Ca2Ni5 nanocomposite: A novel form as anode material in lithium-ion battery

Accepted Manuscript Hollow Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite: A novel form as anode material in lithium-ion battery Manab Kundu, Gopalu Karunakaran, Nguyen Van Minh, Evgeny Kolesnikov, Mikhail V. Gorshenkov, Denis Kuznetsov PII:

S0925-8388(17)31104-0

DOI:

10.1016/j.jallcom.2017.03.302

Reference:

JALCOM 41340

To appear in:

Journal of Alloys and Compounds

Received Date: 16 January 2017 Revised Date:

8 March 2017

Accepted Date: 26 March 2017

Please cite this article as: M. Kundu, G. Karunakaran, N.V. Minh, E. Kolesnikov, M.V. Gorshenkov, D. Kuznetsov, Hollow Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite: A novel form as anode material in lithium-ion battery, Journal of Alloys and Compounds (2017), doi: 10.1016/ j.jallcom.2017.03.302. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Graphical Abstract

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Hollow Cu0.10Mg0.40Zn0.50Fe2O4/ Ca2Ni5 nanocomposite: a novel form as anode material in lithium-ion battery

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Manab Kundu 1,*,#, Gopalu Karunakaran 2, 3,*,#, Nguyen Van Minh2 , Evgeny Kolesnikov2, Mikhail V. Gorshenkov4, and Denis Kuznetsov2

Department of Material Science and Engineering, Norwegian University of Science and

Technology (NTNU), NO-7491 Trondheim, Norway 2

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1

Department of Functional Nanosystems and High-Temperature Materials, National University

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of Science and Technology “MISiS,” Leninskiy Pr. 4, Moscow, 119049, Russia Department of Biotechnology, K. S. Rangasamy College of Arts and Science (Autonomous),

Tiruchengode-637215, Tamil Nadu, India

4Department of Physical Materials Science, National University of Science and Technology “MISiS,” Leninskiy Pr. 4, Moscow, 119049, Russia Corresponding Author’s

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*

E-mail: [email protected] TEL: +47 735 51218

E-mail: [email protected]

Both the author’s contributed equally to this work

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#

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TEL: +7-985-663-75-69

Abstract

In the relentless pursuit of finding new electrode materials for lithium ion batteries

(LIBs), mixed metal oxides (MMOs, containing different metal cations), have confirmed improved electrochemical activities in comparison with simple metal oxides (SMOs, containing single metal cations). On the other hand, electrodes with nano-dimension and hollow microstructure have been confirmed as advantageous candidate in LIBs. The integration of the 1

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two features into one structure can provide another chance to improve the lithium storage capabilities. In this work, for the first time we report the lithium storage property of porous Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite as LIB anode. The nanocomposites anode

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delivers approximately 350 mAh g-1 after 500 cycles at 300 mA g-1. Even at a high rate of 1000 mA g-1, it also showed an excellent performance up to 1000 cycles and 90% Coulombic efficiency with no sign of capacity fading. This outstanding Li storage performance makes

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Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites a promising candidate as LIB anode.

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KEYWORDS: Spray pyrolysis; Nano-composites; Mixed metal oxides; Energy storage and

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conversion; Lithium-ion batteries; Electrochemical performance.

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1. Introduction

The unique advantages such as large energy density, long cycle life, low self-discharge characteristic and absence of memory effect, positioned lithium-ion batteries (LIBs) as most

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important energy storage systems [1]. To satisfy the increasing demand of LIBs in automobile application, developing advanced electrode materials with high energy densities and power densities has attracted great attention. In the relentless pursuit of finding new electrode materials

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for LIBs, a large variety of materials including transition/non-transition metal oxides and sulfides are investigated [2-8]. In recent years, the research focus in the search for a new anode material

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is gradually shifting from the simple metal oxides (SMOs, metal oxides composed of one kind of metal cation) to mixed metal oxides (MMOs, metal oxides composed of different metal cations, stoichiometric or non-stoichiometric) [9]. In last few years, many MMOs such as ZnCo2O4, NiFe2O4, FeCo2O4, Co2Mo3O8, have been explored extensively [10-13]. The improved

