Boron and Nitrogen Co-doped Biomass Carbon Sphere Anode Material: Preparation and Sodium Storage Properties for Sodium-ion Batteries

doi:10.15541/jim20250187

Abstract

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

CLC Number:

O646

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.

Figures/Tables 12

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

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

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

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

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

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

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

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

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

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

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	-

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

References 38

[1]	MAHMUD S, RAHMAN M, KAMRUZZAMAN M, et al. Recent advances in lithium-ion battery materials for improved electrochemical performance: a review. Results in Engineering, 2022, 15: 100472. DOI URL
[2]	JUNG S K, HWANG I, CHANG D, et al. Nanoscale phenomena in lithium-ion batteries. Chemical Reviews, 2020, 120(14): 6684. DOI URL
[3]	SUN J, XU Y, LV Y, et al. Recent advances in covalent organic framework electrode materials for alkali metal-ion batteries. CCS Chemistry, 2023, 5(6): 1259. DOI URL
[4]	HUANG Y, ZHONG X, HU X, et al. Rationally designing closed pore structure by carbon dots to evoke sodium storage sites of hard carbon in low-potential region. Advanced Functional Materials, 2024, 34(4): 2308392. DOI URL
[5]	LI L, CHENG D, ZOU G, et al. Carbon anode from carbon dots-regulated polypyrrole for enhanced potassium storage. Journal of Alloys and Compounds, 2023, 958: 170481. DOI URL
[6]	SIMONE V, BOULINEAU A, DE GEYER A, et al. Hard carbon derived from cellulose as anode for sodium ion batteries: dependence of electrochemical properties on structure. Journal of Energy Chemistry, 2016, 25(5): 761. DOI
[7]	WANG Y, ZHANG M, SHEN X, et al. Biomass-derived carbon materials: controllable preparation and versatile applications. Small, 2021, 17(40): 2008079. DOI URL
[8]	CHU Y, ZHANG J, ZHANG Y, et al. Reconfiguring hard carbons with emerging sodium-ion batteries: a perspective. Advanced Materials, 2023, 35(31): 2212186. DOI URL
[9]	SU D, HUANG M, ZHANG J, et al. High N-doped hierarchical porous carbon networks with expanded interlayers for efficient sodium storage. Nano Research, 2020, 13(10): 2862. DOI
[10]	POTHAYA S, POOCHAI C, TAMMANOON N, et al. Bamboo-derived hard carbon/carbon nanotube composites as anode material for long-life sodium-ion batteries with high charge/ discharge capacities. Rare Metals, 2024, 43(1): 124. DOI URL
[11]	CHEN B, MENG Q, WANG T, et al. Cross-linking matters: building hard carbons with enhanced sodium-ion storage plateau capacities. Journal of Power Sources, 2024, 624: 235566. DOI URL
[12]	ZENG Y, WANG F, CHENG Y, et al. Identifying the importance of functionalization evolution during pre-oxidation treatment in producing economical asphalt-derived hard carbon for Na-ion batteries. Energy Storage Materials, 2024, 73: 103808. DOI URL
[13]	XIE L, SHEN G, LI B, et al. Porous carbon materials derived from waste tea leaves as high-capacity anodes for lithium/sodium ion batteries. Journal of Energy Storage, 2024, 100: 113598. DOI URL
[14]	LU B, SONG J X, DENG D R, et al. Self-doped porous sorghum husk-derived carbon as anode for high performance sodium-ion batteries at low temperatures. Journal of Energy Storage, 2024, 102: 114056. DOI URL
[15]	KIM D Y, LI O L, KANG J. Novel synthesis of highly phosphorus-doped carbon as an ultrahigh-rate anode for sodium ion batteries. Carbon, 2020, 168: 448. DOI URL
[16]	HE B, FENG L, HONG G, et al. A generic F-doped strategy for biomass hard carbon to achieve fast and stable kinetics in sodium/ potassium-ion batteries. Chemical Engineering Journal, 2024, 490: 151636. DOI URL
[17]	QUAN B, JIN A, YU S H, et al. Solvothermal-derived S-doped graphene as an anode material for sodium-ion batteries. Advanced Science, 2018, 5(5): 1700880. DOI URL
