Synergistic effect of graphene nanoperforation on the reversibility of the conversion reaction of a SnO2/nanoperforated graphene composite

doi:10.1016/j.cej.2021.128542

Chemical Engineering Journal

Volume 417, 1 August 2021, 128542

https://doi.org/10.1016/j.cej.2021.128542 Get rights and content

Highlights

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Catalytic carbon gasification introduced graphene nanoperforations.
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Nanoperforations are introduced at the contact points of SnO₂ with graphene.
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Graphene nanoperforations increased Sn/Li₂O interfacial area.
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Nanoperforations improved the conversion reaction of Sn and Li₂O to SnO₂.
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Nanoperforations effectively accommodate the volume change of SnO₂.

Abstract

Metal oxide (MO_x)-based anodes suffer from large capacity loss and low Coulombic efficiency due to the irreversible formation of Li₂O during the conversion reaction. Despite numerous studies addressing this issue, the development of MO_x-based anode materials with high cycle reversibility remains a critical challenge. In this study, the reversibility of the conversion reaction of Sn and Li₂O to SnO₂ is significantly improved through the innovative design of a SnO₂/nanoperforated graphene composite as an anode material. Nanoperforations are introduced at the contact points of SnO₂ with graphene to increase the interfacial area of Sn/Li₂O, which resulted in improved reversibility of the conversion reaction. Ex-situ high-resolution transmission electron microscopy imaging coupled with selected area electron diffraction pattern, ex-situ XRD and XPS analyses corroborate the improved reversibility of the conversion reaction. The specific charge capacity of SnO₂ in the SnO₂/nanoperforated graphene composite is 1446 mAh g⁻¹ at the current density of 100 mA g⁻¹, which is very close to the theoretical capacity of SnO₂ (1494 mAh g⁻¹ based on the fully reversible conversion reaction and alloying/de-alloying reaction). Furthermore, the maintenance of the initial differential capacity plots after 800 cycles demonstrates the improved reversibility of the conversion reaction of the SnO₂/nanoperforated graphene composite over extended cycles. These results provide important insights into the rational design of MO_x-based anode materials using nanoperforated graphene with improved reversibility of the conversion reaction for Li-ion batteries.

Graphical abstract

Introduction

Commercial graphite, a typical anode material for Li-ion batteries (LIBs), has a theoretical capacity of 372 mAh g⁻¹ based on the intercalation reaction. Therefore, developing alternative electrode materials with higher specific capacity is vital for realizing next-generation LIBs with high energy density [1], [2], [3], [4]. Among anode materials, metal oxides (MO_x) that facilitate conversion reaction have attracted extensive attention due to their high specific capacities [3], [4], [5], [6], [7]. For example, tin dioxide (SnO₂) has been considered as one of the most promising alternative anode materials for LIBs [5], [6], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19]. However, MO_x-based anode materials suffer from three main drawbacks: irreversible conversion reaction of M/Li₂O to MO_x during initial cycles, large volume change during lithiation/delithiation processes, and low electrical conductivity [1], [9], [20], [21], [22], [23]. Among these drawbacks, the irreversible conversion reaction associated with the formation of Li₂O is the main cause of large capacity loss and low Coulombic efficiency (CE) [5], [9]. During the conversion reaction, MO_x is converted to metallic M and Li₂O such that metallic M is embedded in the Li₂O layer during the discharge process [2], [9], [22], [24]. During the following charge process, the interface of M and Li₂O acts as a reaction site for the formation of MO_x through the interdiffusion of M and O [25]. Therefore, the interfacial area of the M/Li₂O interface is of critical importance for the conversion reaction [9], [24], [25].

Despite numerous studies on MO_x-based anode materials, the role of the M/Li₂O interface on the reversibility of the conversion reaction of nanosized MO_x has been rarely studied [26], [27], [28], [29]. Recently, Hu et al. reported that the reversibility of the conversion reaction of a magnetic-sputtered SnO₂ film is closely related to the interfacial area of Sn/Li₂O [24]. Additionally, SnO₂ prepared in the form of a nanocomposite with graphene has been reported to exhibit partially improved reversibility of the conversion reaction during initial cycles, because the composite would suppress the aggregation of SnO₂ and increase the electrical conductivity [5], [26]. The incorporation of nanosized transition metals (Co, Ni, Fe, Mn, Cu) as catalysts was also reported to promote the decomposition of inactive Li₂O, leading to improved reversibility of the conversion reaction of Sn/Li₂O to SnO₂ [1], [2], [9], [10], [22], [25], [30]. It should however be noted that, in previous studies, improved reversibility of SnO₂ was observed only in the initial few cycles, and a noticeable capacity decay occurred upon further cycling. Therefore, improving the reversibility of the conversion reaction during prolonged cycling remains a critical challenge for MO_x-based anode materials [31], [32].

