Sn4P3 nanoparticles confined in multilayer graphene sheets as a high-performance anode material for potassium-ion batteries

doi:10.1016/j.jechem.2021.08.043

Journal of Energy Chemistry

Volume 66, March 2022, Pages 413-421

https://doi.org/10.1016/j.jechem.2021.08.043 Get rights and content

Abstract

Phosphorus-based anodes are highly promising for potassium-ion batteries (PIBs) because of their large theoretical capacities. Nevertheless, the inferior potassium storage properties caused by the poor electronic conductivity, easy self-aggregation, and huge volumetric changes upon cycling process restrain their practical applications. Now we impregnate Sn₄P₃ nanoparticles within multilayer graphene sheets (Sn₄P₃/MGS) as the anode material for PIBs, greatly improving its potassium storage performance. Specifically, the graphene sheets can efficiently suppress the aggregation of Sn₄P₃ nanoparticles, enhance the electronic conductivity, and sustain the structural integrity. In addition, plenty of Sn₄P₃ nanoparticles impregnated in MGS offer a large accessible area for the electrolyte, which decreases the diffusion distance for K⁺ and electrons upon K⁺ insertion/extraction, resulting in an improved rate capability. Consequently, the optimized Sn₄P₃/MGS containing 80 wt% Sn₄P₃ (Sn₄P₃/MGS-80) exhibits a high reversible capacity of 378.2 and 260.2 mAh g⁻¹ at 0.1 and 1 A g⁻¹, respectively, and still delivers a large capacity retention of 76.6% after the 1000th cycle at 0.5 A g⁻¹.

Graphical abstract

Sn₄P₃ ultrasmall nanoparticles embedded in multilayer graphene sheets (Sn₄P₃/MGS) were synthesized via a ball-milling method and used as an advanced anode material for potassium-ion batteries.

Introduction

The rapid expansion of commercial electronic vehicles and grid energy storage calls for high-energy–density and inexpensive rechargeable batteries [1], [2], [3], [4]. Potassium, with wide availability of mineral reserves and low standard electrode potential (–2.93 V vs. SHE), close to lithium (–3.04 V vs. SHE), enables potassium-ion batteries (PIBs) an attractive alternative to lithium-ion batteries (LIBs) in stationary energy storage systems [5], [6], [7], [8], [9]. Besides, it has been reported that K ion-based electrolytes can display superior ionic conductivity than those of Li⁺ and Na⁺ caused by the weaker interactions between potassium ions and organic electrolyte solvents, which is favorable for achieving the ideal rate performance of the cell device [10], [11], [12], [13], [14]. Nonetheless, it is a great challenge to overcome the difficulty concerning the huge volumetric changes upon cycling arising from the larger size of K⁺ (1.38 Å) [15], [16], [17], [18], [19], [20].

Tin phosphides have captured considerable attention as a class of materials relying on their unique physical characteristics, chemical properties, and crystal phases. Among these tin phosphides, metal-rich rhombohedral Sn₄P₃ has a great development prospect as an anode material for alkali-ion batteries because it has the advantages of high theoretical capacity, layered crystal structure, and metallic nature [21], [22], [23], [24], [25]. The theoretical capacity of the Sn₄P₃ anode is 614 mAh g⁻¹, which is achieved by the generation of K₃P and KSn phases via sequential conversion and alloying reactions in the potassiation process [26]. However, such reactions are always accompanied by severe volumetric expansion/contraction, giving rise to the pulverization of the anode and poor cycling stability [27], [28]. Guo’s group firstly prepared a Sn₄P₃/C anode of PIBs through a ball-milling method. The obtained electrode showed a high capacity of about 384.8 mAh g⁻¹ at 0.05 A g⁻¹, exceeding most of the reported anodes for PIBs [29]. Unfortunately, though the combination of carbon could enhance the structure stability to some degree, the anode experienced serious capacity decay after only 35 cycles, which resulted from the large particle diameter and self-agglomeration of Sn₄P₃ nanoparticles [30], [31].

