Composite of graphite/phosphorus as anode for lithium-ion batteries

doi:10.1016/j.jpowsour.2015.04.168

Journal of Power Sources

Volume 289, 1 September 2015, Pages 100-104

https://doi.org/10.1016/j.jpowsour.2015.04.168 Get rights and content

Highlights

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Graphite/Phosphorus composite anode shows promising performance.
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The composite anode presents high reversible capacity of 500 mAh g⁻¹ and good cycleability.
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Performance of a composite|LiFePO₄ full-cell shows easy SOC evaluation.
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This paves a new way for exploring new battery chemistry.

Abstract

Graphite/Phosphorus composite anodes are prepared by mixing graphite and the phosphorus/carbon material, which prepared by heating the mixture of red phosphorus and porous carbon. Their electrochemical performances are evaluated as anodes for Li-ion batteries. A graphite/Phosphorus composite|LiFePO₄ full-cell is also attempted. When the phosphorus/carbon content in the composite anode is 28.6 wt.%, the composite anode presents high reversible capacity of 500 mAh g⁻¹ and considerable cycleability comparable to that of graphite anode, showing promising performance.

Introduction

Lithium-ion batteries play important roles in the field of energy storage and electric vehicles, and the increasing demand on the energy density encourages exploration on new battery chemistry [1], [2], [3], [4], [5], [6]. Therefore, it is a hot topic to investigate novel anode or cathode materials with high energy density [7], [8], [9], [10].

Elemental phosphorus is a promising anode candidate due to its high gravimetric and volumetric energy density [11], [12], [13], [14], [15], [16]. Cheol-Min Park and Hun-Joon Sohn [17] prepared black-P/carbon black composite using a high energy mechanical milling technique. The composite shows considerably high coulombic efficiency during the first cycle (90%) and a good cycling performance (600 mAh g⁻¹) between 0.78 and 2 V vs. Li⁺/Li. An amorphous P/C nanocomposite prepared by ball-milling red phosphorus (red-P) and conductive carbon powders was reported by Jiangfeng Qian et al. [18], and shows high lithium storage capacity near the theoretical (2592 mAh g⁻¹) and perfect cycling stability. In detail, its reversible capacity is 2355 mAh g⁻¹ at the 2nd discharge, and the capacity retention is 90% after 100 cycles. Weihan Li et al. [19] prepared porous carbon nanofibers encapsulated with crystalline red P by electrospinning of polyacrylonitrile/poly(methyl methacrylate) and thermal carbonization process. The P-PCNFs delivered a high cyclability of 2030 mAh g⁻¹ at 0.1 C rate after 100 cycles and outstanding rate capability of 380 mAh g⁻¹ at 11C for 10 cycles. Using the sublimation of red-P, our group [20] designed thermal vapour deposition to realize the embedding of red-P nanoparticles into the pores of porous carbon, and the as-prepared composite is named as P@C. The structure of P@C composite is effective to avoid the disadvantages of phosphorus, in terms of poor conductivity, large volume change during lithiation/delithiation, chemical instability in atmosphere and possible safety issue. Furthermore, the composite particle in micro-size is important to fit the state-of-art for mass production of Li-ion batteries, as well as ensuring considerably high volumetric energy density. However, similar to all the novel electrode material (i.e. Si-based anode material), the application of P@C material in a commercial battery still needs more engineering research.

On the other hand, though graphite anode has been well studied and widely used in commercial Li-ion batteries, it still encounters many problems. As we all known, the over-charging and over-discharging of a battery is considered to shorten the service life of a power source. Therefore, it is necessary to regulate the charge and discharge potentials. However, graphite anode delivers relatively flat charging and discharging platforms, so the detectors have to be sensitive and accurate when judging battery charging boundary by voltage. Since the lithiation/delithiation potential of P@C is slightly higher than that of graphite, the capacity boundary of the battery may be tailored by the composite anode consisting of graphite and P@C. Though the higher lithiation potential of P@C leads to lower working voltage of the battery, the increase in capacity may compensate the energy loss. In this sense, graphite/P@C composite anode will facilitate the state of charge management of the battery.

In this paper, we explored the preparation of graphite/P@C composite anode, as well as its electrochemical performance. The results indicate that the novel composite anode presents high specific capacity and merit for easy SOC (State-Of-Charge) evaluation. In addition, the electrochemical performances of graphite/P@C|LiFePO₄ full-cell are also investigated.

Section snippets

Synthesis of the P@C material

The P@C material was prepared by thermal vapour deposition as reported [11]. Activated carbon and excess red phosphorus were placed into a vessel separately, then the vessel was heated to 450 °C. The phosphorus sublimated and diffused into the pores by capillary force and pressure difference, whereupon it was adsorbed and deposited on the internal surface of the activated carbon. The phosphorus in the composite was measured to be 43.47 wt.%.

Preparation of electrodes and batteries

A series of graphite/P@C mixtures, with P@C content of

Results and discussions

The P@C composite was characterized by scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). The SEM images (Fig. S1a, b) and the carbon (Fig. S1c) and phosphorus (Fig. S1d) elemental mapping images show that phosphorus is homogeneously distributed in the framework of the porous carbon, while a little on the external surface. The XRD patterns (Fig. S2) show that all the typical lines for red-phosphous are disappeared except the line near 15°, indicating that the phosphous in

Conclusion

P@C material is pushed forward to practical application for Li-ion batteries by the composite of graphite/P@C as anode electrode in this study. The results show that the capacity, potential, columbic efficiency and cycling stability can be reasonably improved by tuning the content of the graphite/P@C composite anode. In particular, when the content of P@C material is 28.6 wt.%, the composite anode presents considerably high reversible capacity (500 mAh g⁻¹) and cycleability when comparing with

Acknowledgements

This work is supported by NFSC (No. 20901046), MOST (Grant No. 2011CB935902), Beijing Municipal Program (Grant No. YETP0157).

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Short communicationComposite of graphite/phosphorus as anode for lithium-ion batteries

Highlights

Abstract

Introduction

Section snippets

Synthesis of the P@C material

Preparation of electrodes and batteries

Results and discussions

Conclusion

Acknowledgements

J. Power Sources

J. Power Sources

Electrochem. Commun.

Electrochim Acta

Carbon

Nature

Adv. Mater.

Chem. Mater.

J. Mater. Chem.

J. Am. Chem. Soc.

Short communication
Composite of graphite/phosphorus as anode for lithium-ion batteries