DOI:10.30919/es5e1006

Received: 09 Feb 2020
Revised: 23 Mar 2020
Accepted: 21 Apr 2020
Published online: 01 May 2020

Facile Synthesis of LiMn0.75Fe0.25PO4/C Nanocomposite Cathode Materials of Lithium-Ion Batteries through Microwave Sintering

Chunping Hou,1,2 Jiao Hou,3 Hao Zhang,1 Yong Ma,1,4,* Xiaowei He,1 Wangchang Geng1 and Qiuyu Zhang1,*

1 Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, Northwestern Polytechnical University, Xi an Shanxi 710129, China
2 College of Materials Science and Engineering, North Minzu University, Yinchuan Ningxia 750021, China
College of Chemistry and Chemical Engineering, North Minzu University, Yinchuan Ningxia 750021, China
4 School of Material Science and Engineering, Shandong University of Science and Technology, Qingdao Shandong 266590, China

*: courage2010@126.com (Y. Ma); and  qyzhang@nwpu.edu.cn (Q. Zhang)

Abstract

Lithium ion batteries (LIBs) have been widely applied as energy storage devices for large-scale electrical vehicle markets. Designing and ameliorating new or existing anodes are in high demand to meet the requirements of the next generation LIBs with higher energy/power densities, more excellent rate capability and longer cycling performance. Co3O4-based materials have drawn great attention as potential alternatives to the current graphite anodes due to the high capacity, abundant reserves of resource, moderate price, and simple preparation process. However, their inherent shortcoming of low conductivity and huge volume changes limit the practical applications. Different approaches have been applied to overcome these drawbacks. Herein, we summarize the recent developments in high-performance Co3O4anode materials from their architectures, including 0D nanostructures (nanospheres, nanocrystals, nanoparticles, nanocages and nanocubes), 1D nanostructures (nanowires, nanofibers, nanorods and nanotubes), 2D nanostructures (nanosheets, nanofoils, nanoflakes and nanofilms), and 3D structures (microsized cages, hollow structures, mesoporous structure, flower-like structure). We expect that this review will shed light on the structure-property relationship for rational design and synthesis of Co3O4-based materials and promote the practical application.

Keywords: Li-ion batteries; Cathode material; Microwave sintering; Lattice parameters; Electrochemical performance


1. Introduction

Since Padhi’s first report,[1] lithium manganese phosphate (LiMnPO4) has been considered as a promising cathode material for Li-ion batteries due to its lower cost, abundant source, environmental compatibility, good thermal stability, and long cycle life, especially for the uses of electric or hybrid electric vehicles, and dispersed energy storage.[2-10] In comparison with lithium iron phosphate (LiFePO4), lithium manganese phosphate (LiMnPO4) possesses a higher redox potential (4.1 V vs. Li/Li+) and larger theoretical energy density (701 Wh kg-1). Furthermore, LiMnPO4 is well compatible with the currently used electrolytes for 4 V positive electrodes such as lithium cobalt oxide (LiCoO2) and lithium manganese oxide (LiMn2O4) cathodes. However, LiMnPO4 suffers from low electronic conductivity (<10-10 S cm-1),[11-13] low Li+ diffusion coefficient,[14,15] local structure distortion caused by Jahn-Teller effect of active Mn3+ ions[16] and a large cell volume change between LiMnPO4 and MnPO4 during the charge/discharge process.[17,18] To overcome these shortcomings, different strategies have been adopted to optimize the properties of LiMnPO4 by using nanoscale particles,[19] doping,[20-22] carbon coating,[23,24] conductive additive loading,[25] and various synthesis techniques.[26-31] Thereinto, Fe substitution has been proved to be more effective to improve the electrochemical characteristics of LiMnPO4 cathode material and is promising for large-scale applications.[23,32] It can dramatically improve Li+ and electron transport in the bulk and charge transfer on the surface of the nanocrystals.[33]

Although the common solid-phase synthesis has many advantages, such as simple process and low cost, the electrochemical properties of the prepared material are poor. Compared to solid-phase synthesis, the materials fabricated by liquid-phase synthesis possess good electrochemical performances. However, much more complicated synthesis processes and higher energy consumption lead to some limitations in practice. Therefore, it is necessary to consider a facile synthesis method to prepare LiMnPO4 with better electrochemical performances and energy-saving spontaneously, which is also a low cost and time-saving synthetic method with great industrial application prospects.

