磷掺杂微晶石墨的制备及其在锂离子电池负极材料中的电化学性能研究

doi:10.11949/0438-1157.20241521

化工学报 ›› 2025, Vol. 76 ›› Issue (7): 3615-3625.DOI: 10.11949/0438-1157.20241521

磷掺杂微晶石墨的制备及其在锂离子电池负极材料中的电化学性能研究

吴鹂霄¹(), 燕溪溪¹(), 张素娜¹, 徐一鸣¹, 钱佳颖¹, 乔永民², 王利军¹^,³

^1.上海第二工业大学能源与材料学院，上海 201209
^2.郴州杉杉新材料有限公司，湖南郴州 423400
^3.南通复米新材料科技有限公司，江苏南通 226200

收稿日期:2024-12-30 修回日期:2025-03-07 出版日期:2025-07-25 发布日期:2025-08-13
通讯作者: 燕溪溪
作者简介:吴鹂霄（2001—），男，硕士研究生，863290955@qq.com
基金资助:
郴州2022年国家可持续发展议程创新示范区建设省级专项(2022sfq26)

The preparation of phosphorus-doped microcrystalline graphite and its electrochemical performance as an anode material for lithium-ion batteries

Lixiao WU¹(), Xixi YAN¹(), Suna ZHANG¹, Yiming XU¹, Jiaying QIAN¹, Yongmin QIAO², Lijun WANG¹^,³

^1.School of Energy and Materials, Shanghai Key Laboratory of Engineering Materials Application and Evaluation, Shanghai Polytechnic University, Shanghai 201209, China
^2.Chenzhou Shanshan New Material Co. , Ltd. , Chenzhou 423400, Hunan, China
^3.Nantong Fumi New Material Technology Co. , Ltd. , Nantong 226200, Jiangsu, China

Received:2024-12-30 Revised:2025-03-07 Online:2025-07-25 Published:2025-08-13
Contact: Xixi YAN

摘要/Abstract

摘要：

现有的阳极技术已接近性能极限。微晶石墨作为阳极材料中常用的石墨类材料的一种，其在实际应用中的潜力尚未得到充分开发。开发具有高能量密度和快速充放电能力的负极材料已经成为锂离子电池领域的热点课题。采用一种简便且高效的水热合成法，通过高温煅烧，成功制备了磷掺杂的微晶石墨负极材料。通过磷酸水热法对微晶石墨进行表面改性，实现了磷元素的有效掺杂，并确保了在高温煅烧过程中掺杂元素的稳定附着和均匀分布。结果表明，磷掺杂能够显著提升微晶石墨的化学活性，初次放电比容量实现501.56 mAh/g，在3C高倍率的放电比容量仍保持在121.98 mAh/g，相较于原样提升了大约3倍。

关键词: 锂离子电池, 阳极材料, 微晶石墨, 磷掺杂, 电化学

Abstract:

Existing anode technology has reached its performance limit. As one of the most commonly used graphite materials in anode materials, microcrystalline graphite has not been fully developed in practical applications. Therefore, the development of anode materials with high energy density and fast charge and discharge capabilities has become a hot topic in the field of lithium-ion batteries. A hydrothermal synthesis method was ingeniously employed to successfully fabricate phosphorus-doped microcrystalline graphite anode materials. The surface of microcrystalline graphite was modified by phosphoric acid hydrothermal method, which achieved effective doping of phosphorus element and ensured the stable adhesion and uniform distribution of doping elements during high-temperature calcination. The results indicate that phosphorus doping markedly boosts the surface chemical activity of microcrystalline graphite, achieving an initial discharge specific capacity of 501.56 mAh/g. Furthermore, at a high current density of 3C, the discharge capacity sustains at 121.98 mAh/g, approximately triple that of the undoped material.

