磷酸钒锂正极材料的氮掺杂碳包覆与Ti4+共掺杂协同改性研究

doi:10.11949/0438-1157.20251052

摘要/Abstract

摘要：

离子掺杂是一种有效提升单斜相磷酸钒锂Li₃V₂（PO₄）₃（LVP）正极材料电化学性能的常用方法。本研究通过喷雾干燥辅助溶胶凝胶法，以2-甲基咪唑（C₄H₆N₂）作为碳源和氮源，实现了氮掺杂碳包覆层的原位合成。并在氮掺杂碳包覆层的基础上，进一步采用Ti⁴⁺掺杂对Li₃V₂（PO₄）₃/NC（简称LVP/NC）进行双重修饰改性，制备了不同Ti⁴⁺掺杂比例的Li₃V₂_-xTi_x（PO₄）₃/NC（简称LVT_xP/NC）。XPS分析在该纳米复合材料中观察到Ti⁴⁺特有的2p^3/2和2p^1/2峰，表明Ti⁴⁺已成功掺入晶格并取代部分V³⁺位置。与未掺杂的 Li₃V₂（PO₄）₃/C（简称LVP/C）相比，所制备的LVT_xP/NC具有更高的可逆容量、更优异的高倍率性能和更好的循环性能。特别是LVT_0.1P/NC样品，在10C倍率（3.0~4.3 V）下经过1000次循环后，容量下降至99.47 mAh∙g^-1，容量保持率为94.02%。而在5C倍率（3.0~4.8 V）下LVT_0.1P/NC的初始容量为164.63mAh∙g^-1，1000次循环后容量保持率可达94.11%，循环性能稳定。LVT_0.1P/NC的良好电化学性能得益于氮掺杂碳包覆与Ti⁴⁺共掺杂的协同效应，有效提高了材料的电子导电性和锂离子扩散系数，为高倍率锂离子电池正极材料的设计提供了参考。

关键词: 锂离子电池, 磷酸钒锂, 氮掺杂碳包覆, Ti⁴⁺掺杂, 协同改性

Abstract:

Ion doping is often employed as an effective method to enhance the electrochemical performance of monocliniclithium vanadium phosphate Li₃V₂(PO₄)₃ (LVP) cathode material. In this study, spray drying-assisted sol-gel method was employed, with 2-methylimidazole (C₄H₆N₂) serving as both carbon source and nitrogen source to realize the in-situ synthesis of nitrogen-doped carbon coating. Building on this nitrogen-doped carbon coating, the material was further modified by Ti⁴⁺ doping, resulting in a dually modified Li₃V₂(PO₄)₃/NC (denoted as LVP/NC). A series of materials with different Ti⁴⁺ doping ratios, formulated as Li₃V_2-xTiₓ(PO₄)₃/NC (abbreviated as LVT_xP/NC), were successfully prepared.In this designed nanocomposite, the characteristic 2p^3/2 and 2p^1/2 peaks of Ti⁴⁺ were detected by XPS, confirming that Ti⁴⁺ successfully replaced part of the V³⁺ sites. Compared with the undoped Li₃V₂(PO₄)₃/C (abbreviated as LVP/C), the prepared LVT_xP/NC exhibits higher reversible capacity, superior high-rate performance and better cyclic performance. In particular, the LVT_0.1P/NC sample shows a capacity of 99.47 mAh∙g⁻¹ with a capacity retention rate of 94.02% after 1000 cycles at 10C rate (3.0~4.3 V). At 5C rate (3.0~4.8 V), the initial capacity of LVT_0.1P/NC is 164.63 mAh∙g⁻¹, and the capacity retention rate can reach 94.11% after 1000 cycles, showing stable cyclic performance. The excellent battery performance of LVT_0.1P/NC is mainly attributed to the synergistic effect between the nitrogen-doped carbon coating and Ti⁴⁺ co-doping, which effectively enhanced the electrical conductivity and lithium ion diffusion coefficient, offering a valuable strategy for the design of high-rate LIB cathode materials.

Key words: lithium-ion batteries, lithium vanadium phosphate, nitrogen-doped carbon layer, Ti⁴⁺ doping, cooperative modification

中图分类号:

TM911.4

宋刘斌, 李澳, 陈涛涛, 陈丽霞, 鄢立祥, 熊逸雨, 匡尹杰, 赵亭亭. 磷酸钒锂正极材料的氮掺杂碳包覆与Ti⁴⁺共掺杂协同改性研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251052.

LiuBin SONG, Ao LI, Taotao CHEN, Lixia CHEN, Lixiang YAN, Yiyu XIONG, Yinjie KUANG, Tingting ZHAO. Study on Synergistic Modification of Nitrogen-Doped Carbon Coating and Ti⁴⁺ Co-Doping for Lithium Vanadium Phosphate Cathode Materials[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251052.

