Regular Article
Organic molecule confinement reaction for preparation of the Sn nanoparticles@graphene anode materials in Lithium-ion battery

https://doi.org/10.1016/j.jcis.2020.12.086Get rights and content

Abstract

Sn@Graphene composites as anode materials in Lithium-ion batteries have attracted intensive interest due to the inherent high capacity. On the other side, the high atomic ratio (Li4.4Sn) induces the pulverization of the electrode with cycling. Thus, suppressing pulverization by designing the structure of the materials is an essential key for improving cyclability. Applying the nanotechnologies such as electrospinning, soft/hard nano template strategy, surface modification, multi-step chemical vapor deposition (CVD), and so on has demonstrated the huge advantage on this aspect. These strategies are generally used for homogeneous dispersing Sn nanomaterials in graphene matrix or constructing the voids in the inner of the materials to obtain the mechanical buffer effect. Unfortunately, these processes induce huge energy consumption and complicated operation.

To solve the issue, new nanotechnology for the composites by the bottom-up strategy (Organic Molecule Confinement Reaction (OMCR)) was shown in this report. A 3D organic nanoframes was synthesized as a graphene precursor by low energy nano emulsification and photopolymerization. SnO2 nanoparticles@3D organic nanoframes as the composites precursor were in-situ formed in the hydrothermal reaction. After the redox process by the calcination, the Sn nanoparticles with nanovoids (~100 nm, uniform size) were homogeneously dispersed in a Two-Dimensional Laminar Matrix of graphene nanosheets (2DLMG) by the in-situ patterning and confinement effect from the 3D organic nanoframes. The pulverization and crack of the composites were effectively suppressed, which was proved by the electrochemical testing. The Sn nanoparticles@2DLMG not delivered just the high cyclability during 200 cycles, but also firstly achieved a high specific capacity (539 mAh g−1) at the low loading Sn (19.58 wt%).

Introduction

Developing high-efficiency storage energy devices was a key prerequisite to promise the rapidly growing demand of portable and mobile devices. Over the past four decades, Lithium-ion batteries (LIB) was chosen as the most successful commercial product and prevalent research object of the second battery owing to its unique properties like eco-friendliness, lightness, safety, and so on [1], [2], [3]. Designing high-efficiency anode materials in LIB was expected to solve the energy storage issue [4], [5].

Sn-based materials in LIB were favored due to the high theoretical specific capacity (993 mAh g−1) and the low discharge potential (<0.5 V versus Li/Li+) in the alloying-dealloying reaction, which was explained by the high number ratio between Sn and lithium (4Li : Sn) [6], [7], [8], [9], [10], [11]. However, the poor cyclability of the composites hampered its application in practice. It resulted from the pulverization and cracking of the electrode induced by the huge volume change during lithiation and delithiation. Thus, alleviating the volume change was the kernel for developing the high-performance Sn-based anode materials. To address the issue, the materials by dispersing metallic Sn in the carbon matrix was a reasonable and high potential design due to the surreal properties of carbon such as the mechanic buffer effect, the excellent electroconductivity, and the low density. To attain, the research has to tackle the two issues (1) Which type of the Sn@carbon materials can improve the electrochemical cyclability? (2) How to get the structure in a simple and low energy consumption way?

The first issue has been perfectly resolved by an unremitting effort of the pioneers. In the early period, G.X. Wang [12] and Jaephil Cho [13] composited Sn and carbon by the ball milling of graphite and metallic Sn or the hydrothermal reaction of Sn salt and glucose, respectively. However, the result showed the specific capacity fast faded less than 30 cycles. Afterward, Bruno Scrosati [14], [15] dramatically increased the homogeneity of Sn nanoparticles in the carbon matrix by calcination of the impregnated Sn precursor@resorcinol–formaldehyde resin. The reversible specific capacity reached up to 450 mAh g−1 during 100 cycles. Then, A series of strategies for amorphous carbon-based materials was developed to increase the homogeneity of Sn nanoparticles. For example, the core (Sn)-shell (carbon) nanoporous structure prepared by the in-situ transformation from the metal–organic frameworks to carbon shell [16]. On the other side, the importance of voids in the inner of the composites for alleviating the volume change was recognized. The composites including voids were favored, such as the yolk (Sn)-shell (carbon) nanoparticles prepared by the SiO2 hard template [17], the core (irregular Sn nanoparticles)-hollow carbon microfiber prepared by the coaxial electrospinning technology [18], the core (irregular Sn nanoparticles)-hollow carbon nanotube prepared by in-situ catalysis growth of CVD [19] or by the MnOx hard template method [20]. Finally, the reversible capacity was improved to around 750 mAh g−1 within 200 cycles. It was worth mentioning that a modified Bruno Scrosati’s method [14], [15] by introducing a pore-forming agent Pluronic F127 in resorcinol–formaldehyde resin to form a porous structure. As a result, the sponge-like porous carbon-Sn composites were synthesized, whose specific capacity was continually increased with cycles until 1300 mAh g−1 at 300 cycles [21]. However, the specific capacity was not steady on account of amorphous carbon’s low electroconductivity.