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electrochemical performance of MMOs than SMOs, related with the synergic effects of multiple metal species and much better electrical conductivity, made these anodes more attentiongrabbing. For example, spinal NiCo2O4 (in which one Co atom is replaced by Ni), possesses

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much better electrical conductivity and higher electrochemical activity than NiO or Co3O4. [14] As a result, NiCo2O4 exhibits exceptionally high specific capacity than that of corresponding

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single-metal oxides [15]. However, even in case of MMOs, stubborn issue like large volume deformation during repeated charge–discharge cycles, still persist which leads inevitable capacity fading and thus, an undesired cycling stability [16]. In order to optimizing electrode structures to withstand a large volume expansion, it is realized that the hollow nano-sphere can provide enough spaces to adapt the unbearable bulk changes. In addition to this, hollow structured greatly shorten the transport path lengths of lithium ions and electrons during the

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delithiation/lithiation processes, thus resulting in a significant improvement of the electrochemical performance such as high specific capacities, fast rate performances, and long cycle lives [17]. For instance, Cho et al. reported the synthesis of hollow-structured NiO by one-

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pot spray pyrolysis method, showing superior reversible capacity and excellent rate performance over solid NiO [18]. In another report, Wang et al. demonstrated the promising electrochemical performance of CoxFe3-xO4 hollow spheres supported by carbon nanotubes via an impregnation-

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reduction-oxidation process [19]. In recent years, various methods have been successfully applied to prepare hollow nanopowders including template assisted synthesis, liquid-phase

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deposition, hydrothermal and chemical precipitation method [20-23]. In spite of the improvement accomplished till date, the up-to-date methods are usually time-consuming and quite tedious because of the need of template synthesis and the multistep process. Recently, spray pyrolysis process has been successfully applied in the preparation of various electrode

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materials with impressing electrochemical performance. The benefit of this synthesis process is its short production period and easy to obtain large-scale products [24]. The resultant products are fine spherical particles with a uniform chemical composition and a narrow particle size

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distribution and can be easily used for real time large-scale applications [25, 26].

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Based on the above consideration, in this work, hollow Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nano-composites are prepared by a spray pyrolysis route, and used as LIB anode material for the first time. The lithium storage properties have been discussed based on the cyclic voltammetry (CV), galvanostatic charge discharge, long term cycling and electrochemical impedance spectroscopy measurements. The results show that the nano-composites exhibit high specific capacity with good cycle stability, indicating potential anode candidates for lithium-ion batteries.

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2. Experimental 2.1 Materials Used and Production of Nanocomposites

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Copper nitrate Cu(NO3)2.6H2O, Zinc nitrate Zn(NO3)2.6H2O, Nickel nitrate Ni(NO3)2.6H2O, Calcium nitrate Ca(NO3)2·4H2O, Magnesium nitrate Mg(NO3)2.6H2O and Iron nitrate Fe(NO3)2.6H2O were taken to prepare precursor solutions using water as solvent, (Milli-Q Water, Millipore, Germany). The precursor solution after filtration with whatman filter three

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times, filled in the ultrasonic generator (DK, Mist Maker). Once the ultrasonic generator was

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turned on, it generates small aerosol droplets which are further allowed to travel inside silica reactor under flow rate of around 16 L/min which was maintained by using two flask pump (KNF Berger, D7911). The silicon reactor was maintained at 1200 oC temperature using tube furnace (Nabetherme 20/250/13). Aerosols generator was further allowed till the solution gets ends up. After the complete generation of aerosol, the ultrasonic generator and the furnace were

were

obtained

from

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allowed to cool to room temperature. After about 10 to 15 hours, the prepared nanocomposites the

chamber.

Finally,

the

formation

mechanism

of

the

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Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nano-composites is presented in Fig. 1.