Liquid-phase synthesis, such as hydrothermal, sol-gel, solvothermal, polyol, can make the material’s particles in a refined nanoscale. Recently, composite materials based on LiMnPO4 have been obtained and exhibited significant performances with the combination of liquid-phase synthesis and conventional technologies. For example, Wu et al.[34] prepared LiMnPO4/C cathode materials by a sol-gel method combined ball milling and liquid nitrogen quenching method. It is revealed that quenching inhibited the growth and agglomeration of LiMnPO4/C particles and resulted in the formation of defects in LiMnPO4 crystals, therefore greatly improving the electrochemical performance of LiMnPO4/C. Microwave-assisted synthesis is taken as an energy-saving and fast synthesis method for the electrode materials. For example, Kim et al.[35] synthesized LiMn0.75Fe0.25PO4/C microspheres through using a microwave-assisted process with a complexing agent, and found that the prepared product had a high tap density of 1.3 g cm-3 and delivered a reversible capacity of 163 mAh g-1 at a 0.05 C-rate. Furthermore, 57% capacity retention at a 60 C-rate as well as 99.3% capacity retention after 100 cycles at 1 C-rate were obtained. Yu et al.[36] adopted both condition-controlled microwave heating and conventional heating to synthesize LiFePO4/C microspheres, respectively. It was found that the microwave heated LiFePO4/C sample had a 3D porous structure with a particle size of about 20-30 nm, which exhibited higher capacities, excellent rate capability, and a better dynamic performance (higher Li+ diffusion and lower polarization). Although the microwave-assisted method was frequently used in both hydrothermal synthesis and solvothermal synthesis for LiMnPO4, there are few literatures about microwave heating sintered LiMnPO4 cathode material. In this paper, the LiMn0.75Fe0.25PO4/C powders were prepared by a facile hydrothermal and ball-milling method and then sintered by microwave heating. The improvement of the electrical conductivity and the enhancement of Li+ diffusion for LiMnPO4 cathode material were researched in detail.

2. Experimental section

2.1 Preparation of LiMn0.75Fe0.25PO4/C composites

LiMn0.75Fe0.25PO4 nanoparticles were synthesized by a facile hydrothermal method.[24] The as-prepared LiMn0.75Fe0.25PO4 precursor was mixed with a sucrose solution in a 10:2 weight ratio, and the mixture was milled at 40 Hz for 24 h with a ball-to-material ratio of 10:1 (Shanghai Dingpai Mechanical Equipment Co., Ltd., 0.4 L). The slurry was spray dried on a GZ-5 spray dryer with an inlet temperature of 220 °C and an outlet temperature of 120 °C. Then, the spherical LiMn0.75Fe0.25PO4/sucrose composite obtained by secondary granulation was heated to 350 °C at a rate of 2 °C min-1 and maintained for 4 h in an N2-filled box furnace (KBF13Q). Afterward, the composite was raised to 550 °C at a rate of 2 °C min-1, and sintered for 10 h, then naturally cooled down to room temperature and sieved through a 200 mesh to obtain the LiMn0.75Fe0.25PO4/C nanoparticles (marked as contrast sample A). Meanwhile, the LiMn0.75Fe0.25PO4/sucrose composite was treated with a MobileLab Microwave Station (4 kW, 2450 MHz (220 V)), heated to 350 °C at a rate of 10 °C min-1 and maintained for 2 h, and then heated to 550 °C and maintained for 5 h. Finally, the microwave sintered LiMn0.75Fe0.25PO4/C nanoparticles were obtained (marked as sample B). The schematic illustration of the preparation process of LiMn0.75Fe0.25PO4/C composites calcined by ordinary heating sintering and microwave sintering is exhibited in Scheme 1.

