GeP3/Ketjen Black Composite: Preparation via Ball Milling and Performance as Anode Material for Sodium-ion Batteries

doi:10.15541/jim20240360

Abstract

Abstract:

Metal phosphides have been studied as prospective anode materials for sodium-ion batteries (SIBs) due to their higher specific capacity compared to other anode materials. However, rapid capacity decay and limited cycle life caused by volume expansion and low electrical conductivity of phosphides in SIBs remain still unsolved. To address these issues, GeP₃ was first prepared by high-energy ball milling, and then Ketjen black (KB) was introduced to synthesize composite GeP₃/KB anode materials under controlled milling speed and time by a secondary ball milling process. During the ball milling process, GeP₃and KB form strong chemical bonds, resulting in a closely bonded composite. Consequently, the GeP₃/KB anodes was demonstrated excellent sodium storage performance, achieving a high reversible capacity of 933.41 mAh·g^-1 at a current density of 0.05 A·g^-1 for a special formula of GeP₃/KB-600-40 sample prepared at ball milling speed of 600 r/min for 40 h. Even at a high current density of 2 A·g^-1 over 200 cycles, the capacity remains 314.52 mAh·g^-1 with a retention rate of 66.6%. In conclusion, this work successfully prepares GeP₃/KB anode-carbon composite for electrodes by high-energy ball milling, which can restrict electrode volume expansion, enhance capacity, and improve cycle stability of SIBs.

Key words: sodium-ion battery, GeP₃/C composite, Ketjen black, ball milling

CLC Number:

TM911

YANG Shuqi, YANG Cunguo, NIU Huizhu, SHI Weiyi, SHU Kewei. GeP₃/Ketjen Black Composite: Preparation via Ball Milling and Performance as Anode Material for Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2025, 40(3): 329-336.

Figures/Tables 10

Fig. 1 Characterization of synthetic GeP3/KB (a) Schematic diagram of GeP3/KB synthesis; (b) XRD patterns of GeP3 and GeP3/KB composites; (c) Raman spectra of GeP3 and GeP3/KB composites

Fig. 2 High resolution XPS spectra of GeP3/KB nanocomposites (a) C1s XPS spectrum of GeP3/KB-600-40; (b-d) P2p XPS spectra of (b) GeP3/KB-600-40, (c) GeP3/KB-300-40 and (d) GeP3/KB-500-40. Colorful figures are available on website

Fig. 3 SEM images and EDS mappings of (a-c) GeP3 and (d-i) GeP3/KB-600-40 (a) SEM image of GeP3; (b, c) EDS mappings of P and Ge in GeP3; (d) SEM image of GeP3/KB-600-40; (e-i) EDS mappings of C, O, P and Ge in GeP3/KB-600-40

Fig. 4 (a, b) TEM images and (c, d) SAED patterns of GeP3/KB-600-40

Fig. 5 Electrochemical performance of GeP3 and GeP3/KB composites (a) Initial and (b) second charge-discharge curves of bare GeP3 and GeP3/KB electrodes; (c) Rate performance of bare GeP3 and GeP3/KB electrodes at 0.05, 0.1, 0.5, 1 and 2 A·g-1; (d) Cycling performance of all electrodes at 2 A·g-1 Colorful figures are available on website

Fig. 6 CV curves of (a) GeP3 and (b) GeP3/KB-600-40, and (c) Nyquist plots of all electrodes with inset showing equivalent circuit Colorful figures are available on website

Fig. S1 XPS survey spectra of GeP3/KB

Fig. S2 CV curves with calculated capacitive contribution of GeP3/KB-600-40 Scan rates of (a) 0.2, (b) 0.4, (c) 0.6 (d) 0.8 and (e) 1.0 mV·s-1

Fig. S3 (a) Relationship between peak current and scan rate in logarithmic format and (b) capacitance contribution at different scan rates of GeP3/KB-600-40

Fig. S4 SEM images of (a, b) bare GeP3 and (c, d) GeP3/KB-600-40 (a, c) before and (b, d) after 100 cycles

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GeP₃/Ketjen Black Composite: Preparation via Ball Milling and Performance as Anode Material for Sodium-ion Batteries

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