Followingly, the Sn@graphene composites were studied due to the good electroconductivity and mechanical strength [22], [23], [24], [25], [26], [27], [28], [29], [30]. For example, Chengxin Wang [31] dispersed Sn nanoparticles on the surface of vertically aligned graphene nanosheets (VAGN) by microwave plasma-enhanced chemical vapor deposition (MPECVD), and Chunnian He [32] dispersed Sn nanoparticles on the surface of 3D porous graphene networks (Sn@G-PGNW) by a soft template method, respectively. The specific capacity was finally stable at around 1100 mAh g−1 after 100 cycles. Recently, Yunfeng Lu [11] presented an extremely complicated strategy, which involved the CVD, using of hard template, and modifying hydrophilic and hydrophobic surface processes. Sn nanoparticles were finally encapsulated in a double-layer graphene tube (Sn nanoparticles@DLGT). Compared to Sn- carbon nanotube composited [19], [20], smaller and more homogeneous Sn nanoparticles in the Sn nanoparticles@DLGT were obtained. In consequence, the specific capacity was stable at 918 mAh g−1 after 500 cycles.

Thus, the Sn@graphene composites have generally presented the superiority compared to the Sn@amorphous carbon composites as anode materials [33], [34], [35], [36], [37], [38]. On the other side, More homogeneity and voids in the composites will result in higher electrochemical performance. However, the reported strategies for the preparation of Sn nanoparticles@graphene composites involved higher energy consumption and more complicated nanotechnologies [39].

To solve the issue, the simplicity of the preparation strategy has been attracted intensive interest [40]. In this report, the new synthesis strategy was proposed by the organic molecule confinement reaction (OMCR) [41]. In the strategy, the 3D organic nanoframes were obtained as the graphene precursor by polymerizing and crosslinking of the monomer (having multi-functional groups) dissolved in the liquid nanodroplets-reactor. The liquid nanodroplets-reactor was prepared by spontaneous emulsification, which was selected due to the simplicity, the size/its distribution controllability of nanoemulsions, and the low energy process [42], [43]. The SnO2 nanoparticles@3D organic nanoframes were synthesized by the conventional hydrothermal reaction just using nanoemulsions instead of ultra-pure water. The transformation of SnO2 nanoparticles@3D organic nanoframes to Sn nanoparticles@2DLMG was achieved by the redox reaction during calcination, in which 3D organic nanoframes around SnO2 nanoparticles supported the reduction and confinement environment due to breaking of Csingle bondH bond and the steric hindrance. As a consequence, the SnO2 nanoparticles were directly transformed to Sn nanoparticles with nanovoids and confined into a Two-Dimensional Laminar Matrix of graphene nanosheets (2DLMG).

In consequence, the Sn nanoparticles@2DLMG composites was prepared by the OMCR. The OMCR not only achieved the extremely homogeneous dispersing of Sn nanoparticles with nanovoids in the matrix of graphene nanosheets, but also the simplicity, low energy consumption, and eco-friendliness of the whole procedure rendered the practical value meaning [44].