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2.2. Characterization of Nanocomposties The collected powder was used for further characterization using different techniques. To

identify the crystalline phase of the nanocomposite, X-ray powder (XRD) diffraction analysis was performed (Difray, Russia). The chemical bonds and elements of nanocomposites were revealed by using Fourier transform (FTIR) infrared spectrophotometer (Nicolet, Thermo Scientific, USA). The presence of elements was confirmed by Energy dispersive spectrum (EDS) (EDX SSD X-MAX, JAPAN) and Inductively coupled plasma atomic emission spectroscopy 5

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ICP-AES iCAP 6300 Radial View company Thermo Fisher Scientific Inc., United States). To figure out the dimension and structure of the nanocomposites, scanning electron microscopy (JSM – 6610 LV, SEM-JEOL, Japan) and transmission electron microscopy (TEM, JEM-2010,

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JEOL, Japan) technique were used. In addition, High resolution Transmission electron microscopy (HRTEM) was carried out using JEOL JEM-2100 operated at 200 kV equipped with an energy-dispersive X-ray spectroscopy (EDS). The elemental mapping was performed using

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scanning transmission electron microscopy mode using the same microscope. For the elemental mapping Kα characteristic X-ray lines of the corresponding elements were used. Nitrogen

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adsorption isotherms of the synthesized nanoparticles were analyzed by using Nova 1200e analyzer (Quantachrome Instruments, USA). The surface area of the powder was calculated using Brunauere-Emmette-Teller (BET) method. The pore size and pore volume was calculated using Barrett-Joyner-Halenda (BJH) method. Finally, in order to check the morphological change

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after 1000 cycles at 1000 mA g-1, field-emission transmission electron microscopy (FE-SEM, Zeiss Ultra) technique was used.

typical

electrode

was

prepared

from

a

slurry

of

the

synthesized

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2.3. Electrochemical Characterizations of Nanocomposties

Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites (70 wt%), acetylene black (20 wt%) and polyvinylidene fluoride (PVDF binder) (10 wt%) in n-methyl pyrrolidinone (NMP) solvent. The slurry was coated on to a copper foil current collector and dried at 110 °C in a vacuum oven for overnight. After pressing at 3 tons, circular disks of 16.3 mm in diameter were cut and used as electrode. 2016 type coin cells were assembled with these electrodes using Li metal as counter as well as reference electrode and LiPF6 in EC: DEC (1:1 vol%) as electrolyte and Celgard 2300 as 6

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separator within an argon filled glove box (M’BRAUN, Germany) where the moisture and oxygen levels were kept below 1.0 ppm. Cyclic voltammetry (CV), Electrochemical Impedance

window of 0.0–3.0 V using a Biologic VMP3 battery tester.

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3. Results and Discussion

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Spectroscopy (EIS) and Galvanostatic charge–discharge cycles were carried out in the voltage

XRD pattern depicted in Fig. 2a shows the crystalline phase of the synthesized

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nanocomposite. The major peaks at ~48 º, ~54 º, ~65 º, ~73 º, ~90 º and ~100 º which are in close agreement with Cu0.10Mg0.40Zn0.50Fe2O4 phase (JCPDS file no. 00-051-0385) reveals the cubic phase. In addition, major peaks at ~38 º, ~48 º, ~52 º, ~65 º, ~73 º, ~90 º and ~93 º are best matched with Ca2Ni5 phase (JCPDS file no. 00-019-0243) which confirms the hexagonal face of the

obtained

nanocomposite.

Thus,

the

obtained

nanocomposite

possesses

major

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Cu0.10Mg0.40Zn0.50Fe2O4 and minor Ca2Ni5 phase. The Fig. 2b represents the FTIR spectrum explains about the occurrence of various

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elemental functional groups. Nanocomposites absorption bands mainly occurred at wave numbers such as 742, 813, 1045, 1334, 1635, 1789, and 3517 cm-1 which are assigned for

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bending vibration, absorption bands and stretching vibration due to the metal oxide presence in nanocomposites. The observed peaks at 742 and 813 cm-1 are due to the presence of Zn-O and Ca-O, respectively [27, 28]. Whereas, the bands obtained at 1045, 1334, 1635 and 1789 cm-1 are due to the presence of Ni-O[29], Mg-O [30], Cu-O [31] and Fe-O [32, 33], respectively. However, major band observed at 3517 cm-1 represents O-H vibration which may be of water presence.

