硼氮共掺杂生物质碳球负极材料的制备及其储钠性能

doi:10.15541/jim20250187

摘要/Abstract

摘要：

硬碳具有成本低廉、来源广泛、使用寿命长等优点, 是一种极具发展前景的钠离子电池负极材料。然而, 其较低的首次库仑效率(ICE)和较差的倍率性能, 限制了实际应用。目前, 杂原子掺杂是调控无定形碳微观结构, 提高碳基材料储钠性能的有效方法。与单原子掺杂相比, 多原子掺杂产生的协同效应有利于增强材料的电化学反应活性。本研究以从马铃薯淀粉加工废液中提取的废渣为前驱体, 通过水热反应合成了碳球, 在此基础上采用尿素、四硼酸钠作为掺杂源, 利用球磨和热解的方法制备了硼氮共掺杂生物质碳球。随后, 探究了多原子掺杂对碳材料微观形貌及储钠性能的影响。结果表明: 硼、氮共掺杂提高了材料的无序度, 扩大了层间距, 同时形成了合适的、有利于生成稳定固体电解质界面膜的C=O键。在50 mA·g^-1的电流密度下, 其可逆比容量为284.3 mAh·g^-1, ICE为77.0%。在2 A·g^-1下循环500圈后, 比容量衰减至122.5 mAh·g^-1, 容量保持率为56.1%。

关键词: 钠离子电池, 负极材料, 马铃薯废渣, 纳米碳球, 硼氮共掺杂

Abstract:

Hard carbon is a promising anode material for sodium-ion batteries due to its low cost, wide source and long lifespan. However, its lower initial Coulombic efficiency (ICE) and poor capacity limit its practical applications. At present, heteroatom doping is an effective strategy to modulate the amorphous carbon microcrystalline structure and improve the sodium storage performance of carbon materials. The synergistic effect generated by combined heteroatom doping is more conducive to enhancing the electrochemical reactivity of carbon materials than single heteroatom doping. In this study, carbon spheres were synthesized by hydrothermal reaction, with waste residue extracted from potato starch processing waste liquid as precursor, based on which boron and nitrogen co-doped biomass carbon spheres were prepared by ball milling and pyrolysis using urea and sodium tetraborate as doping sources. Subsequently, the effects of B and N co-doping on the microstructure and sodium storage properties of carbon materials were investigated. The results indicated that B and N co-doping increased disorder and enlarged layer spacing of carbon materials, while forming suitable C=O bonds that were conducive to stabilizing solid electrolyte interphase film generation. The as-prepared electrode exhibited a reversible capacity of 284.3 mAh·g^-1 at a current density of 50 mA·g^-1 with an ICE of 77.0%. After 500 cycles at 2 A·g^-1, its capacity decayed to 122.5 mAh·g^-1, with 56.1% capacity retention. Therefore, boron and nitrogen co-doped biomass carbon sphere anode material is a promising one for sodium-ion batteries with superior sodium storage properties.

Key words: sodium-ion battery, anode material, potato residue, carbon nanosphere, boron and nitrogen co-doping

中图分类号:

O646

马晓佳, 耿欣宇, 张卫珂. 硼氮共掺杂生物质碳球负极材料的制备及其储钠性能[J]. 无机材料学报, 2026, 41(4): 469-478.

MA Xiaojia, GENG Xinyu, ZHANG Weike. Boron and Nitrogen Co-doped Biomass Carbon Sphere Anode Material: Preparation and Sodium Storage Properties for Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2026, 41(4): 469-478.

图/表 12

图1 N@NHCS-600、B@N@NHCS-900和NHCS-900的制备流程图

Fig. 1 Schematic diagram of synthesis process for N@NHCS-600, B@N@NHCS-900 and NHCS-900

图2 (a, b) N@NHCS-600、(c, d) B@N@NHCS-900和(e, f) NHCS-900的SEM照片

Fig. 2 SEM images of (a, b) N@NHCS-600, (c, d) B@N@NHCS-900 and (e, f) NHCS-900

图3 (a) NHCS-900和(b) B@N@NHCS-900的HRTEM照片(插图为方框区域层间距的FFT谱图); (c) B@N@NHCS-900的STEM照片及C、O、N、B元素分布图

Fig. 3 (a, b) HRTEM images of (a) NHCS-900 and (b) B@N@NHCS-900 with inserts showing the corresponding FFT patterns for measuring the interlayer distance in square areas; (c) STEM image and C, O, N and B element mappings of B@N@NHCS-900

图4 N@NHCS-600、B@N@NHCS-900和NHCS-900的(a) XRD图谱、(b)拉曼谱图、(c)氮气吸脱附等温曲线和(d)孔径分布图

Fig. 4 (a) XRD patterns, (b) Raman spectra, (c) N2 adsorption-desorption isotherms and (d) pore size distributions of N@NHCS-600, B@N@NHCS-900 and NHCS-900

