Layered materials for supercapacitors and batteries: Applications and challenges

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Abstract

Layered materials displaying a unique anisotropic structure with strong in-plane bonds but weak interaction between layers have been widely investigated as electrodes for batteries and supercapacitors. However, the limited capacity and sluggish ion diffusion impede their satisfaction of the requirements for higher energy and power density. Much effort has been expended and many new developments have been achieved in recent years. This review provides a critical overview of the current progress on these topics in different layered materials. It systematically summarized the application and improvement strategies of several typical layered materials, i.e., graphite, black phosphorus, transition metal dichalcogenides, MXene, layered oxide/hydroxides, nanosheets, and nanosheet-derived layered materials as electrodes of lithium ion batteries, sodium ion batteries, supercapacitors, and Li-S batteries. For each layered material, current methods such as expanding the interlayer spacing, tuning the surface group, changing the chemical composition, co-intercalation of the electrolyte molecules, nanosheet heterostructures, etc., were discussed based on their influences on stability, ion diffusion, phase change, capacity, and voltage. We highlighted the importance of nanosheet heterostructures and interlayer modification as a generally promising direction. It is believed that molecule-level electrode design (structure and functionality) is significant for the energy storage of layered materials in the future.

Introduction

Currently, electric energy sources are becoming increasingly varied. Examples include solar energy, wind energy, biomass energy, tidal energy, geothermal energy, and nuclear energy. Among them, renewable clean energy is favorable to alleviate the environmental issues caused by the combustion of fossil fuels. However, most clean energy sources are not high-quality, because their outputs are not stable. Therefore, second ion energy storage devices are critical to covert present clean energies to a stable and continuous output. Now, practical applications impose more requirements on the second electric energy storage devices. For example, mobile devices, such as mobile phones, notebook computers, and E-book readers, need light energy sources with long battery life for better portable performance, which require a long and stable low-power output. Large electric equipment, such as electric vehicles, electric cranes, and electric hatches, has special requirements for short-term, high-power output to respond to certain occasions requiring large force. Meeting all these requirements in one energy storage device remains a fascinating but significant challenge. A series of electric energy storage devices has been developed as shown by the Ragone diagram in Fig. 1 [1]. Each of them has unique advantages in terms of energy density, power density, cost, lifetime, etc. In this review, we focus on the topic of supercapacitors and batteries, which include lithium ion batteries (LIBs), sodium ion batteries (SIBs), and Li-S batteries.

Layered materials have been widely investigated as cathodes and anodes in batteries and supercapacitors. They have been proved too important for energy storage that many excellent review papers were reported. Doeff et al. gave a comprehensive review on the NMCs (LiNixCoyMnzO2) cathodes of LIB [2]. They focused on various strategies to improve the performance and to understand the limitations of these NMC cathodes. Attention on other special kinds of layered materials, such as MXene [3], [4], transition metal dichalcogenides (TMDCs) [5], [6], Mn-based layered oxide [7], MoS2 [8], etc., were also popular, which would prefer to summarize all the applied field beyond energy storage. Artificial layered materials by restacking exfoliated 2D materials have attracted much attention due to the sophisticated structure and composition design. Wang et al. reviewed the battery application of hybrid 2D materials, including preparation, application in LIB, SIB, MIB (magnesium ion battery) and microscopic mechanism of 2D electrode nanomaterials in detail [9]. They highlighted the features and application of 2D hybrid materials based on graphene and TMDCs nanosheets. A more general overview of layered materials for energy storage and conversion was done by Zhai et al. [10] recently, extensively showing the advantages of layered materials in metal ion battery, supercapacitor and catalysis in HER and OER. Nevertheless, few reviews have systematically surveyed different kinds of layered materials and related performance enhancement strategies of energy storage, then gave a general idea to improve the performance of layered materials, which is significant to promote the rational design of layered materials for electrochemical performance improvements.

The intercalation/extraction of ions into/from the galleries is the natural manner of their operation, which occurs in a highly reversible way with small volume change and long lifetime. However, the reversibility is limited to a certain lithiation/delithiation degree to maintain the layered structure, and the slow diffusion speed of ions in solid electrodes cannot allow a rapid charge/discharge process. The former determines that intercalation in layered materials has a relative low capacity. Especially for larger ions, e.g., Na+, the capacity decreases noticeably compared to small Li+ ions [11], [12], [13]. The latter greatly limits the application of layered materials in supercapacitors, which require a high-power output and favor the rapid surface reaction. To overcome the difficulties above, much effort has been expended to enhance the properties of layered materials, such as tuning the composition of host layers [14], [15], expanding the interlayer spacing [16], [17], [18], and making artificial layered materials according to designs [19], [20].

Different layered materials exhibit various electrochemical performances owing to their composition, interlayer environment, surface functional groups, etc. Apart from the unique strategies, there are certain common methods to tune the properties. For example, expanding the interlayer spacing is effective to enhance the diffusion speed of ions in the bulk solid, and to alleviate the volume expansion. A careful adjustment of the charge/discharge degree is important to limit the irreversible phase transition [21], [22], [23]. Comparisons and analogies of different methods from various layered materials are very useful for finding innovative ideas. Therefore, when intercalation was introduced to supercapacitors as in batteries, intercalation pseudocapacitors (IPCs) emerged [24], [25], which exhibited capacitive behaviors in the intercalation manner, and delivered higher energy densities than the surface reactions. In this review, we survey the structure and electrochemical performance of six types of layered materials, and further summarize the common methods to enhance the performance of different materials. We also highlight the importance of heterostructures and interlayer modification in the future.