Section snippets

Results and discussion

A new synthesis strategy (OMCR) has been demonstrated, which was exclusively designed for the graphene-based composites. Pure 2DLMG has been synthesized by OMCR in our previous report [41]. In this context, OMCR was used to obtain the Sn nanoparticles@2DLMG composites to further improve the electrochemical performance of anode materials in LIB. Firstly, following the conventional hydrothermal reaction for the preparation of SnO2 nanoparticles [45], the SnO2 nanoparticles@2DLMG composites were

Conclusion

In conclusion, a new strategy named organic molecule confinement reaction (OMCR) has been introduced to synthesize Sn naoparticles@graphene composites in context. Compared to the previous related research, homogeneously dispersed Sn nanoparticles were completely embedded into a Two-Dimensional Laminar Matrix of graphene nanosheets (2DLMG). There were not Sn nanoparticles on the surface of the matrix. In addition, the nanovoids were formed beside each Sn nanoparticles. Thus, the special

Experimental section

Materials: Labrafac® WL 1349 (Gattefossé S.A., Saint-Priest, France), Medium-chain triglyceride, was used in the preparation of nano-droplets, which is a mixture of capric and caprylic acid triglycerides as a model of parenteral-grade oil. Nonionic surfactant Kolliphor ELP® (BASF, Ludwigshafen, Germany, Highly purified) is a polyoxyethylated-35 castor oil, HLB = 12 ~ 14, used as a surfactant. Tri(propylene glycol) diacrylate (TPGDA, as monomer, 90%), 1-Hydroxycyclohexyl phenyl ketone (HCPK, as

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:

The authors would like to acknowledge the funding from Foundation of ShaanXi University of Science and Technology (Grant No. 126021823), Natural Science Foundation of ShaanXi Province in China (Grant No. 2018JQ5164), Natural Science Foundation of Educational Department in ShaanXi Province, China (Grant No. 18JK0114), the National Natural Science Foundation of China (No. 11574273).

References (54)

  • X. Zhao et al.

    SnP0.94 nanoplates/graphene oxide composite for novel potassium-ion battery anode

    Chem. Eng. J.

    (2019)
  • X. Hu et al.

    Co3Sn2/SnO2 heterostructures building double shell micro-cubes wrapped in three-dimensional graphene matrix as promising anode materials for lithium-ion and sodium-ion batteries

    Chem. Eng. J.

    (2019)
  • S. Ding et al.

    Millimeter-scale laminar graphene matrix by organic molecule con fi nement reaction

    Carbon N. Y.

    (2020)
  • N. Anton et al.

    The universality of low-energy nano-emulsification

    Int. J. Pharm.

    (2009)
  • J.O. Besenhard et al.

    Filming mechanism of lithium-carbon anodes in organic and inorganic electrolytes

    J. Power Sources.

    (1995)
  • H. Bryngelsson et al.

    How dynamic is the SEI?

    J. Power Sources.

    (2007)
  • S. Lou et al.

    Pseudocapacitive Li + intercalation in porous Ti 2 Nb 10 O 29 nanospheres enables ultra-fast lithium storage

    Energy Storage Mater.

    (2018)
  • D. Andre et al.

    Characterization of high-power lithium-ion batteries by electrochemical impedance spectroscopy. I. Experimental investigation

    J. Power Sources.

    (2011)
  • M. Yao et al.

    Long cycle-life LiFePO 4 / Cu-Sn lithium ion battery using foam-type three-dimensional current collector

    J. Power Sources.

    (2010)
  • J. Xie et al.

    A retrospective on lithium-ion batteries

    Nat. Commun.

    (2020)
  • M.T. McDowell et al.

    25th anniversary article: Understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries

    Adv. Mater.

    (2013)
  • B. Li et al.

    Li0.35La0.55TiO3 Nanofibers Enhanced Poly(vinylidene fluoride)-based composite polymer electrolytes for all-solid-state batteries

    ACS Appl. Mater. Interfaces.

    (2019)
  • T. Kim et al.

    Lithium-ion batteries: outlook on present, future, and hybridized technologies

    J. Mater. Chem. A.

    (2019)
  • G.L. Zhu et al.

    Fast charging lithium batteries: Recent progress and future prospects

    Small.

    (2019)
  • H. Li et al.

    Circumventing huge volume strain in alloy anodes of lithium batteries

    Nat. Commun.

    (2020)
  • K. Feng et al.

    Silicon-based anodes for lithium-ion batteries: From fundamentals to practical applications

    Small.

    (2018)
  • M. Zheng et al.

    Hierarchically nanostructured transition metal oxides for lithium-ion batteries

    Adv. Sci.

    (2018)
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    Mr. Shukai and Mr. Wei have contributed equally to this work.

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