中空FeS2/NiS2/Ni3S2@NC立方体复合材料的制备及其电化学性能

doi:10.11901/1005.3093.2023.261

材料研究学报

2024, Vol. 38

Issue (6): 453-462 DOI: 10.11901/1005.3093.2023.261

研究论文

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中空FeS₂/NiS₂/Ni₃S₂@NC立方体复合材料的制备及其电化学性能

刘莹, 陈平(

), 周雪, 孙晓杰, 王瑞琪

大连理工大学化工学院精细化工重点实验室大连 116024

Preparation and Electrochemical Properties of Hollow FeS₂/NiS₂/Ni₃S₂@NC Cube Composites

LIU Ying, CHEN Ping(

), ZHOU Xue, SUN Xiaojie, WANG Ruiqi

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

引用本文:

刘莹, 陈平, 周雪, 孙晓杰, 王瑞琪. 中空FeS₂/NiS₂/Ni₃S₂@NC立方体复合材料的制备及其电化学性能[J]. 材料研究学报, 2024, 38(6): 453-462.
Ying LIU, Ping CHEN, Xue ZHOU, Xiaojie SUN, Ruiqi WANG. Preparation and Electrochemical Properties of Hollow FeS₂/NiS₂/Ni₃S₂@NC Cube Composites[J]. Chinese Journal of Materials Research, 2024, 38(6): 453-462.

全文: PDF(11621 KB) HTML

摘要:

以Cu₂O立方体为自牺牲模板，进行协同刻蚀-沉淀(CEP)路线、高温煅烧、聚多巴胺(PDA)涂层包覆和高温硫化，制备出中空FeS₂/NiS₂/Ni₃S₂@NC纳米立方体复合材料并研究其电化学性能。结果表明，通过CEP路线并引入Ni和Fe金属元素，制备过程较为简单和安全。这种材料的中空立方体结构，能抑制体积膨胀和减小锂离子嵌入脱出产生的机械应力。引入N掺杂碳层(NC)能极大地提高材料的导电性和结构稳定性，更好地维持立方体结构。在电流密度为0.2 A·g^-1的条件下经过100次循环后，FeS₂/NiS₂/Ni₃S₂@NC纳米立方体复合材料的放电比容量保持在899.4 mAh·g^-1，表明其具有较高的比容量、良好的循环稳定性和倍率性能(3.0 A·g^-1电流密度下比容量为427.5 mAh·g^-1)。

关键词 ：复合材料, 锂离子电池, 负极材料, 过渡金属硫化物

Abstract：

A novel composite hollow FeS₂/NiS₂/Ni₃S₂@NC cube is synthesized through collaborative etch-precipitation (CEP) route, high-temperature calcination, polydopamine coating and high-temperature vulcanization with a pre-prepared Cu₂O cube as sacrificial template. The preparation process is safe, while Ni and Fe are successfully incorporated through the CEP route. The hollow cube structure can effectively restrain the volume expansion and slow down the mechanical stress caused by lithium-ion embedding and release. The introduction of N-doped carbon layer (NC) can greatly improve the conductivity and structural stability of the composite material, so that it can better maintain the stability of the cube structure. Furthermore, after 100 cycles at a current density of 0.2 A·g^-1, the specific discharge capacity of the FeS₂/NiS₂/Ni₃S₂@NC cube composite can be maintained at 899.4 mAh·g^-1, showing high specific capacity, good cycle stability, and great rate performance (427.5 mAh·g^-1 at 3.0 A·g^-1).

Key words： composite lithium-ion batteries anode materials transition metal sulfides

收稿日期: 2023-05-17

ZTFLH:

TM 912

基金资助:兴辽英才项目(XLYC1802085);国家自然科学基金(51873109);大连市科技创新基金重大项目(2019J11CY007)

通讯作者: 陈平，教授，pchen@dlut.edu.cn, 研究方向为高性能高分子材料与先进聚合物基复合材料与功能一体化设计与制备

Corresponding author: CHEN Ping, Tel: (0411)84986100, E-mail: pchen@dlut.edu.cn

作者简介: 刘莹，女，1998年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2023.261 或 https://www.cjmr.org/CN/Y2024/V38/I6/453

图1 制备中空FeS2/NiS2/Ni3S2@NC立方体的示意图

图2 Cu2O、NF-OH和NFO的XRD谱、FeS2/NiS2/Ni3S2@NC与FeS2/NiS2/Ni3S2的XRD谱的对比以及 FeS2/NiS2/Ni3S2@NC的拉曼谱

图3 FeS2/NiS2/Ni3S2@NC的红外光谱、N2吸附/脱附等温线和孔径分布

图4 FeS2/NiS2/Ni3S2@NC的全谱以及Ni 2p、 Fe 2p、 S 2p、 C 1s和N 1s的XPS谱

图5 Cu2O、NF-OH、FeS2/NiS2/Ni3S2以及FeS2/NiS2/Ni3S2@NC的SEM像

图6 FeS2/NiS2/Ni3S2@NC不同放大倍率下的TEM图像、FeS2/NiS2/Ni3S2@NC的HRTEM图像以及FeS2/NiS2/Ni3S2@NC对应的EDS元素分布

图7 扫描速率为0.1 mV·s-1时FeS2/NiS2/Ni3S2@NC的CV曲线、电流密度为0.2 A·g-1时FeS2/NiS2/Ni3S2@NC第1、2、5、10、50和100次循环的GCD分布、FeS2/NiS2/Ni3S2@NC和FeS2/NiS2/Ni3S2阳极的倍率性能以及电流密度为0.2 A·g-1时FeS2/NiS2/Ni3S2@NC和FeS2/NiS2/Ni3S2的循环性能

图8 电流密度为1.0 A·g-1时FeS2/NiS2/Ni3S2@NC和FeS2/NiS2/Ni3S2循环500圈后性能的对比

图9 FeS2/NiS2/Ni3S2@NC和FeS2/NiS2/Ni3S2未循环前的阻抗对比和FeS2/NiS2/Ni3S2@NC循环100圈后阻抗对比图

图10 FeS2/NiS2/Ni3S2@NC在不同扫速下的CV曲线、不同氧化还原峰处的lg(i)与lg(ʋ)的比值、不同扫速下的赝电容和扩散控制电容贡献率以及0.8 mV·s-1下的赝电容贡献

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