[18]	ZHANG T, ZHANG T, WANG F, et al. High-efficiently doping nitrogen in kapok fiber-derived hard carbon used as anode materials for boosting rate performance of sodium-ion batteries. Journal of Energy Chemistry, 2024, 96: 472. DOI URL
[19]	LIU Z, JIANG L, SHENG L, et al. Oxygen clusters distributed in graphene with “paddy land” structure: ultrahigh capacitance and rate performance for supercapacitors. Advanced Functional Materials, 2018, 28(5): 1705258. DOI URL
[20]	WANG Y, LI H, ZHAI B, et al. Highly crystalline poly(heptazine imide)-based carbonaceous anodes for ultralong lifespan and low- temperature sodium-ion batteries. ACS Nano, 2024, 18(4): 3456. DOI URL
[21]	FENG W, FENG N, LIU W, et al. Liquid-state templates for constructing B, N, Co-doping porous carbons with a boosting of potassium-ion storage performance. Advanced Energy Materials, 2021, 11(4): 2003215. DOI URL
[22]	CUI K, WANG C, LUO Y, et al. Enhanced sodium storage kinetics of nitrogen rich cellulose-derived hierarchical porous carbon via subsequent boron doping. Applied Surface Science, 2020, 531: 147302. DOI URL
[23]	OH J A S, DEYSHER G, RIDLEY P, et al. High-performing all-solid-state sodium-ion batteries enabled by the presodiation of hard carbon. Advanced Energy Materials, 2023, 13(26): 2300776. DOI URL
[24]	WARREN B E. X-ray diffraction in random layer lattices. Physical Review, 1941, 59(9): 693. DOI URL
[25]	FENG S, LI K, HU P, et al. Solvent-free synthesis of hollow carbon nanostructures for efficient sodium storage. ACS Nano, 2023, 17(22): 23152. DOI PMID
[26]	QIU C, LI M, QIU D, et al. Ultra-high sulfur-doped hierarchical porous hollow carbon sphere anodes enabling unprecedented durable potassium-ion hybrid capacitors. ACS Applied Materials & Interfaces, 2021, 13(42): 49942.
[27]	ZHU C L, WANG H L, FAN W J, et al. Large-scale doping- engineering enables boron/nitrogen dual-doped porous carbon for high-performance zinc ion capacitors. Rare Metals, 2022, 41(7): 2505. DOI URL
[28]	XIANG J, MA L, SUN Y, et al. Ball-milling-assisted N/O codoping for enhanced sodium storage performance of coconut- shell-derived hard carbon anodes in sodium-ion batteries. Langmuir, 2024, 40(45): 23853. DOI URL
[29]	LIU Y, YIN J, WU R, et al. Molecular engineering of pore structure/interfacial functional groups toward hard carbon anode in sodium-ion batteries. Energy Storage Materials, 2025, 75: 104008. DOI URL
[30]	ZHANG F, XIONG P, GUO X, et al. A nitrogen, sulphur dual-doped hierarchical porous carbon with interconnected conductive polyaniline coating for high-performance sodium- selenium batteries. Energy Storage Materials, 2019, 19: 251. DOI URL
[31]	XIA Q, YANG H, WANG M, et al. High energy and high power lithium-ion capacitors based on boron and nitrogen dual-doped 3d carbon nanofibers as both cathode and anode. Advanced Energy Materials, 2017, 7(22): 1701336. DOI URL
[32]	BALAJI S S, KARNAN M, ANANDHAGANESH P, et al. Performance evaluation of B-doped graphene prepared via two different methods in symmetric supercapacitor using various electrolytes. Applied Surface Science, 2019, 491: 560. DOI URL
[33]	WU D, SUN F, QU Z, et al. Multi-scale structure optimization of boron-doped hard carbon nanospheres boosting the plateau capacity for high performance sodium ion batteries. Journal of Materials Chemistry A, 2022, 10(33): 1722.
[34]	YUAN M, CAO B, LIU H, et al. Sodium storage mechanism of nongraphitic carbons: a general model and the function of accessible closed pores. Chemistry of Materials, 2022, 34(7): 3489. DOI URL
[35]	ALVIN S, CAHYADI H S, HWANG J, et al. Revealing the intercalation mechanisms of lithium, sodium, and potassium in hard carbon. Advanced Energy Materials, 2020, 10(20): 2000283. DOI URL
[36]	CHAO D, LIANG P, CHEN Z, et al. Pseudocapacitive Na-ion storage boosts high rate and areal capacity of self-branched 2D layered metal chalcogenide nanoarrays. ACS Nano, 2016, 10(11): 10211. PMID
[37]	HONG Z, ZHEN Y, RUAN Y, et al. Rational design and general synthesis of S-doped hard carbon with tunable doping sites toward excellent Na-ion storage performance. Advanced Materials, 2018, 30(29): 1802035. DOI URL
[38]	WU S, PENG H, XU J, et al. Nitrogen/phosphorus co-doped ultramicropores hard carbon spheres for rapid sodium storage. Carbon, 2024, 218: 118756. DOI URL