Elsevier

Energy Storage Materials

Volume 34, January 2021, Pages 735-754
Energy Storage Materials

A review of recent developments in Si/C composite materials for Li-ion batteries

https://doi.org/10.1016/j.ensm.2020.10.026Get rights and content

Abstract

Rechargeable lithium batteries play an increasingly significant role in our daily lives. Hence, the development of high capacity secondary lithium batteries has become a research hotspot. In the past decade, silicon has been extensively studied as anode material for Li-ion batteries because of its extremely high specific capacity. However, the dramatic volume change and troublesome SEI (solid electrolyte interface) issues during lithiation and delithiation hinder the commercialisation of Si anode materials. To circumvent these issues, carbon materials have been widely utilized in composites with Si materials due to their excellent electrochemical and physical properties. Established preparation methods of Si/C composite materials facilitate the design of novel Si/C composites. Different forms of carbon can improve the electrochemical performance of silicon materials in different ways. Advanced characterisation techniques further verify and explain the contribution of carbon materials to the performance improvement of Si. Si/C composite materials are anticipated to be the anode material for the next generation of commercial lithium batteries.

Introduction

The advent of portable electronic products and alternative fuel vehicles has led to an increased demand for advanced lithium (Li)-ion batteries. High performance Li-ion batteries provide electric endurance support in electronic products [1], [2], wherein battery performance is primarily affected by the battery's anode materials. Graphite is a popular low-cost commercial anode material with high conductivity and stable reversibility. However, the material's relatively low capacity has limited its further development.

Electrochemical alloys of Li metal with other compounds (e.g. Si, Sn, P, and Sb) can be used as alternatives. Si-based anode materials are a popular candidate for next generation Li-ion batteries due to an extremely high specific capacity of over 10 times that of commercial graphite. [3], [4] However, Si-based anodes exhibit large volume changes and form an unstable solid electrolyte interface (SEI) during electrochemical processes (Fig. 1(a-c)) [5]. Recently, composites of carbon and Si (Si/C) based on various carbon materials and structural designs have been developed to overcome these issues concerning volume expansion and continuous SEI formation (Fig. 1(d-f)) [6], [7], [8]. Carbon coating and controlled porosity have been found to prevent the pulverization of Si particles [6]. Carbon coating can also ensure the stability of the solid electrolyte interphase, thus preventing the consumption of the inner Si by the continuously formed SEI [7]. Careful design of Si/C material structures can ensure strong bonding between the electrode materials and current collector [8]. Overall, the improved performance of Si-based anode materials has been attributed to unique structural designs and the excellent properties of the carbon materials. Several literature reviews have explored the development of Si/C composite anode materials for Li-ion batteries from different perspectives. For instance, Dou et al. [9] assessed Si/C composite materials with different dimensions in great detail, Zhang et al. [10] introduced nanostructured Si/C materials and related electrolytes and binders, and Shen et al. [11] summarized the progress in Si/C materials by highlighting different material structures. However, a comprehensive review introducing various Si/C composite anode materials and their preparation methods along with advanced characterization techniques has not yet been published. This review focuses on the use and preparation of carbon materials to enhance the performance of Si materials, giving a detailed description of one-dimensional (1D) carbon nanofibers (CNFs) and nanotubes (CNTs), two-dimensional (2D) graphene (G) sheets and transition metal carbides and carbonitrides (referred to as MXenes), and three-dimensional (3D) graphene shell or amorphous carbon shell-coated Si particles and Si/graphite composites. The excellent performance of Si/C composites is further verified and explained using several advanced characterization techniques. As for zero-dimensional (0D) carbon materials,we only include carbon black in this category.In addition, research on Si/carbon black composites is rarely reported, so we will not introduce these materials.

Section snippets

Advanced preparation methods of carbon materials

Different Si materials have been designed and synthesized for Li-ion batteries using various methods, including Si-nanowire synthesis by vapor-liquid-solid processing [12] and solvent-mediated phenylsilane decomposition [13], Si-nanosphere growth on SiO2 by chemical vapor deposition (CVD) [14], Si-nanoparticle synthesis by the reverse micelles method [15], and Si-film deposition using a radiofrequency/direct current (RF/DC) magnetron sputtering system [16]. Furthermore, diverse silicon–oxygen