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Elemental analysis by the EDX experiment confirms that the produced nanocomposites have all the six metals which are used for the synthesis of nanocomposites (Fig. 2c). In addition, the mass percentage in the elemental composition present of the nanocomposites was further

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analyzed by ICP-AES, the obtained results are depicted in the Table 1. It also confirms the six metals elemental compositions of the nanocomposites and which is also well correlates with the EDX results. The morphology and microstructural features of the as-prepared composites were

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investigated by SEM and TEM. Figs. 2d, 2e, and 2f shows SEM images which represent the spherical and hollow morphology of the nanocomposite with diameter between 420-721 nm. The

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lower and medium magnification SEM image (Figs. 2d and 2e) clearly indicates the uniformity of nanospheres. The higher magnification SEM image (Fig. 2f) clearly reveals the hollow interior with broken hollow spheres.

The hollow interior and geometrical structure of the nanocomposites are further

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elucidated by the following TEM observation. As shown in Figs. 3a, 3b and 3c, the hollow structure is obviously revealed by the sharp contrast between the shell and hollow interior with an average diameter of 420-721 nm. When focusing on the surface of the nanospheres, the

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observed contrast indicates the presence of numerous pores on the shell of the nanospheres. The

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presence of these pores would benefit the improvement of the electrochemical performance as they offer a remarkably increased electrode/electrolyte contact area and facilitate mass transport of the electrolyte within the electrode. Furthermore, close observation for a single nanosphere found that the shell actually is composed of interconnected NPs of 11 nm. The shell is relatively uniform and its thickness is around 36 to 56 nm. Fig. 3d displays the HRTEM images of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 composites. The lattice fringe spacing’s of 0.253 and 0.216 nm can be ascribed to the (311) plane of Cu0.10Mg0.40Zn0.50Fe2O4 and the (200) plane of Ca2Ni5, 8

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respectively. The HRTEM observation result is in agreement with that of the XRD analysis. The elemental mapping of an individual hollow sphere of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 composites performed using energy dispersive X-ray spectroscopy (EDS) in scanning TEM mode and the

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observed results are shown in Fig. 4. The observed results clearly confirms the uniform distribution of Zn, Fe, Cu, Ca, Ni, Mg and O elements in Cu0.10Mg0.40Zn0.50Fe2O4/ Ca2Ni5 composites.

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The specific surface area and porosity of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites was measured by the nitrogen (N2) absorption–desorption isotherm and presented in Figs. 5 a

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and b. The obtained result reveals that the nanocomposite exhibits the surface area of 6.8 m2 g−1. The observed surface area results are similar to the available literature in which the nanocomposites where obtained by spray pyrolysis [34, 35]. Fig. 5b and its inset figure shows the corresponding pore size distribution calculated by Barrett-Joyner-Halenda (BJH) method,

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indicating the narrow pore size distribution centered at around 4 nm. The calculated pore volume is found to be 0.009 cm3 g-1. Such a porous nature could facilitate the diffusion of Li+ and electrolyte into the active materials and supply void space to accommodate the large volume

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variation during the charge–discharge process, thus boosting the lithium storage performance of composite electrode materials.

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Fig. 6a shows the 1st, 2nd, 3rd and 4th cyclic voltammograms (CVs) of the electrode with a

potential range of 0.00–3.0 V vs. Li/Li+ at a sweep rate of 0.1 mV s-1. A well-defined peak at 0.3 V that only appeared in the first cycle should be assigned to the reaction between Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites and lithium ions, in which metallic Cu, Zn and Fe particles were formed and the formation of the solid electrolyte inter-phase (SEI) film. Two broad peaks located at 1.26 and 1.7 V in the anodic scan should be attributed to the re-oxidation

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of metal particles to metal oxides as well as decomposition of SEI film. Note that the cathodic peak shifts positively to 0.60 V in the following cycles. This peak-shift could be attributed to the irreversible lithiation in the first cycle, which is associated with an irreversible structural or

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textural change in the electrode materials due to the formation of Li2O and metallic Cu, Zn and Fe particles. This behavior is well consistent with the previous literature with other anode materials [2]. Second cycle onwards, no such peak shifting is observed, which manifests that the

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lithiation and de-lithiation processes are highly reversible from the second cycle onwards.

