Dual-carbon enhanced silicon-based composite as superior anode material for lithium ion batteries

doi:10.1016/j.jpowsour.2016.01.040

Journal of Power Sources

Volume 307, 1 March 2016, Pages 738-745

https://doi.org/10.1016/j.jpowsour.2016.01.040 Get rights and content

Highlights

•
Dual-carbon enhanced Si-based composite (Si/C/G) was prepared.
•
It exhibits the best Li-storage properties compared to two single-carbon ones.
•
Low-cost and abundant Diatomite mineral was employed as Si raw material.
•
The preparation processes are simple, non-toxic and easy to scale up.

Abstract

Dual-carbon enhanced Si-based composite (Si/C/G) has been prepared via employing the widely distributed, low-cost and environmentally friendly Diatomite mineral as silicon raw material. The preparation processes are very simple, non-toxic and easy to scale up. Electrochemical tests as anode material for lithium ion batteries (LIBs) demonstrate that this Si/C/G composite exhibits much improved Li-storage properties in terms of superior high-rate capabilities and excellent cycle stability compared to the pristine Si material as well as both single-carbon modified composites. Specifically for the Si/C/G composite, it can still deliver a high specific capacity of about 470 mAh g⁻¹ at an ultrahigh current density of 5 A g⁻¹, and exhibit a high capacity of 938 mAh g⁻¹ at 0.1 A g⁻¹ with excellent capacity retention in the following 300 cycles. The significantly enhanced Li-storage properties should be attributed to the co-existence of both highly conductive graphite and amorphous carbon in the Si/C/G composite. While the former can enhance the electrical conductivity of the obtained composite, the latter acts as the adhesives to connect the porous Si particulates and conductive graphite flakes to form robust and stable conductive network.

Graphical abstract

Introduction

Recently, silicon-based materials have drawn considerable attention as one type of promising anode candidates for the next-generation high-energy lithium-ion batteries (LIBs) because of its high theoretical capacity of 4200 mAh g⁻¹, which is above eleven times higher than that (372 mAh g⁻¹) of graphite [1], [2], [3]. Furthermore, it owns lots of advantages for practical application, such as higher and more suitable Li-storage voltage, abundant reserves in the earth's crust, and environmental benignity [4]. However, there are still some critical problems caused by its huge volume variations during cycling [5], including pulverization of active Si particles, excessively thick solid electrolyte interphase (SEI) layers [6], and invalidation of transport pathways for electrons and ions during cycling. These drawbacks will seriously lead to its poor cycle performance and short cycle life when used as anode materials for LIBs [7], [8].

To overcome these weaknesses, many great efforts have been devoted to the rational design of silicon nanoarchitectures [4], [9], [10], [11]. Among them, one of the main methodologies is fabricating sufficient voids to accommodate the volume variations during cycling [12], [13], [14], [15]. For example, Cui and co-workers designed a pomegranate-like silicon-containing hybrid in which enough room was reserved for the expansion and contraction of volume during lithiation and delithiation [16]. As a result of this hierarchical arrangement, superior cycle ability (97% capacity retention after 1000 cycles), high coulombic efficiency (99.87%) and volumetric capacity (1270 mAh cm⁻³) has been attained. Wehrspohn and co-works showed a metal-assisted chemical etching method to prepare the stable mesoporous silicon anodes, which exhibited a high reversible capacity of about 2111 mAh g⁻¹ at the rate of 0.2C, as well as the good rate performance [17]. However, most of the raw materials and preparation processes are highly cost, making them be difficult for large-scale application. Therefore, it is highly desirable to explore low-cost and widespread Si resources and preparation strategies for meeting the demands of large-scale application of LIBs [18], [19] as well as the special architecture for better cycle stability [20].

Diatomite is one kind of biological sedimentary minerals [21], which mainly distributes in China, the United States, Denmark, France and Russia. In China, the reserves of Diatomite are larger than 320 million tons, and its price is lower than US$ 400 per ton. In addition, the components of Diatomite mineral are mainly biocompatible SiO₂ materials as well as small amounts of impurities including Fe₂O₃, MgO, CaO and organics, all of which are ecomaterials. Those features of low-cost and environmental benignity can well guarantee its large-scale application. Furthermore, most of the Diatomite minerals are composed of micrometer-sized particulates with plenty of pores in it, which is inherently beneficial to fabricate superior LIBs anode materials with the ability of volume accommodation.