Key words: lithium-ion batteries, anode materials, microcrystalline graphite, phosphorus doping, electrochemistry

中图分类号:

TM 912

吴鹂霄, 燕溪溪, 张素娜, 徐一鸣, 钱佳颖, 乔永民, 王利军. 磷掺杂微晶石墨的制备及其在锂离子电池负极材料中的电化学性能研究[J]. 化工学报, 2025, 76(7): 3615-3625.

Lixiao WU, Xixi YAN, Suna ZHANG, Yiming XU, Jiaying QIAN, Yongmin QIAO, Lijun WANG. The preparation of phosphorus-doped microcrystalline graphite and its electrochemical performance as an anode material for lithium-ion batteries[J]. CIESC Journal, 2025, 76(7): 3615-3625.

图/表 11

图1 MG以及不同磷酸含量样品在30 μm和5 μm下的SEM图以及对应的C、O、P元素EDS面扫能谱图

Fig.1 SEM images at 30 μm and 5 μm, and the EDS surface-scanning energy spectra of the C, O and P elements of MG and samples with different phosphoric acid contents

图2 MG以及不同磷酸含量样品的XRD谱图和拉曼光谱图

Fig.2 XRD and Raman spectra of MG and samples with different phosphoric acid contents

表1 MG以及不同磷酸含量样品（002）晶面的晶格间距

Table 1 （002） lattice spacing for MG and different phosphoric acid content samples

样品	λ/Å	2θ/(°)	晶格间距/nm
MG	0.15406	26.47204	0.33643
MG-HPO-2	0.15406	26.52727	0.33574
MG-HPO-3	0.15406	26.51931	0.33584
MG-HPO-4	0.15406	26.52919	0.33572
MG-HPO-5	0.15406	26.51398	0.33591
MG-HPO-6	0.15406	26.53285	0.33567

图3 MG以及不同磷酸含量样品的N2吸脱附等温线和孔径分布

Fig.3 N2 adsorption and desorption isotherm curves and pore size distribution curves for MG and samples with different phosphoric acid contents

图4 MG和不同磷酸含量前体在氮气气氛下的热重曲线

Fig.4 Thermogravimetric curves of MG and precursors with different phosphate contents under nitrogen atmosphere

表2 MG以及不同磷酸含量样品的P元素含量

Table 2 Content of element P in MG and samples with different phosphoric acid content

样品	P元素含量/%（质量分数）
MG	0
MG-HPO-2	2.630
MG-HPO-3	2.631
MG-HPO-4	4.963
MG-HPO-5	3.491
MG-HPO-6	2.847

图5 不同磷酸含量样品在循环后的SEM图以及对应的P、F元素EDS面扫能谱图

Fig.5 SEM images and EDS surface scan energy spectra of P and F elements of samples with different phosphoric acid content after cycling

表3 循环后不同磷酸含量样品的P、F元素的含量

Table 3 Mass percentage of P and F elements in samples with different phosphoric acid content after cycling

样品	P元素含量/%（质量分数）	F元素含量/%（质量分数）
MG-HPO-2	2.0666	10.8394
MG-HPO-3	2.0666	10.8394
MG-HPO-4	5.2142	19.1342
MG-HPO-5	2.2969	11.4470
MG-HPO-6	2.2814	13.2386

图6 MG和不同磷酸含量样品的电化学性能表征

Fig.6 Electrochemical characterization of MG and samples with different phosphoric acid contents

图7 MG和不同磷酸含量样品的GITT曲线

Fig.7 GITT curves of MG and different phosphoric acid content samples

图8 不同磷酸含量样品的CV曲线和EIS曲线

Fig.8 CV curves and Nyquist impedance spectra for samples with different phosphoric acid contents