The Li-storage properties of the Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites as anode

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materials are further evaluated by galvanostatic charge-discharge. Fig. 6b shows the chargedischarge profiles for selected cycles recorded at a current density of 300 mA g-1 in the potential range of 0.0-3.0 V. The initial discharge and charge specific capacities are 777.58 and 451.62 mAh g-1, respectively, which offer an initial Coulombic efficiency of 58.08 %. The irreversible

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capacity loss of the first cycle can be attributed to the inevitable decomposition of the electrolyte and the formation of solid electrolyte interface (SEI) on the surface of the electrode, which is common in transition-metal oxide anode materials [19]. After first cycle onwards, no obvious

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change can be found for the shape of charge-discharge curves, indicating that the host structure for lithium storage can be firmly maintained during long term cycling. The stable lithiation-

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delithiation behaviors are very much consistent with the variation of peak current in CV curves as shown in Fig. 6a. All these evidences confirm that Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites can be used as reliable lithium storage material. As the cycling stability especially at high rate, is very important aspects for real

application, long-life property of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite scrutinized at 300 and 1000 mA g-1 (Fig. 6c). It is observed that a rapid decay tendency in capacities from 452

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and 362 mAh g-1 of the initial cycle to around 270 and 136 mAh g-1 and then the capacities increase continuously to 350 (after 500 cycles) and 252 (after 1000 cycles) mAh g-1 at the current densities of 300 and 1000 mA g-1 respectively. The phenomenon of increasing trend in capacity

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value after the initial decay, can be attributed to the formation or conditioning of the electrode [36]. The similar phenomenon has been reported in other SMOs and MMOs like CoO-Li2O thinfilm composite [37], nano-flake Fe2O3 [38], and ZnFe2O4 [39]. The average columbic efficiency

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in both cases is approximately 99.7%, demonstrating a stable host structure of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite. Moreover, it is worth to mention that, the

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electrochemical lithium-ion insertion/extraction process is almost reversible at high rate, shows the good lithium storage performance of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites. The galvanostatic discharge-charge rate performance of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites hollow spheres were measured at the different current densities of 50 mA g-1,

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100 mA g-1, 200 mA g-1, 300 mA g-1, 500 mA g-1 and 1000 mA g-1, finally back to 100 mA g-1 as shown in Fig. 7a. Interestingly, even at the high current densities of 500 mA g-1 and 1000 mA g1

, the nanocomposite still provide higher specific capacities of 391 mAh g-1 and 326 mAh g-1,

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indicating that the hollow morphology of the composite can support favorable pathways to make fast kinetics for Li ions insertion-extraction. Remarkably, when the current density returns to 100

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mA g-1, a high specific capacity of 662.7 mAh g-1 is still delivered, signifying, outstanding reversibility and cycling stability. The voltage profiles at different current densities for Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites hollow spheres are exhibited in Fig. 7b. The achievable capacities are about 893.3, 743.7, 596.1, 473.2, 389.1 and 335.9 mAh g-1 at the current densities of 50, 100, 200, 300, 500, 1000 mA g-1, respectively.

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To

clarify

the

favorable

performance

of

the

Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5

nanocomposites, we measured the EIS (Fig. 7c). Before charge-discharge, the spectra consist of a depressed semicircle in the region of high-to-medium frequencies and a sloping line in the

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region of low frequencies. The semicircle reflects the charge transfer resistance (Rct) between the electrode and the electrolyte. The sloping line is related to the diffusion of lithium ions inside the electrode (Rw), and after CV, double semicircles appear clearly, in which semicircles in high

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frequencies correspond to the diffusion resistances of Li+ ions through the SEI layers (Rsf). Evidently, after 4 CV cycling the diameter of the semicircle decreased compared with the fresh

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cell, indicating the charge transfer resistance decreased apparently due to improvements in kinetics [40].