Herein, by using the widely distributed, low-cost and environmentally friendly Diatomite as the silicon source, an advanced Si-based micro/nanocomposite (Si/C/G) composed of micrometer-sized secondary particulates has been developed as outstanding anode material for LIBs. In the micro/nanocomposite, there are also commercial flaky graphite with high conductivity and amorphous carbonaceous materials acted as the adhesives between porous Si and conductive graphite. Electrochemical tests demonstrate that the dual-carbon enhanced Si/C/G composite exhibits much improved Li-storage properties compared to the other two Diatomite-derived Si-based materials, Si/G and Si/C, which are modified by only graphite or amorphous carbon respectively.

Section snippets

Materials

Diatomite was obtained from the Chang-Bai Li Wei diatomite products Co. Ltd.. Mg powder (average particle size: 100 μm, purity: 99.5%, Aladdin) and glucose (molecular formula: C₆H₁₂O₆, the Tianjin Institute of fine chemicals) were used as received. All solutions were prepared by using deionized water as the solvent. All chemical reagents were in analytical grade.

Preparation of porous Si

The natural diatomite was firstly sintered at 700 °C for 2 h in air to remove the organics and then poured into 6 mol L⁻¹ H₂SO₄

Results and discussion

Typically, silicon anode materials will suffer from huge irreversible capacity loss and poor capacity retention, thus impeding their practicability in LIBs, which mainly results from the huge volume variations during alloying/de-alloying processes and the derivative problems [22]. The composites composed of silicon and carbonaceous materials possess reasonably large contact areas between them, and the employed carbonaceous materials can usually form the three-dimensional conductive network in

Conclusions

Diatomite is one kind of biological sedimentary minerals composed of micrometer-sized silicon oxide particulates with plenty of pores in it, which is inherently beneficial to fabricate superior LIBs anode materials with the ability of volume accommodation. In this paper, one advanced Si-based micro/nanocomposite is prepared by using the widely distributed, low-cost and environmentally friendly Diatomite as silicon raw materials. Electrochemical tests as anode for LIBs demonstrate that the

Acknowledgements

This work was supported by the Science Technology Program of Jilin Province (20140101087JC, 20150520027JH). XL thanks the support of the International Postdoctoral Exchange Fellowship Program.

References (37)

R.A. DiLeo et al.
Nano Energy
(2013)
M.S. Wang et al.
J. Power Sources
(2012)
K. Adpakpang et al.
Electrochim. Acta
(2014)
P. Zuo et al.
Electrochim. Acta
(2007)
M. Gauthier et al.
J. Power Sources
(2014)
V. Subramanian et al.
J. Power Sources
(2010)
G. Liu et al.
J. Power Sources
(2012)
J. Feng et al.
J. Power Sources
(2015)
M.N. Obrovac et al.
Chem. Rev.
(2014)
J.W. Wang et al.
Nano Lett.
(2013)

E. Peled et al.

Nano Lett.

(2015)

X.-L. Wu et al.

Chem. Asian J.

(2013)

J. Xiao et al.

J. Electrochem. Soc.

(2010)

Y. Oumellal et al.

J. Mater. Chem.

(2011)

Y.-S. Hu et al.

ChemSusChem

(2010)

A. Magasinski et al.

Nat. Mater.

(2010)

Y.-G. Guo et al.

Acc. Chem. Res.

(2012)

Y.-X. Yin et al.

Part. Part. Syst. Charact.

