Regular Article
Highly efficient Co3O4/CeO2 heterostructure as anode for lithium-ion batteries

https://doi.org/10.1016/j.jcis.2020.10.050Get rights and content

Abstract

Co3O4 has been extensively studied as an anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity. However, during the charging-discharging processes, the issues of large volume change and low electric conductivity arise, which significantly limit the practical applications of Co3O4. To solve these issues, a Co3O4/CeO2 heterostructure derived from metal-organic frameworks (MOFs) was designed and synthesized through one-step microwave synthesis. Benefiting from the mesoporous structure and presence of hetero-components, Co3O4/CeO2 having the molar ratio of Co/CeĀ =Ā 5:1 (denoted as 5Co3O4/CeO2) exhibits high reversible capacity and excellent cycling stability when used as an anode material for LIBs. Specifically, compared to a single-phase Co3O4 anode, which shows a capacity of 538.6 mAh/g after 100 cycles, 5Co3O4/CeO2 exhibits a higher capacity (1131.2 mAh/g at 100Ā mA/g). This study provides a novel strategy for using rare earth components to modify electrode materials.

Introduction

To realize sustainable technological development, it is essential to design renewable power sources. LIBs have attracted considerable attention as a stable energy storage system because of their high energy density and conversion efficiency, which makes them ideal candidates [1], [2], [3], [4], [5]. The theoretical capacity of graphite electrode materials for use in commercial LIBs is relatively low (372 mAh/g, maximal Li uptake LiC6). Therefore, it is imperative and important to explore and develop new anode materials with higher theoretical capacity. At present, several types of anode materials are available for LIBs, including alloys [6], [7], carbon-based materials [8], [9], metal oxides [10], [11], metal sulfides [12], [13], and metalā€“organic frameworks (MOFs) [14], [15]. Metal oxides have a high theoretical capacity, which is a beneficial characteristic for their application in next-generation LIBs. However, the practical application of metal oxides is still limited because of their fast capacity fading, low rate performance, low intrinsic electric conductivity, and short life cycle caused by large volume changes during the lithiation and delithiation processes. To solve these issues, hybrid materials composed of transition metal oxides and various other components are used [16], [17], [18]. Among these, composites fabricated through the integration of two or more transition metal oxides are the most effective materials for LIB application. The purpose of hybridization is to combine the advantages of each component and to enhance the physicochemical properties of metal oxides, such as electrochemical reactivity and mechanical stability [19], [20].

MOFs are typically porous materials composed of metal nodes and organic linkers [21], [22], [23]. Transition metal oxides based on MOF precursors with controlled architectures and chemical compositions, such as Co3O4 [24], CuO [25], Fe2O3 [26], NiO [27], NiCo2O4/NiO [28], NiFe2O4, ZnFe2O4, and CoFe2O4 [29], have attracted considerable research interest. Among these materials, nanostructured Co3O4 demonstrated excellent electrochemical properties because of its high theoretical capacity (890 mAh/g) and low lithium intercalation potential [30]. It has been proven that nanocrystallization can shorten the Li-ion migration path and accommodate the volume change during the cycling process, thus improving the storage performance. Ding et al. reported amorphous Co3O4@TiO2 hollow composites prepared via thermal decomposition of zeolitic imidazolate framework-67 (ZIF-67) and TiO2 coating; these composites exhibited a significantly high cycling performance (1057 mAh/g at 100Ā mA/g after 100 cycles) as anodes for LIBs [31]. Zhong and co-workers synthesized nanostructured Co3O4-CoFe2O4 composites through one-step pyrolysis of bimetallic MOFs [32]. When these composites were used as anodes for LIBs, their excellent electrochemical performance was mainly attributed to the well distribution and small size of the particles. In short, the cycling stability and electrochemical performance of Co3O4 can be improved through reasonable hybridization with other metal oxides. CeO2 is a well-known catalyst in the field of photocatalysis and its degradation properties are significantly enhanced when combined with Co3O4 because of the formation of p-n heterogeneous junctions in Co3O4/CeO2 [33], [34]. Therefore, CeO2 can be used to buffer the volume change of Co3O4, and the Co3O4/CeO2 heterostructure can be used as an anode material for LIBs. However, the electrochemical performance of the Co3O4/CeO2 composite has not been widely investigated.

Herein, a Co3O4/CeO2 heterostructure was fabricated from a bimetallic MOF precursor and applied as an anode material for LIBs. In the Co3O4/CeO2 heterostructure, CeO2 can limit the volume expansion of Co3O4, preventing the electrode from cracking. Benefiting from the unique structure and synergistic effect of the bimetallic composition, 5Co3O4/CeO2 displayed excellent energy storage performance, especially with respect to the rate capacity, and, thus, was shown to be applicable as an anode material for LIBs.

Section snippets

Materials

Polyvinylpyrrolidone (PVP, K30), cobalt nitrate hexahydrate (Co(NO3)2Ā·6H2O), and cerium nitrate hexahydrate (Ce(NO3)3Ā·6H2O) with a purity of 99.99% were purchased from Sinopharm. Pyrazole-3,5-dicarboxylic acid hydrate (H3pdc, C5H4N2O4Ā·H2O, 98%) and N, N-dimethylformamide (DMF, 99.5%) were supplied by Alfa Aesar. All above-mentioned chemicals were used directly without further purification.

Preparation of precursors

Co(NO3)2Ā·6 H2O (1Ā mmol) and Ce(NO3)3Ā·6 H2O (1Ā mmol) were dissolved under stirring in 15Ā mL DMF to attain a

Material characterization

Compared with the common solvothermal method, the microwave method has attracted considerable attention because of its advantages such as fast heating and high thermal energy efficiency. Scheme 1 illustrates the preparation Co3O4/CeO2. The Co-Ce-MOFs materials were prepared following a one-step microwave strategy using H3pdc as the ligand, followed by calcination under air for 3Ā h to obtain the mesoporous Co3O4/CeO2 heterostructure. XRD analysis was performed to identify the structural

Conclusions

Herein, Co3O4/CeO2 composites were prepared using a microwave-assisted solvothermal method followed by subsequent pyrolysis of MOF precursors, which enhanced the lithium storage behavior. The unique heterostructure allows for the combination of the Co3O4 and CeO2 advantages, provides a buffered space to accommodate the volume change, and shortens the Li+ diffusion path during the lithiation-delithiation process. Specifically, 5Co3O4/CeO2 shows an initial discharge capacity of 1090.1 mAh/g and a

CRediT authorship contribution statement

Ying Kang: Investigation, Writing - original draft. Yu-Hang Zhang: Methodology, Writing - review & editing. Qi Shi: Formal analysis, Funding acquisition, Formal analysis, Funding acquisition. Hongwei Shi: Data curation, Formal analysis. Dongfeng Xue: Conceptualization, Resources. Fa-Nian Shi: Supervision, Funding acquisition.

Declaration of Competing Interest

The authors declare that they have no competing interests.

Acknowledgments

The authors acknowledge the projects 21571132 and 21822808 supported by the National Natural Science Foundation of China. This work was also supported by the key project (LZGD2017002) of Department of Education of Liaoning Province, China.

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