Scheme 1. The schematic illustration of the preparation process of LiMn0.75Fe0.25PO4/C composites calcined by (A) ordinary heating sintering and (B) microwave sintering.

2.2 Characterization of LiMn0.75Fe0.25PO4/C composites

The crystal phases of the synthesized composite materials were characterized by an X-ray diffractometer (XRD) (XRD-7000S, Shimadzu, Japan) using Cu Kα radiation (λ=0.15423 nm) (40 kV 200 mA). The microscopic features of the samples were observed by field-emission scanning electron microscopy (SEM, JSM-6700F, JEOL, Japan) with an energy-dispersive X-ray spectroscopy (EDS) and a transmission electron microscopy (TEM, JEM-3010, JEOL, Japan). N2 adsorption/desorption isotherms and specific areas were tested using a Tristar II surface area and porosity analyzer (Micromeritics Instruments Inc., USA).

2.3 Electrochemical measurements

The electrochemical properties of the samples were measured by assembling CR2025 coin cells. The composite electrodes were prepared by mixing LiMn0.75Fe0.25PO4/C composites with carbon black and polyvinylidene difluoride (PVDF) in a weight ratio of 85:8:7 in N-methyl pyrrolidone to form a homogeneous slurry. The slurry was coated on aluminum foil and dried in a vacuum oven at 120 °C for 12 h, then pressed and punched to disks. Finally, the cells were assembled in an Ar-filled glove box (LABSTAR 1250/750, MBRAUN, Germany) with lithium foil as the counter and the reference electrode, a polypropylene microporous film (Celgard 2400, USA) as the separator, and 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate (FEC) (1:1:1, v/v/v) (LD-124B, Shanshan battery material Co., Ltd, China) as the electrolyte. The galvanostatic charge/discharge tests were conducted on a battery testing system (LAND CT2001A, Wuhan Jinnuo Electronics Co., Ltd., China) in the potential range of 2.5-4.5 V (vs. Li+/Li) at rates of 0.1 and 0.2 C (1 C=171 mA g-1). An electrochemical workstation (CHI660E, Shanghai Chenhua Instruments Inc., China) was used to perform the cyclic voltammetry tests by using a scan rate of 0.1 mV s-1 and a voltage range of 2.5-4.5 V (vs. Li+/Li). The electrochemical impedance spectroscopy (EIS) was measured at room temperature. And the spectra were potentiostatically measured by applying an AC voltage of 5 mV from 105 to 10-2 Hz. All the tests were conducted at room temperature.

3. Results and discussion

As shown in Fig. 1, the XRD diffraction peaks of two samples are completely indexed to the orthorhombic Pnmb space group of LiMnPO4 (PDF#740375) based on the olivine structure. The diffraction peaks of Fe-doped samples are slightly shifted to larger 2θ angles compared with those of pure LiMnPO4 owing to the smaller ionic radius of Fe2+ doping homogeneously in a solid solution. The relative intensity of the diffraction peak of LiMn0.75Fe0.25PO4/C prepared by ordinary heating sintering is much higher than that of the sample prepared by microwave sintering. This case indicates that the former process makes the crystal growth more complete, the crystal structure more perfect and the defects much less due to the prolonged heating time. Of particular attention is that there are no characteristic peaks of crystal carbon observed in the patterns, demonstrating that the carbon in the composite is in the form of amorphous structure.

