Regular ArticleOrganic molecule confinement reaction for preparation of the Sn nanoparticles@graphene anode materials in Lithium-ion battery
Graphical abstract
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 CH 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).
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Mr. Shukai and Mr. Wei have contributed equally to this work.