(2013)

Cited by (89)

“Mobius strip-like” FeSn alloy: A novel highly-distorted 3D hierarchical porous anode for ultrafast and stable Li storage
2024, Energy Storage Materials
Tin provides high specific capacity (994 mAh g⁻¹) by forming Li_4.4Sn in lithium-ion batteries (LIBs) yet exhibits poor electrochemical stability. Inspired by the miraculous “Mobius strip” with superior stress-relieving effect in the developable surface, herein, through a facile dealloying and sol-gel pyrolysis method, a “Mobius strip-like” highly-distorted C-wrapped 3D hierarchical porous FeSn integrated anode (HD-3D-HP FeSn@C) is initially designed and utilized to relieve the mechanical stress in Sn-based anode generated during lithiation-delithiation. The anodes are characteristic of highly-distorted bimodal pore-size distribution composed of microporous architecture and homogeneous nanopores on pore walls on the developable surface, which contribute to effective stress relief and rapid mass transfer. Moreover, the wrapped-C is of great significance for maintaining the anode structure and improving the stability of solid electrolyte interface (SEI). Therefore, the HD-3D-HP FeSn@C anodes display the ultrafast Li storage properties with high rate capability (0.23 mAh cm⁻² at 10 mA cm⁻²) and good cycling stability (68.89 % of capacity retention after 1000 cycles at 1 mA cm⁻², only ∼0.03 % capacity decay per cycle). This work provides a novel and universal anode design philosophy towards high-performance LIBs, which may shed light on the evolution of other secondary batteries beyond alkali metal batteries.
A carbon-covered silicon material modified by phytic acid with 3D conductive network as anode for lithium-ion batteries
2023, Advanced Powder Technology
The requirement for silicon-based anode material is growing and has received attentions. Silicon is a promising anode material for lithium-ion batteries due to the high theoretical capacity. However, the high volumetric variability of silicon has led to severe chalking and rapid capacity degradation. To ameliorate these problems, a carbon-covered silicon material with a 3D conductive network structure was prepared employing glucose and phytic acid as carbon sources. When acted as the anode for Lithium-ion batteries, the prepared composite material delivered 1612 mAh/g in the first cycle and approximately 600 mAh/g at 0.1 A/g after 200 cycles. In addition, even at 5 A/g, a high capacity of 503 mAh/g was reached, and when recovered to 0.1 A/g, the capacity of 878 mAh/g was maintained.
Preparation and lithium storage of anthracite-based graphite anode materials
2022, Xinxing Tan Cailiao/New Carbon Materials
Several graphite samples with different microstructures were prepared from anthracite using an industrial silicon powder as a catalyst. The mechanism of the catalytic reaction and the electrochemical properties of the prepared coal-based graphite in lithium anodes were investigated. The correlation between the microstructure and the properties of the graphite was also discussed. Results show that the sample with 5% silicon (G-2800-5%) has the best lithium storage. It has the most graphitic structure with a degree of graphitization of 91.5% as determined from the interlayer spacing. When used as an anode material, a high reversible capacity of 369.0 mAh g⁻¹ was achieved at 0.1 A g⁻¹ and its reversible capacity was 209.0 mAh g⁻¹ at a current density of 1 A g⁻¹. It also had good cycling stability with a capacity retention of 92.2% after 200 cycles at 0.2 A g⁻¹. The highly developed graphite structure, which is favorable for the formation of a stable SEI and therefore reduces lithium ion loss, is responsible for the superior electrochemical performance.
High-performance silicon from quartz product waste as an anode material for Li-ion batteries
2022, Ceramics International
As the demand for quartz products increases year over year, the increase in the production of quartz waste has gradually contributed to increases in resource waste and environmental pollution. To recover quartz from spent quartz product waste and realize its high-value utilization, quartz waste ($0.15/kg) was used as the raw material to prepare high-performance porous silicon as an anode material for lithium ion batteries via a simple high-energy ball-milling method, followed by magnesiothermic reduction. The formation mechanism of silicon from quartz particles with different particle sizes during magnesiothermic reduction was investigated by X-ray diffraction, field-emission scanning electron microscopy, and other methods. The preparation of porous silicon without residual impurities was determined to be highly dependent on the size of the quartz particles after high-energy ball milling. When formed into an anode material for electrochemical measurements, the pure porous silicon (Si-4) anode delivered an initial specific charge capacity of 2712 mAh·g⁻¹ with a high initial Coulombic efficiency of 81% at a current density of 200 mA g⁻¹. The specific capacity was sustained at 923 mAh·g⁻¹ for 300 cycles at a current density of 4000 mA g⁻¹. The results reported herein highlight the feasibility of recovering spent quartz resources for harmless treatment and high-value utilization.
