed to native defects [31]. 3.4. XRD patterns The purity of the resulting NiO products was verified by X-ray diffraction (XRD). Recorded patterns of NiO-1 and NiO-2 samples are shown on Fig. 2a and 4b, respectively. Clear and sharp peaks at 2h  37.26° (1 1 1), 43.30° (2 0 0), 62.88° (2 2 0), 75.41° (3 1 1), 79.39° (2 2 2), 95.04° (0 0 4), 106.96° (3 1 3) and 111.08° (2 0 4) indicate that the NiO-1 and NiO-2 products correspond to cubic NiO (JCPDS file no. 01-078-0429) [16]. The structures of NiO-1 and NiO-2 were confirmed by Rietveld fit in crystallographic refinement program Jana2006 [32]. The average crystallite size of NiO-1 and NiO-2 were determined in the same program using fundamental parameter approach [33], which removes the instrumental part of the diffraction pattern by means of known geometry of the difractometer. For both

Fig. 3. SEM images of a) NiO-1 and b) NiO-2 nanoparticles.

samples we obtained almost the same crystallite sizes, 60.0 nm for NiO-1 and 61.8 nm for NiO-2 3.5. SEM and TEM images The morphology of NiO-1 and NiO-2 nanoparticles was characterized by SEM and TEM. Figs. 3 and 4 show the SEM and TEM images of NiO-1 and NiO-2 samples prepared at 600 °C. These images reveal nanoparticles structure of the products with crystallite sizes ranging from tens to hundred nm, which is in conformity with the calculation of average crystallite sizes from XRD patterns. On the contrary, the images indicate that the average size of the NiO-2 particles is smaller than the size of NiO-1. 3.6. Electrochemical properties Following electrochemical reaction can occur when the NiO is used as material for Li-ion battery anode: þ

NiO þ 2Li þ 2e Ni þ Li2 O

Fig. 2. XRD pattern of a) NiO-1 and b) NiO-2 nanoparticles.

ð1Þ

NiO is conversion-type anode materials. As shown in Fig. 5a and d, the reduction peak around 0.3 V in the first cycle can be associated with reduction of Ni2+ ? Ni and formation of Li2O and solid electrolyte interface (SEI) [34,35]. The oxidation peaks around ~2.2 V can be attributed to the oxidation of Ni and decomposition of the SEI. In the following cycles, the redox peaks are well over-

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Fig. 4. TEM images of NiO-1 (a,b) and NiO-2 (c,d) nanoparticles at two different scales.

lapped representing that NiO anode has well cycling performance. Fig. 5b and 5e show the charge-discharge curves at a current density of 100 mA g1. NiO-1 sample shows 1st discharge capacity of 1394 mA h g1 and charge capacity of 643 mA h g1. The irreversible capacity loss is caused by SEI formation and electrolyte decomposition. The discharge plateau is shifted up to ~1.4 V during the 2nd and 3rd cycles, and the charge plateau shifts are very slight. These results are consistent with the CV measurements. NiO-2 sample shows 1st discharge capacity of 1101 mA h g1 and charge capacity of 520 mA h g1 (Fig. 5e). The change of CV and charge–discharge curves of NiO-2 sample is the same as that of NiO-1 sample. The discharge capacity of NiO-1 is larger than that of NiO-2 sample. Electrochemical impendence spectrum is shown in Fig. 5c and f. The diameter of semi-circle in low frequency range is the charge transfer resistance [36]. NiO-1 sample shows higher charge transfer resistance (100 X) than that of NiO-2 sample (85 X). Cycle and rate performances are shown in Fig. 6. After 50 charge-discharge cycles, NiO-1 electrode displays better cycle performance than that of NiO-2 electrode. At current density of 0.1 A g1, NiO-1 and NiO-2 electrodes exhibit capacities of 538 and 484 mA h g1, respectively. At current density of 1 A g1, they exhibit capacities of 190 and 189 mA h g1, respectively. Therefore, the NiO-1 and NiO-2 electrodes show nearly 35% and 40% capacity

retention when the current density increases from 100 to 1000 mA g1 (Fig. 6b). 4. Conclusions In summary, battery anodes based on NiO nanoparticles shows better electrochemical performance than Li-ion batteries. The 1st discharge capacity for NiO-1 sample was found at 1394 mA h g1 and charge capacity at 643 mA h g1, which is approaching the theoretical capacity of NiO. Also, NiO sample shows decent cycle stability with specific capacities of about 479 at 100 mA g1 after 50 charge-discharge cycles. Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments Financial support from the Golestan University and the National Natural Science Foundation of China (grant nos. 21521092), CASVPST Silk Road Science Found 2018 (GJHZ1854) is acknowledged.

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Fig. 5. Electrochemical Li-ion battery anode performance of NiO-1 (a-c) and NiO-2 (d-f) samples. CV curves at a scan rate of 0.1 mV s1 (a and d), charge-discharge curves at a current density of 100 mA g1 (b and e), and Nyquist plots (c and f).

Fig. 6. Electrochemical Li-ion battery anode performance of NiO-1 and NiO-2 samples. (a) Cycle performance at a current density of 100 mA g1, (b) rate performance of NiO1 and NiO-2 electrode materials at different current densities.

XRD and TEM analysis were supported by the project 18-10504S of the Czech Science Foundation using instruments of the ASTRA lab established within the Operation program Prague Competitiveness e project CZ.2.16/3.1.00/2451.

Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.poly.2020.114360.

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