图5 N@NHCS-600、B@N@NHCS-900和NHCS-900的(a) XPS总谱图, 高分辨(b) C1s、(c) O1s和(d) N1s XPS谱图; (e) B@N@NHCS-900的高分辨B1s XPS谱图

Fig. 5 (a) XPS survey spectra, high resolution (b) C1s, (c) O1s and (d) N1s XPS spectra of N@NHCS-600, B@N@NHCS-900 and NHCS-900; (e) High resolution B1s XPS spectrum of B@N@NHCS-900

图6 (a) N@NHCS-600、(b) B@N@NHCS-900和(c) NHCS-900的CV曲线

Fig. 6 CV curves of (a) N@NHCS-600, (b) B@N@NHCS-900 and (c) NHCS-900 Colorful figures are available on website

图7 N@NHCS-600、B@N@NHCS-900和NHCS-900的电化学性能

Fig. 7 Electrochemical properties of N@NHCS-600, B@N@NHCS-900 and NHCS-900 (a) Rate capability; (b) First charge-discharge curves at a current density of 0.05 A·g-1; (c) Capacity contribution of the slope/plateau region in the 2nd discharge curves; (d, e) Cycling performance at (d) 0.1 and (e) 2 A·g-1. Colorful figures are available on website

图8 B@N@NHCS-900的动力学分析

Fig. 8 Dynamic analysis of B@N@NHCS-900 (a) CV curves from 0.2 to 1.0 mV·s-1; (b) Fitting line of scan rate and peak current; (c) Capacitive contribution at 0.4 mV·s-1; (d) Ratios of diffusion and capacitance contributions at different scan rates. Colorful figures are available on website

图9 N@NHCS-600、B@N@NHCS-900和NHCS-900的(a) GITT曲线和(b)扩散系数曲线

Fig. 9 (a) GITT curves and (b) corresponding diffusion coefficients of N@NHCS-600, B@N@NHCS-900 and NHCS-900

图10 N@NHCS-600、B@N@NHCS-900和NHCS-900的(a) EIS谱图和(b)等效电路图

Fig. 10 (a) EIS spectra of N@NHCS-600, B@N@NHCS-900 and NHCS-900, and (b) corresponding equivalent circuit Colorful figure is available on website

表S1 不同样品的结构参数

Table S1 Structural parameters of different samples

Sample	d₍₀₀₂₎/nm	I_D/I_G	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	XPS content/% (in atom)
Sample	d₍₀₀₂₎/nm	I_D/I_G	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	C	O	N	B
N@NHCS-600	-	2.21	442.4	0.189	89.52	6.79	3.69	-
B@N@NHCS-900	0.385	2.07	249.1	0.109	89.49	5.89	2.98	1.64
NHCS-900	0.378	1.91	94.9	0.064	95.96	3.56	0.48	-

表S2 B@N@NHCS-900负极材料与近期文献报道的钠离子电池负极材料的电化学性能对比

Table S2 Comparison of electrochemical performance of B@N@NHCS-900 anode with other carbon anode materials for sodium ion storage reported in previous literatures

Sample	Rate performance		Cycling performance			Ref.
Sample	Capacity/(mAh·g^-1)	Current density/(A·g^-1)	Capacity/(mAh·g^-1)	Current density /(A·g^-1)	Cycle number	Ref.
BHCS-1200	234	0.03	180	0.1	100	[33]
BHCS-1200	Below 100	2	180	0.1	100	[33]
NPUCS	257.7	0.1	255.1	0.1	200	[38]
NPUCS	157.0	5	110.0	5	2000	[38]
PB-1000	205	0.1	146.9	2	600	[S1]
PB-1000	136.6	2	146.9	2	600	[S1]
CPB-PL	293	0.02	193	0.1	200	[S2]
CPB-PL	77	1	193	0.1	200	[S2]
SC-800	229	0.05	189	0.05	50	[S3]
SC-800	82.0	1	81.0	0.5	2000	[S3]
SAL	285	0.02	141.6	0.2	1000	[S4]
SAL	150	0.5	141.6	0.2	1000	[S4]
HC-1000	242.1	0.025	Below 60	1	800	[S5]
HC-1000	Below 100	0.8	Below 60	1	800	[S5]
YT-1200	261	0.1	235	0.1	200	[S6]
YT-1200	206	2	235	0.1	200	[S6]
N-FLG	264.3	0.1	211.3	0.5	2000	[S7]
N-FLG	148.5	5	211.3	0.5	2000	[S7]
B@N@NHCS-900	274.8	0.1	281.8	0.1	100	This work
B@N@NHCS-900	179.4	2	122.5	2	500	This work

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