Development of eco-efficiency concrete containing diatomite and iron ore tailings: Mechanical properties and strength prediction using deep learning
2022, Construction and Building Materials
The primary objective of this study was to develop eco-efficiency concrete containing diatomite and iron ore tailings (IOTs) so as to reduce greenhouse gas emissions and avoid resource depletion. To this end, 20 concrete mixtures were designed and prepared by incorporating 0%, 5%, 10%, and 15% of diatomite replacing cement and 0%, 25%, 50%, 75%, and 100% of IOTs replacing sand. Mechanical properties, including compressive strength, flexural strength, and splitting tensile strength, were analyzed to investigate the effects of diatomite and IOTs on the concrete. Moreover, a convolutional neural network (CNN) was developed to predict the mechanical properties of the concrete. A comparative analysis of the mechanical properties was performed to predict by the CNN and the design code expressions. The results reveal a critical value representing the transition from the positive to the negative effect of the tailings on the mechanical properties of the concrete. Nevertheless, diatomite has a positive effect on the strength of the concrete regardless of the concrete type. Further comparative analysis shows that the concrete containing 25% tailings and 10% diatomite has the most excellent mechanical properties. The concrete containing 75% tailings and 15% diatomite is a good plan for protecting the environment and sustainability. Furthermore, the prediction accuracy of the developed CNN is higher than that of the design code expressions. This work provides valuable information on the practical applications of the developed concrete, and its findings contribute to devising a novel method for predicting the mechanical properties of concrete.
Natural mineral compounds in energy-storage systems: Development, challenges, prospects
2022, Energy Storage Materials
Citation Excerpt :
But, considering the relative high melting point of NaCl, the low-melting point salts (AlCl3) were introduced, and the capacity of nano-Si microspheres could reach up to 1330 mAh g−1 after 200 cycles at 0.2 Ag−1 [95]. Morevoer, Si@graphene and Si@C@graphere were designed, delivering considerable energy-storage abilities, further demonstrating the promising potential of diatomite [96,97]. Moreover, compared to Si-based samples, the higher theoretical capacity could be noted for SiOx based samples.
The energy-conversion storage systems serve as crucial roles for solving the intermittent of sustainable energy. But, the materials in the battery systems mainly come from complex chemical process, accompanying with the inevitable serious pollutions and high energy-consumption. Natural mineral resources display various merits, such as unique architecture, adsorption capability and rich active sites, which have captured numerous attentions with remarkable advancements. Recently, the minerals compounds, containing 1D structure (halloysites, attapulgites, sepiolite), 2D structure (montmorillonite, vermiculite, molybdenite) and 3D structure (diatomite, pyrites), have been applied in plenty of fields. Aiming at their energy-storage applications, the significant utilizations in electrodes, separators, electrolyte and metal-protection were detailedly reviewed in lithium-ions battery, lithium-sulfur battery, solid-state battery and so on. However, it should be acknowledged that, the simple minerals hardly meet the demand of energy-storage systems, due to their inferior conductivity and less active substances. Thus, series of modified manners are applied for the evolution of phase (from silicate mineral to Si), the incorporating with carbon/polymer and the tailoring of surface traits, which were in-depth discussed as following. The work was expected to summarize the traits about mineral compounds from different architectures, whilst offering significant guidelines for exploring mineral-based materials in energy-storage systems.

View all citing articles on Scopus

View full text

Dual-carbon enhanced silicon-based composite as superior anode material for lithium ion batteries

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Preparation of porous Si

Results and discussion

Conclusions

Acknowledgements

Nano Energy

J. Power Sources

Electrochim. Acta

Electrochim. Acta

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

Chem. Rev.

Nano Lett.

Nano Lett.

Chem. Asian J.

J. Electrochem. Soc.

J. Mater. Chem.

ChemSusChem

Nat. Mater.

Acc. Chem. Res.

Part. Part. Syst. Charact.