In this work, ultrasmall Sn₄P₃ nanoparticles uniformly confined in multilayer graphene sheets (Sn₄P₃/MGS) were fabricated by using a high-energy ball-milling approach and used as an anode material for PIBs. The ultrafine and evenly distributed Sn₄P₃ nanoparticles and highly conductive MGS endue Sn₄P₃/MGS with prominent transporting dynamics for both electrons/ions. Furthermore, MGS can efficiently buffer the expansion of Sn and P upon cycling processes, which maintains the structural integrity of the hybrid. By optimizing the proportion of Sn₄P₃ to MGS, a Sn₄P₃/MGS hybrid with optimal electrochemical properties was obtained, which delivered a reversible capacity of 393.3 mAh g⁻¹ at 0.1 A g⁻¹ after 100 cycles, and good rate performance of 215.7 mAh g⁻¹ at a high current density of 2 A g⁻¹.

Section snippets

Material synthesis

Sn₄P₃ nanoparticles were initially fabricated via a high-energy ball-milling strategy using stannum (Aladdin, 99.5%) and red phosphorus powders (Alfa Aesar, 98.9%) as the raw materials with a molar proportion of 4:3. Then by milling 800 mg Sn₄P₃ and 200 mg expanded graphite (XFNANO) (in a weight ratio of 8:2), the final product Sn₄P₃/MGS-80 can be achieved. All the above ball milling processes were conducted under an Ar atmosphere for 100 min. For comparison, Sn₄P₃/MGS-70 and Sn₄P₃/MGS-90 were

Results and discussion

Fig. 1 shows the detailed synthesis procedures for the Sn₄P₃/MGS-80 nanocomposite. In the first step, the Sn₄P₃ particles were facilely synthesized from the reaction between the tin and phosphorus powder in a high-energy ball-milling tank. Subsequently, these Sn₄P₃ particles were milled with expanded graphite, during which expanded graphite was transformed into multilayer graphene sheets and Sn₄P₃ particles were uniformly confined in these graphene sheets, resulting in the Sn₄P₃/MGS-80 hybrid.

Conclusions

In conclusion, we developed a facile high-energy ball-milling route to homogeneously load Sn₄P₃ nanoparticles between multilayered graphene sheets as new anode materials for PIBs. Benefiting from the large surface area-to-volume ratio, superior structural stability upon the potassiation/depotassiation process, and high overall electronic conductivity, the Sn₄P₃/MGS-80 electrode delivers a large charge capacity (378.2 mAh g⁻¹ at 0.1 A g⁻¹), remarkable rate property (260.2 mAh g⁻¹ at 1 A g⁻¹),

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.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (22075147) and the Natural Science Foundation of Jiangsu Province of China (BK20180086).

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¹: These authors contributed equally to this work.

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Sn4P3 nanoparticles confined in multilayer graphene sheets as a high-performance anode material for potassium-ion batteries

Abstract

Graphical abstract

Introduction

Section snippets

Material synthesis

Results and discussion

Conclusions

Declaration of Competing Interest

Acknowledgments

Joule

J. Energy Chem.

J. Energy Chem.

Nano Energy

Chem. Eng. J.

J. Energy Chem.

Carbon

J. Alloys Compd.

Appl. Surface Sci.

Sci. Bull.

Energy Storage Mater.

J. Energy. Chem.

Nano Energy

J. Alloys Compd.

J. Alloys Compd.

Chem. Eng. J.

Science

Chem. Soc. Rev.

Adv. Mater.

Chem. Rev.

Energy Environ. Mater.

Angew. Chem. Int. Ed.

J. Energy Chem.

Adv. Mater.

Adv. Mater.

Adv. Mater.

Small

Sn₄P₃ nanoparticles confined in multilayer graphene sheets as a high-performance anode material for potassium-ion batteries