GeP3/科琴黑复合材料作为钠离子电池高性能负极材料

doi:10.15541/jim20240360

摘要/Abstract

摘要：

金属磷化物因具有比其他阳极材料更高的比容量而作为潜在的钠离子电池(SIBs)阳极材料。然而, 其体积膨胀和导电性差, 导致SIBs的容量衰减快, 循环寿命短。因此, 本研究采用高能球磨法制备GeP₃, 然后进行二次球磨, 通过引入科琴黑(KB), 合成GeP₃/KB复合阳极材料。球磨过程使得GeP₃和KB紧密结合, 形成强有力的化学键, 因此GeP₃/KB阳极表现出优异的储钠性能。GeP₃/KB-600-40样品(第二次球磨速度600 r/min, 球磨时间40 h)在0.05 A·g^-1的电流密度下获得了933.41 mAh·g^-1的高可逆容量; 在2 A·g^-1的高电流密度下循环200次后容量仍保持在314.52 mAh·g^-1, 容量保持率为66.6%。本研究表明, 通过高能球磨法制备的合金-碳复合阳极材料, 可以缓解阳极在循环过程中产生的体积膨胀, 增大SIBs容量和改善循环稳定性。

关键词: 钠离子电池, GeP₃/C复合材料, 科琴黑, 高能球磨法

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

中图分类号:

TM911

杨舒琪, 杨存国, 牛慧祝, 石唯一, 舒珂维. GeP₃/科琴黑复合材料作为钠离子电池高性能负极材料[J]. 无机材料学报, 2025, 40(3): 329-336.

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.

图/表 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/科琴黑复合材料作为钠离子电池高性能负极材料

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

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