Here, we report the achievement of greatly improved reversibility of the conversion reaction of Sn/Li₂O to SnO₂ during long cycling through the innovative design of a SnO₂/nanoperforated graphene composite. Nanoperforations were introduced at the contact points of SnO₂ and graphene to 1) increase the interfacial area of Sn/Li₂O and 2) effectively accommodate the volume change of SnO₂, which led to improved reversibility of the conversion reaction. The results of ex-situ high-resolution transmission electron microscopy (HRTEM) imaging coupled with selected area electron diffraction (SAED) pattern, ex-situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses, and differential capacity plots corroborated the improved reversibility of the conversion reaction. Remarkably, the specific charge capacity of SnO₂ in the SnO₂/nanoperforated graphene composite is 1446 mAh g⁻¹ at the current density of 100 mA g⁻¹, which is very close to the theoretical capacity of SnO₂ (1494 mAh g⁻¹ based on the fully reversible conversion reaction and alloying/de-alloying reaction). Furthermore, the maintenance of the initial differential capacity plots after 800 cycles suggests the improvement in the reversibility of the conversion reaction of SnO₂/nanoperforated graphene composite over extended cycles.

Section snippets

Preparation of graphene oxide (GO) by Hummer’s method

Graphite oxide was prepared from bulk graphite flakes (∼45 µm, 99.99%, Aldrich) by a modified Hummer’s method using concentrated sulfuric acid (H₂SO₄, 95%, Samchun Chemicals), potassium permanganate (KMnO₄, 99%, Aldrich), and hydrogen peroxide (35 wt% in water, Aldrich) [33]. The as-prepared graphite oxide was then exfoliated and dispersed in deionized water using an ultrasonicator to obtain a stable GO suspension with a concentration of 1.0 mg mL⁻¹.

Preparation of the SnO₂/reduced graphene oxide (RGO) microspherical composite

The SnO₂/RGO microspherical composites were

Results and discussion

Fig. 1 illustrates the schematics of the SnO₂/reduced graphene oxide (SnO₂/RGO) composite (without perforations) and SnO₂/nanoperforated graphene (SnO₂/NPG) composite with 5–10 nm perforations. In previous studies on the solution-based deposition of metal and metal oxide nanoparticles on GO, the nanoparticles were formed on the hydrophilic GO with a planar contact and their morphology was described as hemispherical [35], [36]. For the preparation of SnO₂/RGO, SnCl₂ was added to an aqueous

Conclusions

In this report, we presented the innovative material design of a SnO₂/nanoperforated graphene composite, which greatly improved the reversibility of the conversion reaction of Sn/Li₂O to SnO₂ during prolonged cycling. Precisely controlled nanoperforations generated at the contact points of SnO₂ on graphene effectively enhanced the reversibility of the conversion reaction of Sn/Li₂O to SnO₂ owing to an increase in the interfacial area of Sn/Li₂O and thus the exposure of a larger quantity of SnO₂

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

This research was supported by the Technology Innovation Program (20004958, Development of ultra-high performance supercapacitor and high power module) funded by the Ministry of Trade, Industry & Energy (MOTIE, Korea).

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Citation Excerpt :
The pore size distribution showed a narrow peak at pore size of 4 nm for all samples of N-RSB, PSB, and N-PSB. The narrow peaks observed at ∼4 nm for the samples have been reported to be due to the tensile-strength effect of N2 desorption. [69] Accordingly, this peak observed at ∼4 nm is not related with perforation.
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Synergistic effect of graphene nanoperforation on the reversibility of the conversion reaction of a SnO2/nanoperforated graphene composite

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Preparation of graphene oxide (GO) by Hummer’s method

Preparation of the SnO2/reduced graphene oxide (RGO) microspherical composite

Results and discussion

Conclusions

Declaration of Competing Interest

Acknowledgements

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Highly stable SnO2-Fe2O3-C hollow spheres for reversible lithium storage with extremely long cycle life

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Preparation of SnO₂/carbon composite hollow spheres and their lithium storage properties

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