参考文献 31

[6]	吴德威, 汪郑鹏, 周玥, 等. 固定床法制备锂离子电池硅碳负极材料及其储锂性能研究[J]. 化工学报, 2024, 75(S1): 300-308.
	Wu D W, Wang Z P, Zhou Y, et al. Preparation of silicon carbon anode for lithium-ion batteries by fixed bed and lithium storage properties[J]. CIESC Journal, 2024, 75(S1): 300-308.
[7]	万传云, 吴敏昌, 李辉, 等. 壳核结构改性天然石墨在电池中的应用[J]. 电池工业, 2006, 10(3): 151-153.
	Wan C Y, Wu M C, Li H, et al. Application of micro-encapsulated modified natural graphite in Li-ion batteries[J]. Chinese Battery Industry, 2006, 10(3): 151-153.
[8]	Zhang S S. The puzzles in fast charging of Li-ion batteries[J]. Energy & Environmental Materials, 2022, 5(4): 1005-1007.
[9]	Tang Z, Zhou S Y, Huang Y C, et al. Improving the initial coulombic efficiency of carbonaceous materials for Li/Na-ion batteries: origins, solutions, and perspectives[J]. Electrochemical Energy Reviews, 2023, 6(1): 8.
[10]	Yang S, Zhang S Q, Dong W, et al. Purification mechanism of microcrystalline graphite and lithium storage properties of purified graphite[J]. Materials Research Express, 2022, 9(2): 025505.
[11]	Zhou H Q, Zhang X W, Zhang X C, et al. N-doped microcrystalline graphite for boosting peroxymonosulfate activation with highly efficient degradation of bisphenol A[J]. Carbon, 2024, 216: 118579.
[12]	Kim D S, Lee J U, Kim S H, et al. Electrochemically exfoliated graphite as a highly efficient conductive additive for an anode in lithium-ion batteries[J]. Battery Energy, 2023, 2(5): 20230012.
[13]	Han X, Xu J X, Yu H X, et al. Highly efficient sulfur cathode built from biomass of hierarchical porous carbon for aqueous Cu-S batteries[J]. Inorganic Chemistry Frontiers, 2023, 10(13): 3844-3851.
[14]	Tian C X, Qin K, Suo L M. Concentrated electrolytes for rechargeable lithium metal batteries[J]. Materials Futures, 2023, 2(1): 012101.
[15]	Yu J F, Feng H P, Tang L, et al. Metal-free carbon materials for persulfate-based advanced oxidation process: microstructure, property and tailoring[J]. Progress in Materials Science, 2020, 111: 100654.
[16]	Zhu D L, Yuan J C, Dai Y, et al. High-rate performance of fluorinated carbon material doped by phosphorus species for lithium-fluorinated carbon battery[J]. Energy Technology, 2022, 10(6): 2200155.
[17]	Zhang X, Yang S B, Chen Y H, et al. Effect of phosphorous-doped graphitic carbon nitride on electrochemical properties of lithium-sulfur battery[J]. Ionics, 2020, 26(11): 5491-5501.
[18]	Park H Y, Singh K P, Yang D S, et al. Simple approach to advanced binder-free nitrogen-doped graphene electrode for lithium batteries[J]. RSC Advances, 2015, 5(5): 3881-3887.
[19]	Zhang H B, Liu K, Liu Y Y, et al. Observably improving initial coulombic efficiency of C/SiO _x anode using -C-O-PO₃Li₂ groups in lithium ion batteries[J]. Journal of Power Sources, 2020, 447: 227400.
[20]	Li Y, Cao J, Wang L J, et al. Nitrogen-doped hollow carbon polyhedron derived from metal-organic frameworks for supercapacitors[J]. Journal of Energy Storage, 2022, 55: 105485.
[21]	Pei S F, Cheng H M. The reduction of graphene oxide[J]. Carbon, 2012, 50(9): 3210-3228.
[22]	Wang J, Gao C H, Yang Z, et al. Carbon-coated mesoporous silicon shell-encapsulated silicon nano-grains for high performance lithium-ion batteries anode[J]. Carbon, 2022, 192: 277-284.
