Synthesis and Electrochemical Performance of Red Phosphorus/Carbon Composites

doi:10.15541/jim20140611

Abstract

Abstract:

Effect of different fabrication methods, composition of electrolytes and various carbon substrates on the electrochemical performance of red phosphorus/carbon composites were studied. The red phosphorus (red P)/active carbon (AC) composites synthesized via ball milling method exhibited a low coulombic efficiency and cyclic capacity in the initial cycle, meaning poor utilization ratio of red P. It was found that the optimal electrolyte was 1 mol/L LiPF₆ in an ethyl carbonate (EC)/ethyl methyl carbonate (EMC)/dimethyl carbonate (DMC) mixed solvent. Red P/conductive carbon black (BP2000) and red P/AC composites were synthesized by a vapor deposition method. The morphology, structure and electrochemical performance of the as-prepared composites were characterized by thermal gravity analysis (TGA), X-ray diffraction (XRD), scanning electron microscope (SEM), BET surface analysis and cyclic voltammetry (CV). Electrochemical results reveal that the red P/AC composite (45%P) has a good reversibility with charge/discharge potential plateau at 1.0 V and 0.75 V. The initial discharge/charge special capacity is 1500 and 1200 mAh/g (calculated based on the weight of composites), respectively, showing initial coulombic efficiency of 82.5%. In the subsequent cycles the coulombic efficiency is over 97.5%. The stable cyclic capacity is related to 2.8-electron reaction. Relying on the stable discharge capacity in the second cycle, the capacity retention is calculated to be 75.0% after 50 cycles. The as-prepared red P/AC composites exhibit high cyclic capacity and good cyclic stability, which can be attributed to the uniform dispersion of amorphous red P in the porous structure of AC substrate, especially in the micropores.

Key words: lithium ion batteries, anode, red phosphorous, vapor deposition method, porous carbon

CLC Number:

TM912

TIAN Li-Yuan, YAO Zhi-Heng, LI Feng, WANG Yong-Long, YE Shi-Hai. Synthesis and Electrochemical Performance of Red Phosphorus/Carbon Composites[J]. Journal of Inorganic Materials, 2015, 30(6): 653-661.

Figures/Tables 11

Fig. 1 Electrochemical performance of 45% P/AC composites prepared by a ball-milling method (a) CV curves, (b) Initial three charge (delithiation)-discharge (lithiation) curves of P/AC composite and (c) cycle performance of P/AC composite. Current density is 100 mA/g, the scan rate is 0.1 mV/s

Fig. 2 SEM images of AC (a) and red P/AC composites (b)

Fig. 3 The initial three charge-discharge curves (a, b and c) and cycle performance (d, e and f) of P/AC composite in different electrolytes

Fig. 4 XRD patterns of pure phosphorous, carbon and composites

Fig. 5 SEM images of BP2000 (a), P/BP2000 (b), AC (c) and P/AC (d)

Table 1 Surface area and pore-structure parameters of carbon substrates and corresponding red P/carbon composites

Sample	S/(m²·g^-1)			V /(cm³·g^-1)		Pore size/nm
Sample	S_BET	S_meso	S_micro	V_meso	V_micro	D_meso	D_micro
Blank BP2000	1128.1	758.2	369.9	0.86	0.57	2.00	0.63
Red P/BP2000	275.2	378.2	164.4	0.50	0.08	2.48	1.06
Subtracted value	852.9	380	205.5	0.36	0.49	-	-
Blank AC	1528.2	627.5	900.7	0.46	0.88	1.93	0.64
Red P/AC	127.1	185.9	55.6	0.20	0.02	2.55	1.05
Subtracted value	1401.1	441.6	844.4	0.26	0.86	-	-

Fig. 6 CV curves of P/BP2000 (a) and P/AC (b) composites

Fig. 7 Initial three charge-discharge curves (a) and cycle performance (b) of P/BP2000 composite (45%), initial three charge-discharge curves (c) and cycle performance (d) of P/AC composite (45%)

Fig. S1 The capacity contribution of inactive component. (a and b) The initial 3 charge/discharge curves and cycle performance of BP2000 blank anode (BP2000, PTFE and AB with weight ratio of 38.5:10:20). (c and d) The initial 3 charge/discharge curves and cycle performance of AC blank anode (AC, PTFE and AB with weight ratio of 38.5:10:20)

Fig. S2 TGA of the as-prepared red P/BP2000(a)and red P/AC(b)composites

Fig. S 3 Raman Spectra of pure carbon and composites

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