图/表 15

图1 LVTxP/NC合成示意图

Fig 1 Schematic diagram of LVTxP/NC synthesis

图2 LVP/NC、LVP/C与LVP的XRD图谱

Fig.2 XRD patterns of LVP/NC、LVP/C and LVP

图3 不同包覆量材料的SEM图:(a)NC-1; (b)NC-2; (c)NC-3; (d)NC-4;(e)NC-5;(f)LVP/C注:(d) NC-4; (e) NC-5;(f)LVP/C

Fig.3 SEM images of materials with different amounts of coating: (a) NC-1; (b) NC-2; (c) NC-3;

图4 (a)NC-3样品的SEM图；(b-f)C、N、O、V、P的EDS能谱

Fig.4 (a) SEM image of NC-3 sample; (b-f) EDS energy spectra of C, N, O, V, P

图5 (a)、(b)NC-3的TEM图像;(c-g)NC-3的EDS

Fig.5 (a)(b) NC-3 TEM images;(c-g) EDS of NC-3

图6 (a)不同碳包覆材料的循环性能曲线；(b)不同碳复合材料的倍率性能曲线注:(c)NC-3在1c倍率下的充放电曲线;(d)NC-3在不同倍率下的充放电曲线

Fig.6 (a)Cycling Performance Curves of Different Carbon Coated Materials;(b) Rate performance curves of different carbon composites;(c)Charge-discharge curve of NC-3 at 1c rate;(b)Charge/discharge curves of NC-3 at different rates

图7 (a) NC-3的XPS谱图:(a)全谱图;注:(b) V 2p精细谱;(c) C 1s精细谱;(d) N 1s精细谱

Fig 7 XPS spectra of NC-3: (a)full spectrum; (b) V 2p refined spectrum; (c) C 1s refined spectrum; (d) N 1s refined spectrum

图8 0.1 mV∙s-1下的循环伏安曲线：(a)3.0~4.3V；(b)3.0~4.8V

Fig 8 Cyclic voltammetry curves at 0.1 mV∙s-1: (a) 3.0~4.3 V; (b) 3.0~4.8 V

图9 不同掺杂量样品的XRD图谱

Fig 9 XRD patterns of samples with different doping amounts

图10 (a)LVT0.1P/NC的SEM;(b-g)C、O、V、N、P、Ti的EDS能谱

Fig 10 (a) SEM of LVT0.1P/NC; (b-g) EDS energy spectra of C, O, V, N, P, Ti

图11 (a)、(b)LVT0.1P/NC的TEM图像；(c)LVP/NC的晶格条纹强度曲线；(d) LVT0.1P/NC的晶格条纹强度曲线

Fig 11 (a), (b) TEM images of LVT0.1P/NC；(c) Lattice stripe intensity curve of LVP/NC; (d) Lattice stripe intensity curve of LVT0.1P/NC

图12 (a) LVTxP/NC（x=0、0.05、0.1、0.15、0.2）样品在1C下循环性能图；(b)LVTxP/NC倍率性能图；(c)LVTxP/NC容量变化趋势图；(d)首次充放电曲线LVTxP/NC（4.3V）；(e)LVT0.1P/NC与LVP/NC首次充放电曲线对比图（4.8V）

Fig 12 (a) Cycling performance plot of LVTxP/NC (x=0, 0.05, 0.1, 0.15, 0.2) samples at 1C; (b) LVTxP/NC Rate performance plot; (c) LVTxP/NC Capacity trend plotrve; (d) First charge/discharge curve（4.3V）； (e)Comparison of Initial Charge-Discharge Curves for LVT0.1P/NC and LVP/NC（4.8V）

图13 CV曲线(0.1~0.5 mV∙s-1)：(a) LVT0.1P/NC；(b) LVP/NC；(c)LVT0.1P/NC和LVP/NC的EIS曲线及等效电路；Ip与v1/2关系的线性拟合：(d) 氧化过程；(e) 还原过程；(f)Zreal与ω-1/2的线性拟合

Fig 13 CV curves (0.1~0.5 mV∙s-1) for (a) LVT0.1P/NC; (b) LVP/NC; (c) EIS curves and equivalent circuits for LVT0.1P/NC and LVP/NC; Linear fitting between Ip and v1/2: (d) oxidize process; (e) reduce process;(f) linear fit of Zreal to ω-1/2

表1 LVT0.1P/NC和LVP/NC的锂离子扩散系数DLi+

Table 1 Diffusion coefficients （DLi+） of the LVT0.1P/NC ＆ LVP/NCsamples cm2 s-1Unit： cm2 s-1

LVT_0.1P/NC	氧化过程	还原过程	LVP/NC	氧化过程	还原过程
0.1 mV∙s^-1	1.765×10^-9	0.902×10^-9	0.1 mV∙s^-1	4.137×10^-10	2.128×10^-10
0.2 mV∙s^-1	1.076×10^-9	1.492×10^-9	0.2 mV∙s^-1	3.939×10^-10	3.647×10^-10
0.3 mV∙s^-1	1.341×10^-9	1.745×10^-9	0.3 mV∙s^-1	3.886×10^-10	4.764×10^-10
0.4 mV∙s^-1	1.406×10^-9	2.325×10^-9	0.4 mV∙s^-1	3.854×10^-10	5.624×10^-10
0.5 mV∙s^-1	2.002×10^-9	3.053×10^-9	0.5 mV∙s^-1	4.003×10^-10	6.553×10^-10

表2 LVP/NC和LVT0.1P/NC的韦伯因子σ和锂离子扩散系数DLi+

Table 2 Warburg coefficient （σ） and Diffusion coefficient （DLi+） for LVP/NC and LVT0.1P/NC

样品	R_s (Ω)	R_ct (Ω)	σ (Ω∙s^-1/2)	D_Li+ (cm² s^-1)
LVT_0.1P/NC	14.79	163.28	8.046	1.710×10^-9
LVP/NC	3.43	190.58	32.278	1.063×10^-10

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磷酸钒锂正极材料的氮掺杂碳包覆与Ti⁴⁺共掺杂协同改性研究

Study on Synergistic Modification of Nitrogen-Doped Carbon Coating and Ti⁴⁺ Co-Doping for Lithium Vanadium Phosphate Cathode Materials

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