[23]	Valero-Romero M J, García-Mateos F J, Rodríguez-Mirasol J, et al. Role of surface phosphorus complexes on the oxidation of porous carbons[J]. Fuel Processing Technology, 2017, 157: 116-126.
[24]	Yang X Y, Zhen H G, Liu H Z, et al. Environmental-friendly and effectively regenerate anode material of spent lithium-ion batteries into high-performance P-doped graphite[J]. Waste Management, 2023, 161: 52-60.
[25]	Shi Q S, Zhang S N, Yan X X, et al. Acid-base encapsulation prepared N/P co-doped carbon-coated natural graphite for high-performance lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2024, 952: 117990.
[26]	Xu Z L, Gang Y, Garakani M A, et al. Carbon-coated mesoporous silicon microsphere anodes with greatly reduced volume expansion[J]. Journal of Materials Chemistry A, 2016, 4(16): 6098-6106.
[27]	Li J B, Li J L, Ding Z B, et al. In-situ encapsulation of Ni₃S₂ nanoparticles into N-doped interconnected carbon networks for efficient lithium storage[J]. Chemical Engineering Journal, 2019, 378: 122108.
[1]	陈昕, 赵宁, 刘桂贤, 等. 当前固体电解质与固态电池技术成熟度分析[J]. 电源技术, 2024, 48(6): 969-984.
	Chen X, Zhao N, Liu G X, et al. Analysis of technology readiness level of solid-state electrolyte and solid-state battery[J]. Chinese Journal of Power Sources, 2024, 48(6): 969-984.
[2]	胡成志, 王国贤, 唐伟建, 等. 高比能锂离子电池高镍正极材料的表面包覆改性研究进展[J]. 化工学报, 2024, 75(11): 4020-4036.
	Hu C Z, Wang G X, Tang W J, et al. Research progress on surface coating modification of nickel-rich cathode materials for high energy density lithium-ion battery[J]. CIESC Journal, 2024, 75(11): 4020-4036.
[3]	史淇森, 燕溪溪, 吴敏昌, 等. 锂离子电池石墨负极材料改性研究进展[J]. 电源技术, 2023, 47(7): 838-843.
	Shi Q S, Yan X X, Wu M C, et al. Research progress on modification of graphite anode materials for lithium ion batteries[J]. Chinese Journal of Power Sources, 2023, 47(7): 838-843.
[4]	赵子寿, 王家钧, 付甜甜. 锂离子电池前沿技术[J]. 电源技术, 2024, 48(5): 767-770.
	Zhao Z S, Wang J J, Fu T T. Frontier technology of lithium ion battery[J]. Chinese Journal of Power Sources, 2024, 48(5): 767-770.
[5]	Skowroński J M, Knofczyński K. Catalytically graphitized glass-like carbon examined as anode for lithium-ion cell performing at high charge/discharge rates[J]. Journal of Power Sources, 2009, 194(1): 81-87.
[28]	Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J]. ChemInform, 2004, 104(10): 4303-4418.
[29]	Yang M M, Kong Q Q, Feng W, et al. Hierarchical porous nitrogen, oxygen, and phosphorus ternary doped hollow biomass carbon spheres for high-speed and long-life potassium storage[J]. Carbon Energy, 2022, 4(1): 45-59.
[30]	Yang X Y, Zhan C Z, Ren X L, et al. Nitrogen-doped hollow graphite granule as anode materials for high-performance lithium-ion batteries[J]. Journal of Solid State Chemistry, 2021, 303: 122500.
[31]	Zhou X, Liu X H, Qi F L, et al. Efficient preparation of P-doped carbon with ultra-high mesoporous ratio from furfural residue for dye removal[J]. Separation and Purification Technology, 2022, 292: 120954.

磷掺杂微晶石墨的制备及其在锂离子电池负极材料中的电化学性能研究

The preparation of phosphorus-doped microcrystalline graphite and its electrochemical performance as an anode material for lithium-ion batteries

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