Si/1D carbon composite materials

Carbon nanotubes (CNTs) and CNFs are 1D carbon materials that can be used to form Si/carbon nanotube and nanofiber composite materials. CNTs are widely used in photonics, optoelectronics, catalysis, and battery applications. Specifically, CNTs composited with Si materials show great promise for use in Li-ion batteries due to several advantages, including high electrical conductivity and impressive mechanical and thermal stabilities [51]. These properties are crucial for satisfactory electrode

Advanced characterization techniques

Electrode materials may be evaluated based on macroscopic performance testing and microscopic composition and structure characterization, where the macroscopic properties and performance of a material are highly dependent on its microstructure. Long-term cycling performance, rate performance, cyclic voltammetry measurements, and EIS are common macroscopic performance tests used in the study of Li-ion batteries. These parameters provide a good indication of the material's electrochemical

Conclusion and perspective

A wide range of strategies can be applied to synthesize Si/C composite materials. CVD and electrospinning methods are typically used to produce 1D carbon nanofiber and carbon nanotubes; Hummer's method is predominantly used to produce 2D graphene sheets from graphite, and CVD or thermal treatment are used to coat 3D carbon on the surface of Si.

Neither Si nor carbon electrodes alone meet the requirements of next generation commercial batteries, butthe Si content can be optimized to enhance the

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relatonships that could have appeared to influence the work reported in this paper.

Qitao Shi received his bachelor of science degree from the Department of physics and optoelectronic energy at Soochow University, Suzhou, China, in 2016. Currently, he works as doctoral researcher at the Soochow Institute for Energy and Materials Innovations (SIEMIS) and the College of Energy at Soochow University China in Prof. Mark H. Rümmeli's group. His current research focuses on solving the pulverization issues of Si particles as anode materials by space engineering or structure

References (140)

  • H. Jiang et al.

    Free-standing Si/graphene paper using Si nanoparticles synthesized by acid-etching Al-Si alloy powder for high-stability Li-ion battery anodes

    Electrochim. Acta

    (2016)
  • V. Singh et al.

    Graphene based materials: past, present and future

    Prog. Mater Sci.

    (2011)
  • J. Zhou et al.

    Chemical fixation of CO2 on activated Si: producing graphitic carbon-stabilized Si particles for Li-storage

    Energy Storage Mater.

    (2020)
  • D. Sui et al.

    A high-performance ternary Si composite anode material with crystal graphite core and amorphous carbon shell

    J. Power Sources

    (2018)
  • J. Han et al.

    Creating graphene-like carbon layers on SiO anodes via a layer-by-layer strategy for lithium-ion battery

    Chem. Eng. J.

    (2018)
  • Z. Yi et al.

    A flexible micro/nanostructured Si microsphere cross-linked by highlyelastic carbon nanotubes toward enhanced lithium ion battery anodes

    Energy Storage Mater.

    (2019)
  • H. Zhang et al.

    A robust hierarchical 3D Si/CNTs composite with void and carbon shell as Li-ion battery anodes

    Chem. Eng. J.

    (2019)
  • S. Cui et al.

    Si nanoparticles encapsulated in CNTs arrays with tubular sandwich structure for high performance Li ion battery

    Ceram. Int.

    (2020)
  • S. Liu et al.

    Boosting electrochemical performance of electrospun silicon-based anode materials for lithium-ion battery by surface coating a second layer of carbon

    Appl. Surf. Sci.

    (2019)
  • S.-M. Jang et al.

    The preparation of a novel Si–CNF composite as an effective anodic material for lithium–ion batteries

    Carbon

    (2009)
  • X. Kong et al.

    Necklace-like Si@C nanofibers as robust anode materials for high performance lithium ion batteries

    Sci. Bull.

    (2019)
  • W. Stöber et al.

    Controlled growth of monodisperse silica spheres in the micron size range

    J. Colloid Interfaces Sci.

    (1968)
  • Y. Wang et al.

    Foamed mesoporous carbon/silicon composite nanofiber anode for lithium ion batteries

    J. Power Sources

    (2015)
  • C.N.R. Rao et al.

    Synthesis, properties and applications of graphene doped with boron, nitrogen and other elements

    Nano Today

    (2014)
  • H. Xiang et al.

    Graphene/nanosized silicon composites for lithium battery anodes with improved cycling stability

    Carbon

    (2011)
  • X. Tang et al.

    Stable silicon/3D porous N-doped graphene composite for lithium-ion battery anodes with self-assembly

    Appl. Surf. Sci.

    (2018)
  • K. Feng et al.