Sucrose is used as the carbon source to improve the electronic conductivity of the resulting product and inhibits the grain growth of LiMn0.75Fe0.25PO4. The lattice parameters of LiMn0.75Fe0.25PO4/C prepared with different sintering ways by the Rietveld refinement method are listed in Table 1. The lattice parameters of a pure LiMnPO4 are a=6.1000 Å, b=10.4600 Å, and c=4.7440 Å, which are larger than those listed in Table 1. This situation manifests that Fe partial substitution of Mn makes the cell volume shrink. Moreover, all the lattice parameters of the sample prepared by microwave sintering (a=6.0760 Å, b=10.4067 Å, and c=4.7310 Å) are smaller than those of one prepared by ordinary heating sintering (a=6.0774 Å, b=10.4149 Å, and c=4.7342 Å), and the cell volume also shrinks from 299.66 to 299.15 Å3. Because of a faster heating rate, shorter sintering time and a quick cooling process, microwave sintering can suppress the grain growth. The effect is similar to the quenching process of LiMnPO4 synthesis.

Table 1. Lattice parameters of LiMn0.75Fe0.25PO4/C composites calcined by ordinary heating sintering and microwave sintering.

 

Sample

A

 (Å)

b

(Å)

C

 (Å)

Cell volume (Å3)

Ordinary heating sintering

6.0774

10.4149

4.7342

299.66

Microwave sintering

6.0760

10.4067

4.7310

299.15

 

 

Fig. 1 XRD patterns of LiMn0.75Fe0.25PO4/C composites calcined by ordinary heating sintering and microwave sintering.

 

Fig. 2 SEM images of (A) LiMn0.75Fe0.25PO4 precursor and (B) corresponding enlarged part.

Fig. 2A displays the SEM image of LiMn0.75Fe0.25PO4 precursor and Fig. 2B is the corresponding enlarged image of the box area in Fig. 2A. It is found that the LiMnPO4 precursor shows a rodlike shape with a diameter of about 200 nm and a length of about 1 μm and has an orientated array growth. The precursor structure is much bigger than that of the milled and sintered sample (about 50 nm).

The specific surface areas of the materials can be obtained by employing N2 adsorption/desorption isotherms.[37-39] From Fig. 3 of N2 adsorption/desorption isotherms, the specific surface areas of the LiMn0.75Fe0.25PO4/C composites obtained by ordinary heating sintering and microwave sintering are 20.227 and 21.212 m2 g-1, respectively. The latter possesses a slightly larger specific surface area than the former. This fact is consistent with the variation trend of the lattice parameters measured by XRD. The microwave sintering process makes the heating rate increase faster and keeps a portion of carbon as stereochemical net structure, which results in the increment of the porosity and the specific surface area. Furthermore, microwave sintering inhibits the grain growth of the composites, followed by the formation of smaller particles and less agglomeration. This situation gives rise to a shorter Li+ ion diffusion path and promotes electrochemical properties such as electronic conductivity.

 

Fig. 3 N2 adsorption/desorption isotherms of LiMn0.75Fe0.25PO4/C composites calcined by ordinary heating sintering and microwave sintering.

Fig. 4 shows the SEM images of the spray-drying LiMn0.75Fe0.25PO4/C composites which are in the shape of spherical aggregate particles. It is noteworthy that the surface morphologies of the microspheres prepared by different processes are remarkably different. In Fig. 4A1, the surface of the microspheres fabricated by ordinary heating sintering is rough, and the primary particles have not been distributed evenly in size. At a high magnification of Fig. 4A2, it is found that some sintered aggregates and primary particles are larger than 200 nm on the surface. However, there are two situations on the surface of microspheres prepared by microwave sintering: Fig. 4C presents a dense surface covering, and the size of uniformly distributed primary particles is about 100 nm; Fig. 4D shows no dense surface covering, but the size distribution of particles is more uniform than that of the ones prepared by ordinary heating sintering. EDS analyses in Table 2 exhibit that the carbon content of the area C is slightly higher than that of area D, implying that there may be a carbon shell structure. The existence of a carbon shell structure enhances the conductivity of the resulting composite. With respect to the composite obtained by ordinary heating, the size increase and the agglomeration of particles lead to the diffusion path increase and the Li+ diffusion more difficult, thus reducing the conductivity of the composite.