磷掺杂石墨相氮化碳的制备及其在锂硫电池中的应用

张旭; 杨绍斌

doi:10.13801/j.cnki.fhclxb.20201111.005

磷掺杂石墨相氮化碳的制备及其在锂硫电池中的应用

doi: 10.13801/j.cnki.fhclxb.20201111.005

张旭^{1, 2,},
杨绍斌^2, ,

1.
辽宁工程技术大学　矿业学院，阜新 123000
2.
辽宁工程技术大学　材料科学与工程学院，阜新 123000

基金项目: 国家自然科学基金(51274119；51774175)

详细信息

通讯作者:
杨绍斌，博士，教授，博士生导师，研究方向为新能源储能材料　E-mail：lgdysb@163.com

中图分类号: TM911
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- 被引次数: 0
出版历程
- 收稿日期: 2020-09-17
- 录用日期: 2020-10-28
- 网络出版日期: 2020-11-11
- 刊出日期: 2021-05-01

Preparation of phosphorus-doped graphitic carbon nitride and its application in lithium-sulfur batteries

ZHANG Xu^{1, 2
,},
YANG Shaobin^{2
, ,}

1.
College of Mining, Liaoning Technical University, Fuxin 123000, China
2.
College of Materials Science and Engineering, Liaoning Technical University, Fuxin 123000, China

摘要

摘要: 通过热缩聚合成法，采用尿素为原料，制备石墨相氮化碳(g-C₃N₄)，以磷酸氢二胺作为磷源，制备不同磷含量的磷掺杂g-C₃N₄ (xP-CN)，研究磷掺杂对xP-CN的微观结构、形貌及xP-CN/S复合材料作为锂硫电池正极材料电化学性能的影响。研究表明，磷掺杂后xP-CN的层间距增大，导电性提高，比表面积变大，10% P-CN的比表面积最大达到101.741 m²·g⁻¹。10% P-CN/S复合材料在0.05 C (1 C=1675 mA·h·g⁻¹)下首次放电比容量达到1383.8 mA·h·g⁻¹，在0.2 C下循环100次后可逆比容量为860.0 mA·h·g⁻¹，而g-C₃N₄/S复合材料比容量仅为178.3 mA·h·g⁻¹；10% P-CN/S复合材料经过倍率测试后比容量可以回复到0.2 C时的93.6%，表现出良好的循环性能和倍率性能。
- 锂硫电池 /
- 石墨相氮化碳(g-C₃N₄) /
- 电极材料 /
- 磷元素 /
- 掺杂
Abstract: Graphite-phase carbon nitride (g-C₃N₄) was prepared by heat shrinkage polymerization method using urea as raw material, and phosphorus-doped g-C₃N₄ with different phosphorus content (xP-CN) was prepared by using hydrogen phosphate diamine as a phosphorus source. The effect of doping on the microstructure, morphology, and electrochemical performance of xP-CN/S composites as cathode materials for lithium-sulfur batteries was studied. The studies show that the layer spacing of xP-CN increases after phosphorus doping, the electrical conductivity increases, and the specific surface area becomes larger. The specific surface area of the 10% P-CN reaches 101.741 m²·g⁻¹. The initial discharge specific capacity of the 10% P-CN/S composite at 0.05 C (1 C=1675 mA·h·g⁻¹) reaches 1383.8 mA·h·g⁻¹. The reversible specific capacity after 100 cycles at 0.2 C is 860.0 mA·h·g⁻¹, the reversible specific capacity of g-C₃N₄/S composite is only 178.3 mA·h·g⁻¹; The specific capacity of 10% P-CN/S composite can be restored to 93.6% at 0.2 C after the rate test, showing good cycle performance and rate performance.
- lithium-sulfur batteries /
- graphitic carbon nitride (g-C₃N₄) /
- electrode materials /
- phosphorus /
- doping

HTML全文

图 1 石墨相氮化碳(g-C₃N₄)和不同磷含量的磷掺杂g-C₃N₄ (xP-CN)的XRD图谱

Figure 1. XRD patterns of graphite-phase carbon nitride (g-C₃N₄) and phosphorus-doped g-C₃N₄ with different phosphorus content (xP-CN)

下载: 全尺寸图片幻灯片

图 2 S、g-C₃N₄/S和xP-CN/S复合材料的XRD图谱

Figure 2. XRD patterns of S, g-C₃N₄/S and xP-CN/S composites

下载: 全尺寸图片幻灯片

图 3 g-C₃N₄和xP-CN的FTIR图谱

Figure 3. FTIR spectra of g-C₃N₄ and xP-CN

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图 4 g-C₃N₄的的XPS图谱: (a)全谱; (b) C1s; (c) N1s; 10%P-CN的的XPS图谱: (d)全谱; (e) C1s; (f) N1s; (g) P2p

Figure 4. XPS spectra of g-C₃N₄: (a) Total; (b) C1s; (c) N1s; XPS spectra of 10% P-CN: (d) Total; (e) C1s; (f) N1s; (g) P2p

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图 5 g-C₃N₄ (a)、2% P-CN (b)、10%P-CN (c)、20% P-CN (d)及g-C₃N₄/S (e)、10% P-CN/S (f)复合材料的SEM图像

Figure 5. SEM images of g-C₃N₄ (a), 2% P-CN (b), 10%P-CN (c), 20% P-CN (d) and g-C₃N₄/S (e), 10% P-CN/S (f) composites

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图 6 g-C₃N₄ (a)和10% P-CN (b)的TEM图像

Figure 6. TEM images of g-C₃N₄ (a) and 10% P-CN (b)

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图 7 g-C₃N₄/S ((a)~(d))和10% P-CN/S ((e)~(i))复合材料元素的EDS面扫图

Figure 7. Elemental EDS maps of g-C₃N₄/S ((a)-(d)) and 10% P-CN/S ((e)-(i)) composites

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图 8 g-C₃N₄/S和xP-CN/S复合材料的电化学性能：(a)首次充放电曲线; (b)倍率性能曲线; (c)循环性能曲线

Figure 8. Electrochemical performance of g-C₃N₄/S and xP-CN/S composites: (a) Initial charge and discharge curve; (b) Rate performance curve; (c) Cycling performances curve

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图 9 g-C₃N₄和xP-CN对多硫化物的吸附实验

Figure 9. Experiment of polysulfide adsorption by g-C₃N₄ and xP-CN

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图 10 g-C₃N₄/S和10% P-CN/S复合材料的循环伏安曲线和电化学阻抗曲线

Figure 10. Cyclic voltammetry and electrochemical impedance spectroscopy curves of g-C₃N₄/S and 10% P-CN/S composites

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表 1 g-C₃N₄和xP-CN中P元素含量

Table 1. Element contents of P in g-C₃N₄ and xP-CN

Line Type P/wt%

g-C₃N₄ K 0
2% P-CN K 1.63
10% P-CN K 8.07
20% P-CN K 19.02

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