In order to get more insight about the morphological change due to the long term cycling, FE-SEM of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nano-composites after 1000 cycles at 1000

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mA g-1 was carried out. The FE-SEM images with different magnification in Figs. 8a and 8b show the morphology of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nano-composites after 1000 cycles. Although the presence of a large amount of conducting agent (carbon black), PVDF binders, and

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the decomposed electrolyte made more complicated but the hollow structure is still visible clearly. The result indicates that the hollow nature of the Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nano-

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composites is stabilized during the repeated cycling even at a very high rate of 1000 mA g-1 reflected in enhanced rate capability and cycling stability of the electrode material. Based on the above results, the superior lithium storage performance of the

Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5

nanocomposites

can

be

attributed

to

unique

hollow

microstructural feature. The hollow spheres can effectively alleviate the volume changes during the lithiation/delithiation processes for cycling stability. In addition, the hollow nanostructure

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could facilitate the electrolyte infiltration for fast Li ions insertion/extraction in the electrodes as a result of their stable structure with high surface area which enhanced the rate capability as well as cycle performance of hollow Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite. Moreover, the

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porosity of the shell can further provide a short path for Li+ diffusion, which can improve the rate capability. On the other hand, the presence of graphene would further improve conductivity and shorten Li+ path length [41]. Hence, using the 3D graphene architecture as an excellent scaffold

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to host Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite would be smart idea for further

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improvement in lithium storage properties.

4. Conclusions

Hollow Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites were prepared by spray pyrolysis methods and evaluated as LIB anode material for the first time. The nanocomposites anode

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exhibited a higher initial lithiation/de-lithiation capacities of 777.6/451 mAh g-1 than those of commercial graphite, and the reversible capacity was maintained at approximately 350 mAh g-1 after 500 cycles at 300 mA g-1. Even at a high rate of 1000 mA g-1, it also showed an excellent

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performance up to 1000 cycles and 90% Coulombic efficiency with no sign of capacity fading. This outstanding Li storage performance makes hollow Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5

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nanocomposites a promising anode candidate for high performance LIBs application.

Acknowledgement

The work was carried out with financial support from the Ministry of Education and Science of the Russian Federation in the framework of increase Competitiveness Program of NUST "MISIS", implemented by a governmental decree dated 16th of March 2013,

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number 211. The authors greatly acknowledge Shilpa Kumari for her help to collect FESEM data of the electrode materials after cycling.

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Table 1. Elemental analysis of nanocomposites by ICP-AES Analyte

Spectral

Mass

lines (nm) percentage

19.0

Zn

202.5

12.9

Ni

221.6

11.8

Ca

317.9

8.8

Mg

279.5

4.6

Fe

259.9

12.2

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224.7

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Cu

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(%)

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Figure Captions Fig. 1 The formation mechanism of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nano-composites

(EDS) and d, e, f) SEM under different magnification.

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Fig. 2 Characterization of nanocomposite a) XRD b) FTIR spectrum c) Elemental analysis

Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites

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Fig. 3 a, b and c) TEM observations at different magnifications and d) HRTEM image of the

Fig. 4 Elemental mapping of Zn, Cu, Ca, Ni, Mg and O for an individual hollow particle of the

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Fig. 5 c) BET surface area plot and d) N2sorption/desorption isotherms, Inset: the corresponding pore size distribution of the Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites. Fig. 6 a) The initial four CV curves at a scan rate of 0.1 mV s-1, b) The selective charge discharge profile at 300 mA g-1 and c) cycling performance at 300 and 1000 mA g-1 of

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Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposites.

Fig. 7 a) Discharge capacities at different current densities ranging from 50 to 1000 mA g-1, b) Galvanostatic charge-discharge profiles at various current densities, c) EIS spectra of the

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Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite, before and after CV, Insets: zoomed view.

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Fig. 8 a, and b) FE-SEM images of Cu0.10Mg0.40Zn0.50Fe2O4/Ca2Ni5 nanocomposite after 1000 charge-discharge cycles with different magnifications.

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Research Highlights •

This is the first report on hollow Cu0.10Mg0.40Zn0.50Fe2O4/ Ca2Ni5 nanocomposites as anode material for lithium ion battery.

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• The hollow nanocomposites were synthesized by one-pot ultrasonic spray pyrolysis process.

• The nanocomposites provide a reversible capacity of 350 mAh g-1 after 500 cycles at 300 mA g-1.

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• Such superior performance is endowed by the synergic effect and hollow structures of

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the composite materials.