Preparation of B-doped porous carbon nanosheets and their lithium storage performance

doi:10.16085/j.issn.1000-6613.2023-0753

Abstract

Abstract:

Anode materials are one of the critical factors affecting the electrochemical performance of lithium-ion batteries (LIBs). Pore structure modulation and heteroatom doping effectively improve the electrochemical performance of anode materials. In this paper, coal-based carbon nanosheets (CS) were prepared by using lignite as a precursor chemical oxidation method. Then B-doped porous carbon nanosheets (BPCS) were obtained using boron oxide (B₂O₃) as an additive. The microstructures of CS and BCPS were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Raman spectroscopy (Raman), nitrogen adsorption-desorption and X-ray photoelectron spectroscopy (XPS), and the electrochemical properties of CS and BPCS as anode materials for LIBs were investigated. The results showed that B₂O₃ had triple functions of template, pore-making and doping. When the dosage of B₂O₃ was 0.5g, BPCS-0.5 exhibited a three-dimensional porous structure with a specific surface area of 1216.20m²/g, a total pore volume of 1.027cm³/g, and content of B atom of 4.20%. The porous structure of BPCS-0.5 provided sufficient space and channels for ion storage and transport, and the introduction of B element increased the surface chemical activity of BPCS, which enhanced the lithium storage performance. When BPCS-0.5 as anode material of LIBs, the first reversible capacity reached 826mA·h/g at a current density of 0.05A/g and the reversible capacity still reached 143mA·h/g at a high current density of 5A/g, and the capacity retention rate of 500 cycles was 172%, indicating that the anode materials had high lithium storage capacity and excellent cycle life.

Key words: lignite, boron-doped, porous carbon nanosheets, lithium-ion batteries, electrochemical performance

摘要：

负极材料是影响锂离子电池（LIBs）性能的关键因素之一，孔隙结构调控和杂原子掺杂是提高负极材料电化学性能的有效手段。以褐煤为前体，采用化学氧化法制备煤基碳纳米片（CS），再以氧化硼（B₂O₃）为添加剂，得到B掺杂多孔碳纳米片（BPCS）；采用扫描电镜（SEM）、透射电镜（TEM）、X射线衍射（XRD）、拉曼光谱（Raman）、氮气吸附仪、X射线光电子能谱（XPS）等手段对CS和BPCS微观结构和用作锂离子电池负极材料的电化学性能表征与测试。结果表明，B₂O₃具有模板、造孔、掺杂三重作用，当B₂O₃用量为0.5g时，BPCS-0.5呈现三维多孔结构，比表面积为1216.20m²/g，总孔容1.027cm³/g，B原子含量为4.20%；BPCS-0.5的多孔结构为离子的存储和传输提供足够的空间和通道，B元素的引入增加了BPCS的表面化学活性，从而增强了储锂性能。BPCS-0.5用作锂离子电池负极材料时，在0.05A/g电流密度下首次可逆容量达826mA·h/g，且在5A/g大电流密度下可逆容量仍有143mA·h/g，循环500次的容量保持率为172%，表明该材料具有较高的储锂容量和优异的循环寿命。

关键词: 褐煤, B掺杂, 多孔碳纳米片, 锂离子电池, 电化学性能

CLC Number:

TQ536

SUN Yue, XING Baolin, ZHANG Yaojie, FENG Laihong, ZENG Huihui, JIANG Zhendong, XU Bing, JIA Jianbo, ZHANG Chuanxiang, CHEN Lunjian, ZHANG Yue, ZHANG Wenhao. Preparation of B-doped porous carbon nanosheets and their lithium storage performance[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3209-3220.

孙悦, 邢宝林, 张耀杰, 冯来宏, 曾会会, 蒋振东, 徐冰, 贾建波, 张传祥, 谌伦建, 张越, 张文豪. B掺杂多孔碳纳米片的制备及其储锂性能[J]. 化工进展, 2024, 43(6): 3209-3220.

Figures/Tables 13

样品名称	比表面积/m²·g^-1	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	微孔率/%	中孔孔容/cm³·g^-1	中孔率/%	大孔孔容/cm³·g^-1	大孔率/%
CS	440.78	0.316	0.292	92.40	0.055	5.53	0.007	2.21
BPCS-0.25	1298.10	1.174	0.474	40.41	0.611	52.05	0.088	7.53
BPCS-0.5	1216.20	1.027	0.415	40.37	0.561	54.66	0.051	4.95
BPCS-1	301.04	0.451	0.087	19.31	0.222	49.33	0.141	31.35

样品名称	C含量						O含量	B含量
样品名称	总含量	C—B	C $̿$ C/C—C	C—O	C $̿$ O	COOH	总含量	总含量	BC₃	BC₂O	BCO₂
CS	91.11	—	79.40	12.00	5.40	3.00	7.24	—	—	—	—
BPCS-0.25	85.07	1.48	75.41	14.49	5.72	2.89	11.73	3.20	23.33	72.39	4.27
BPCS-0.5	83.49	1.73	72.61	15.89	6.22	3.35	12.31	4.20	17.54	74.37	8.00
BPCS-1	77.21	2.40	71.78	16.53	5.43	3.84	16.25	6.54	14.87	80.23	4.89

样品名称	C含量						O含量	B含量
样品名称	总含量	C—B	C $̿$ C/C—C	C—O	C $̿$ O	COOH	总含量	总含量	BC₃	BC₂O	BCO₂
CS	91.11	—	79.40	12.00	5.40	3.00	7.24	—	—	—	—
BPCS-0.25	85.07	1.48	75.41	14.49	5.72	2.89	11.73	3.20	23.33	72.39	4.27
BPCS-0.5	83.49	1.73	72.61	15.89	6.22	3.35	12.31	4.20	17.54	74.37	8.00
BPCS-1	77.21	2.40	71.78	16.53	5.43	3.84	16.25	6.54	14.87	80.23	4.89

样品	不同电流密度下的第10次充电比容量/mA·h·g^-1
样品	0.05A·g^-1	0.1A·g^-1	0.2A·g^-1	0.5A·g^-1	1A·g^-1	2A·g^-1	5A·g^-1	0.05A·g^-1
CS	285	246	218	184	164	143	88	312
BPCS-0.25	641	471	390	302	234	171	94	498
BPCS-0.5	715	559	457	360	296	231	143	571
BPCS-1	570	443	375	304	250	195	124	507

序号	样品	比容量/mA·h·g^-1，电流密度/A·g^-1	比容量/mA·h·g^-1，循环次数，电流密度/A·g^-1	参考文献
1	0.5BN-CQD	130，3	485，100，0.1	[32]
2	B-CNT	345，0.1	261，500，0.5	[49]
3	B-G	353，0.5	548，30，0.1	[51]
4	BNCF-800	417，0.1	416，450，0.1	[52]
5	Py-B-CNTs	474，0.05	548，300，0.1	[53]
6	B-CQD	443，0.1	405，100，0.1	[54]
7	BPCS-0.5	715，0.05 559，0.1 360，0.5	486，500，1	本工作

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