Section snippets

Layered materials

Layered materials are a large family, exhibiting various structures and functionalities. Generally, they can be divided into two classes, i.e., natural (or crystallographic) layered materials and artificial layered materials. As the name suggests, the former layered structures originate from their unique crystal features, and the latter are organized according to special designs, although they are nonlayered crystal structures in nature. All the layered materials have two-dimensional (2D)

Graphite

For graphite, each carbon atom being sp2 hybridized binds with three other carbon atoms via three σ bonds and one π bond. The covalent σ bonds (~0.14 nm) organize the C atoms into a 2D honeycomb structure, which is the so-called “graphene.” Graphene layers are further glued together via π-π interaction between adjacent layers, forming 3D graphite crystals (Fig. 2a). Owing to the low interlayer binding energy (~57 ± 4 meV/C atom) [80], the relative sliding of layers is easy, making graphite a

Discussion

It is clear that the advantage of layered materials lies in high reversibility. However, the cost of reversibility, i.e., maintaining layered structure, is limited ion storage, which means low capacity and low energy density. In this section, we will talk about the capacity and voltage in theoretical view, which directly related with the energy density of electrodes. Here, we mainly focus on layered oxide, which is the most representative layered materials for battery application in SIB or LIB.

Nanosheet heterostructure film

Maier’s group reported a new material by mixing the “super-ionic” conductor RbAg4I5 and electronic conductor graphite, to produce a so-called “mixed conductor” [293]. The conductor exhibited impressively improved ion diffusion kinetics owing to an interfacial ambipolar diffusion, which has a chemical diffusion coefficient even larger than that of NaCl in water. This is attributed to the unique working mechanism of the composites (Fig. 39a). For classic bulk materials, the transport of both

Concluding remarks and prospective

Layered materials are probably one of the most successful families for energy storage electrodes, considering the successful commercial application of LiCoO2 and graphite in LIBs. The unique 2D structure has strong in-plane bonds but with weak interaction between the host layers, which facilitates ionic migration in the gallery between layers. The concept of intercalation/extraction of cations, such as Li+, Na+, or even Mg2+, Al3+, etc., between the gallery is the fundamental aspect of this

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.

Acknowledgements

We acknowledge the financial support from the Sate Key Program of National Natural Science of China (No. 51532005), National Nature Science Foundation of China (Nos. 51472148, 51602181, 51272137), the Tai Shan Scholar Foundation of Shandong Province, General Financial Grant from the China Postdoctoral Science Foundation (No. 2015M582088), and the Fundamental Research Fund of Shandong University.

Chengxiang Wang received his PhD degree from School of Materials Science and Engineering, Shandong University in 2010 under the supervision of Professor Longwei Yin. Then he worked as a postdoctor in National Institute of Materials Science (NIMS), Japan from 2011 to 2014. Currently, he is an associate professor of Shandong University. His research interests focus on controlled synthesis and modification of layered materials to improve their energy storage performance.

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  • Cited by (0)

    Chengxiang Wang received his PhD degree from School of Materials Science and Engineering, Shandong University in 2010 under the supervision of Professor Longwei Yin. Then he worked as a postdoctor in National Institute of Materials Science (NIMS), Japan from 2011 to 2014. Currently, he is an associate professor of Shandong University. His research interests focus on controlled synthesis and modification of layered materials to improve their energy storage performance.

    Luyuan Zhang received his B.S. in physics from Lanzhou University in 2001, and obtained his Ph.D. degree in materials science at Shandong University, Jinan China, in 2012. Now, he works as an engineer to operate High Resolution Transmission Electron Microscopy in the school of Materials Science and Engineering of Shandong University. His research interests include structure characterization of layered materials, quantum dots synthesis and photovoltaics device fabrication.

    Zhiwei Zhang received her PhD degree from School of Materials Science and Engineering, Shandong University in 2017 under the supervision of Professor Longwei Yin. Currently, she is a research associate of Shandong University. Her current research interests focus on the preparation of nanomaterials and energy storage applications to improve the performance of secondary batteries such as lithium batteries and sodium batteries.

    Ruizheng Zhao is a PhD candidate at school of Materials Science and Engineering, Shandong University now. Her current research interests are preparation and exfoliation of layered materials and their electrochemical energy storage application, such as supercapacitor, Li ion battery, Na ion battery, etc.

    Danyang Zhao is a PhD candidate at school of Materials Science and Engineering, Shandong University now. Her current research interests are preparation and exfoliation of MXene and their electrochemical energy storage application, such as supercapacitor, Li ion battery, Na ion battery, etc.

    Renzhi Ma is an Associate Principal Investigator at the International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Japan. He received his PhD in Materials Processing Engineering from Beijing Tsinghua University in 2000. He worked as a postdoc for three years before becoming a staff researcher at NIMS in 2004. His work focuses on the synthetic chemistry of inorganic 1D nanotubes and 2D nanosheets, and advanced energy storage/conversion materials.

    Longwei Yin is a distinguished professor and director of Institute of Materials Physics & Chemistry, Shandong University, China. He received his PhD. in 2001 in Shandong University. Then he worked as a JSPS postdoctoral fellow from 2003 to 2006 in Prof. Yoshio Bando’s group at National Institute for Materials Science (NIMS), Japan. He won the National Science Fund for Distinguished Young Scholars of China in 2011. His present research interests mainly focus on energy conversion & storage devices, including Li or Na based secondary batteries, supercapacitors, photocatalysis and solar cell.

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