    Implementing an in-situ carbon network in Si/reduced graphene oxide for high performance lithium-ion battery anodes

    Nano Energy

    (2016)
  • Q. Xu et al.

    Scalable synthesis of spherical Si/C granules with 3D conducting networks as ultrahigh loading anodes in lithium-ion batteries

    Energy Storage Mater.

    (2018)
  • G. Zhao et al.

    Decoration of graphene with silicon nanoparticles by covalent immobilization for use as anodes in high stability lithium ion batteries

    J. Power Sources

    (2013)
  • G. Lin et al.

    Graphene nanowalls conformally coated with amorphous/ nanocrystalline Si as high-performance binder-free nanocomposite anode for lithium-ion batteries

    J. Power Sources

    (2019)
  • J.-M. Tarascon et al.

    Issues and challenges facing rechargeable lithium batteries

    Nature

    (2001)
  • B. Dunn et al.

    Electrical energy storage for the grid: a battery of choices

    Science

    (2011)
  • M.N. Obrovac et al.

    Alloy negative electrodes for Li-ion batteries

    Chem. Rev.

    (2014)
  • Y. Jin et al.

    Challenges and recent progress in the development of Si anodes for lithium-ion battery

    Adv. Energy Mater.

    (2017)
  • F. Dou et al.

    Silicon/carbon composite anode materials for lithium-ion batteries

    Electrochem. Energy Rev.

    (2019)
  • C.K. Chan et al.

    High-performance lithium battery anodes using silicon nanowires

    Nat. Nanotechnol.

    (2008)
  • C.K. Chan et al.

    Solution-grown Silicon nanowires for lithium-ion battery anodes

    ACS Nano

    (2010)
  • Y. Yao et al.

    Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life

    Nano Lett.

    (2011)
  • H. Kim et al.

    A critical size of silicon nano-anodes for lithium rechargeable batteries

    Angew. Chem. Int. Ed.

    (2010)
  • J. Tu et al.

    Straightforward approach toward SiO nanospheres and their superior lithium storage performance

    J. Phys. Chem. C

    (2014)
  • J. Cho

    Porous Si anode materials for lithium rechargeable batteries

    J. Mater. Chem.

    (2010)
  • M. Inagaki et al.

    Carbon nanofibers prepared via electrospinning

    Adv. Mater.

    (2012)
  • JR.W.S. Hummers et al.

    Preparation of graphitic oxide

    J. Am. Chem. Soc.

    (1958)
  • N.I. Kovtyukhova et al.

    Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations

    Chem. Mater.

    (1999)
  • D.P. Wong et al.

    Binder-free rice husk-based silicon–graphene composite as energy efficient Li-ion battery anodes

    J. Mater. Chem. A

    (2014)
  • M. Ko et al.

    Elastic a-Silicon nanoparticle backboned graphene hybrid as a self-compacting anode for high-rate lithium ion batteries

    ACS Nano

    (2014)
  • J. Ren et al.

    Silicon–graphene composite anodes for high-energy lithium batteries

    Energy Technol.

    (2013)
  • X. Xin et al.

    A 3D porous architecture of Si/graphene nanocomposite as high-performance anode materials for Li-ion batteries

    J. Mater. Chem.

    (2012)
  • F. Sun et al.

    A rationally designed composite of alternating strata of Si nanoparticles and graphene: a high-performance lithium-ion battery anode

    Nanoscale

    (2013)
  • X. Gao et al.

    A multilayered silicon-reduced graphene oxide electrode for high performance lithium-ion batteries

    ACS Appl. Mater. Interfaces

    (2015)
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    Qitao Shi received his bachelor of science degree from the Department of physics and optoelectronic energy at Soochow University, Suzhou, China, in 2016. Currently, he works as doctoral researcher at the Soochow Institute for Energy and Materials Innovations (SIEMIS) and the College of Energy at Soochow University China in Prof. Mark H. Rümmeli's group. His current research focuses on solving the pulverization issues of Si particles as anode materials by space engineering or structure optimization.a

    Mark H. Rümmeli heads the electron microscopy and LIN labs at the Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, where he is a full professor. He is also director of the characterization center at the College of Energy and SIEMES. Moreover, he is a full professor of the Polish Academy of Sciences (CMPW PAN) in Zabrze and has full habilitation rights. He obtained his Ph.D. from London Metropolitan University and then worked as a postdoc at the German Aerospace Center. His research focuses on the growth mechanisms of 2D nanostructures, their functionalization and application in energy and biomedicine.

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